PHOSPHORESCENT C^C* PLATINUM(II) COMPLEXES WITH BORONIC LIGANDS AND THEIR USE AS EMITTERS IN OLEDS
20240043460 · 2024-02-08
Inventors
Cpc classification
C09K2211/185
CHEMISTRY; METALLURGY
C09B57/10
CHEMISTRY; METALLURGY
International classification
C07F15/00
CHEMISTRY; METALLURGY
Abstract
The invention relates to novel platinum(II) complexes with C{circumflex over ()}C* and borate ligands of the following formula (I), processes for their preparation and their use in OLEDs.
##STR00001##
Claims
1. A platinum(II) complex represented by the following formula (I) ##STR00037## where (a) A.sup.1 to A.sup.4 denote: A.sup.1 N or CR.sup.A1, A.sup.2 N or CR.sup.A2, A.sup.3 N or CR.sup.A3, A.sup.4 N or CR.sup.A4, and (b) X.sup.1 to X.sup.3 are: (i) X.sup.1 NR.sup.9, X.sup.2 CR.sup.10, and X.sup.3 CR.sup.11, or (ii) X.sup.1 CR.sup.12, X.sup.2 NR.sup.13, and X.sup.3 CR.sup.14, or (iii) X.sup.1 NR.sup.15, X.sup.2 N, and X.sup.3 CR.sup.16, or (iv) X.sup.1 NR.sup.17, X.sup.2 CR.sup.18, and X.sup.3 N, or (v) X.sup.1 CR.sup.19, X.sup.2 NR.sup.20, and X.sup.3 N, or (vi) X.sup.1 S, X.sup.2 CR.sup.21, and X.sup.3 CR.sup.22, and (c) R.sup.A1 to R.sup.A4 and R.sup.1 to R.sup.22 are each independently H, with the proviso that R.sup.9, R.sup.13, R.sup.15, R.sup.17, R.sup.20 are each not H: H, halogen atom, donor substituent, acceptor substituent, linear or branched, substituted or non-substituted alkyl radical having 1 to 20 carbon atoms, in which optionally at least one carbon atom is replaced by a heteroatom, substituted or non-substituted cycloalkyl radical having 3 to 20 carbon atoms, in which optionally at least one carbon atom is replaced by a heteroatom, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical having 5 to 30 carbon and/or hetero atoms, or two or more of the following radicals together with the atoms to which they are bonded form one or more rings and/or one or more fused aromatic ring systems having in each case 5 to 30 carbon and/or hetero atoms, which are in each case substituted or unsubstituted: R.sup.A1 to R.sup.A4 and/or when X.sup.3 is CR.sup.11: R.sup.9 to R.sup.11 when X.sup.3 is CR.sup.14: R.sup.12 to R.sup.14; when X.sup.3 is CR.sup.16: R.sup.15, R.sup.16; when X.sup.3 is N and X.sup.1 is NR.sup.17: R.sup.17, R.sup.18; when X.sup.3 is N and X.sup.1 is CR.sup.19: R.sup.19, R.sup.20; or when X.sup.3 is CR.sup.22: R.sup.21, R.sup.22; and/or two or more of the radicals from the respective radical group R.sup.1 to R.sup.3, R.sup.4 to R.sup.6 and/or R.sup.7 and R.sup.8 form, within the radical group, in each case together with the atoms to which they are bonded, a ring or a fused aromatic ring system having 5 to 30 carbon and/or heteroatoms, the ring or the fused aromatic ring system being substituted or unsubstituted.
2. A platinum(II) complex according to claim 1, wherein R.sup.1 to R.sup.8 are each: H, a halogen atom, donor substituent, acceptor substituent, linear or branched, substituted or unsubstituted alkyl radical having 1 to 4 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical having 5 to 18 carbon and/or hetero atoms, or two or more of the radicals from the respective radical group R.sup.1 to R.sup.3, R.sup.4 to R.sup.6 and/or R.sup.7 and R.sup.8 form, within the radical group, in each case together with the atoms to which they are bonded, a ring or a fused aromatic ring system having 5 to 30 carbon atoms and/or heteroatoms, the ring or the fused aromatic ring system being substituted or unsubstituted.
3. A platinum(II) complex according to claim 1, wherein R.sup.A1 to R.sup.A4 as well as R.sup.9 to R.sup.22 are each independently of the other, with the proviso that R.sup.9, R.sup.13, R.sup.15, R.sup.17, R.sup.20 are each not H: H, a halogen atom, donor substituent, acceptor substituent, linear or branched, substituted or unsubstituted alkyl group having 1 to 9 carbon atoms, in which optionally at least one carbon atom is replaced by a heteroatom, substituted or unsubstituted cycloalkyl group having 3 to 9 carbon atoms, in which optionally at least one carbon atom is replaced by a heteroatom, substituted or unsubstituted aryl group having 6 to 18 carbon atoms, substituted or unsubstituted heteroaryl radical having 5 to 18 carbon and/or hetero atoms, or two or more of the following radicals together with the atoms to which they are bonded form one or more rings and/or one or more fused aromatic ring systems having in each case 5 to 18 carbon and/or hetero atoms, the ring or the fused aromatic ring system being substituted or unsubstituted: R.sup.A1 to R.sup.A4 and/or when X.sup.3 is CR.sup.11: R.sup.9 to R.sup.11; when X.sup.3 is CR.sup.14: R.sup.12 to R.sup.14; when X.sup.3 is CR.sup.16: R.sup.15, R.sup.16; when X.sup.3 is N and X.sup.1 is NR.sup.17: R.sup.17, R.sup.18; when X.sup.3 is N and X.sup.1 is CR.sup.19: R.sup.19, R.sup.20; or when X.sup.3 is CR.sup.22: R.sup.21, R.sup.22.
4. A platinum(II) complex according to claim 1, wherein the respective acceptor substituent and/or donor substituent is each selected from the group consisting of halogen radicals, including F, Cl, Br, I, alkoxy radicals, carbonyl radicals (C(O)R), amine radicals (NH.sub.2, NHR, NR.sub.2), amide radicals, CF.sub.3 groups, CN groups, NC groups, SCN groups, the nitro or NO.sub.2 group, bordiorganyl groups BR.sub.2, where R in each case represents any organic radical.
5. A platinum(II) complex according to claim 1, wherein X.sup.1 to X.sup.3 mean: (i) X.sup.1 NR.sup.9, X.sup.2 CR.sup.10, and X.sup.3 CR.sup.11; (ii) X.sup.1 CR.sup.12, X.sup.2 NR.sup.13, and X.sup.3 CR.sup.14; (iii) X.sup.1 NR.sup.15, X.sup.2 N, and X.sup.3 CR.sup.16; (iv) X.sup.1 NR.sup.17, X.sup.2 CR.sup.18, and X.sup.3 N; or (v) X.sup.1 CR.sup.19, X.sup.2 NR.sup.20, and X.sup.3 N.
6. A platinum(II) complex according to claim 1, wherein R.sup.A1 to R.sup.A4 are each independently H, a halogen or methyl, donor or acceptor substituent, or R.sup.A2 and R.sup.A3 or R.sup.A3 and R.sup.A4 together with the atoms to which they are attached form a fused aromatic ring system having 5 to 18 carbon and/or heteroatoms, wherein the fused aromatic ring system is substituted or unsubstituted.
7. A platinum(II) complex according to claim 1, wherein X.sup.1 to X.sup.3 are: (i) X.sup.1 NR.sup.9, X.sup.2 CR.sup.10, and X.sup.3 CR.sup.11; (iii) X.sup.1 NR.sup.15, X.sup.2 N, and X.sup.3 CR.sup.16; (iv) X.sup.1 NR.sup.17, X.sup.2 CR.sup.18, and X.sup.3 N; or (v) X.sup.1 CR.sup.19, X.sup.2 NR.sup.20, and X.sup.3 N.
8. A platinum(II) complex according to claim 1, wherein X.sup.1 to X.sup.3 are: (i) X.sup.1 NR.sup.9, X.sup.2 CR.sup.10, and X.sup.3 CR.sup.11; (iv) X.sup.1 NR.sup.17, X.sup.2 CR.sup.18, and X.sup.3 N; or (v) X.sup.1 CR.sup.19, X.sup.2 NR.sup.20, and X.sup.3 N.
9. A process for preparing a platinum(II) complex according to claim 1 comprising contacting platinum compounds suitable therefor, selected from the group consisting of Pt(COD)Cl.sub.2 (COD=cycloocta-1,5-diene), Pt(PPh.sub.3).sub.2Cl.sub.2, Pt(pyridine).sub.2Cl.sub.2, Pt(NH.sub.3).sub.2Cl.sub.2, Pt(acac).sub.2, PtCl.sub.2, K.sub.2PtCl.sub.4, Pt(COD)Cl.sub.2, with a C{circumflex over ()}C* ligand or a C{circumflex over ()}C* ligand precursor, and the following formula (II), ##STR00038## wherein X.sup.1 to X.sup.3 and A.sup.1 to A.sup.4 have the same meanings as described in claim 1, and X.sup. denotes an anion, such as a halide ion, or an anion selected from the group consisting of BF.sub.4.sup., PF.sub.6.sup., N(SO.sub.2CF.sub.3).sub.2.sup., SbF.sub.6.sup., ClO.sub.4.sup., SO.sub.4.sup.2, and a bis(pyrazolyl)borate ligand.
10. Use of a platinum(II) complex according to claim 1 in an OLED.
Description
EXAMPLES
[0088] The following examples, in particular the methods, reagents, reaction conditions, process parameters, apparatus and the like described therein, are provided for the purpose of illustrating the present invention and are not to be construed as narrowing the invention. Percentages given herein or otherwise in connection with the invention are in weight % and any ratios given are weight ratios unless otherwise indicated. Superscript numbers at the respective C{circumflex over ()}C* ligand precursors refer to references (1) through (8) above.
General Synthesis Rule
[0089] In a heated Schlenk tube, 1 eq of the appropriate C{circumflex over ()}C* ligand precursor and 0.5 eq of silver(I) oxide are placed under an argon atmosphere and suspended in DMF. The mixture is stirred at the indicated temperature (T.sub.1) for 21 h. Subsequently, 1 eq of Pt(COD)Cl.sub.2 is added and stirring is carried out first for 3 h at room temperature and later for 21 h at the indicated temperature (T.sub.2). In the following, 2 eq of the corresponding bis(pyrazolyl)borate ligand is added at room temperature and the reaction is stirred for 21 h at 50 C. At the end of the reaction time, all volatiles are removed under high vacuum, the residue is extracted with dichloromethane (DCM) and the extract is filtered over Celite. Purification is carried out by column chromatography on silica gel 60 with the indicated eluent or a mixture of eluents adapted to the polarity. Appropriate eluent mixtures can be prepared, for example, from dichloromethane (DCM) and iso-hexane, the mixing ratio being adapted to the polarity. The solid obtained is washed with iso-hexanes and diethyl ether and dried under high vacuum.
[1-(Dibenzo[b,d]furan-4-yl-C.SUP.3.)-3-methyl-1/imidazolin-2-ylidene-C.SUP.2.][dihydrobis(pyrazol-1-yl-N.SUP.2.)borate]platinum(II) (A)
[0090] ##STR00013##
[0091] Synthesis analogous to the general synthesis procedure. 0.301 g (0.8 mmol) 1-(dibenzo[b,d]furan-4-yl)-3-methyl-1H-imidazolium iodide, and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=45 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 0.298 g (1.6 mmol, 2 eq) potassium dihydrobis(pyrazol-1-yl)borate is added. Eluent mixture: iso-hexane/DCM (2:3). Yield: 257 mg (55%); melting point: 239 C.; molecular formula: C.sub.22H.sub.19BN.sub.6OPt; molar mass: 589.32 g/mol. 1H NMR in CDCl.sub.3 (600 MHz): =8.14 (d, J=2.0 Hz, 1H, CH.sub.arom), 7.93-7.88 (m, 1H, CH.sub.arom), 7.80 (d, J=2.1 Hz, 1H, CH.sub.arom), 7.73 (d, J=2.0 Hz, 1H, CH.sub.arom), 7.66 (d, J=2.3 HZ, 1H, CH.sub.arom), 7.65 (d, J=2.3 Hz, 1H, CH.sub.arom), 7.60-7.55 (m, 1H, CH.sub.arom), 7.55 (d, J=8.2 Hz, 1H, CH.sub.arom), 7.46-7.41 (m, 1H, CH.sub.arom), 7.37-7.30 (m, 2H, CH.sub.arom), 6.89 (d, J=2.0 Hz, 1H, CH.sub.arom), 6.29 (t, J=2.2 Hz, 1H, CH.sub.arom), 6.21 (t, J=2.2 Hz, 1H, CH.sub.arom), 3.65 (s, 3H, NCH.sub.3). .sup.13C NMR in CDCl.sub.3 (151 MHz): =157.5 (C.sub.i), 155.9 (C.sub.i), 142.8 (C.sub.i), 142.2 (CH.sub.arom), 141.4 (CH.sub.arom), 136.3 (CH.sub.arom), 136.1 (CH.sub.arom), 131.2 (C.sub.i), 129.5 (C.sub.i), 129.4 (CH.sub.arom), 126.6 (CH.sub.arom), 124.8 (C.sub.i), 123.1 (CH.sub.arom), 122.9 (C.sub.i), 121.5 (CH.sub.arom), 120.5 (CH.sub.arom), 118.7 (CH.sub.arom), 116.2 (CH.sub.arom), 111.5 (CH.sub.arom), 105.2 (CH.sub.arom), 105.1 (CH.sub.arom), 37.6 (NCH.sub.3). .sup.195Pt NMR in CDCl.sub.3 (64 MHz): =3810.7 (s). MS (ESI): m/z=588.4 [MH].sup.+, 1196.4 [2M+NH.sub.4].sup.+. Elemental analysis: calculated C, 44.84%; H, 3.25%; N, 14.26%; found C, 44.69%; H, 2.92%; N, 14.09%.
[1-(Dibenzo[b,d]furan-4-yl-C.SUP.3.)-3-methyl-1H-imidazolin-2-ylidene-C.SUP.2.][dihydrobis(3,5-dimethylpyrazol-1-yl-N.SUP.2.)borate]platinum(II) (B)
[0092] ##STR00014##
[0093] Synthesis analogous to the general synthesis procedure. 0.301 g (0.8 mmol) 1-(dibenzo[b,d]furan-4-yl)-3-methyl-1H-imidazolium iodide, and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=45 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 0.387 g (1.6 mmol, 2 eq) potassium dihydrobis(3,5-dimethylpyrazol-1-yl)borate is added. Eluent mixture: iso-hexane/DCM (1:2). Yield: 120 mg (23%); melting point: 279 C.; molecular formula: C.sub.26H.sub.27BN.sub.6OPt; molar mass: 645.43 g/mol. 1H NMR in CDCl.sub.3 (300 MHz): =8.11 (d, J=2.0 Hz, 1H, CH.sub.arom), 7.88 (dd, J=7.2, 1.2 Hz, 1H, CH.sub.arom), 7.62-7.45 (m, 2H, CH.sub.arom), 7.41 (td, J=8.2, 7.8, 1.4 Hz, 1H, CH.sub.arom), 7.31 (td, J=7.5, 1.1 Hz, 1H, CH.sub.arom), 7.27-7.21 (m, 1H, CH.sub.arom), 6.88 (d, J=2.1 Hz, 1H, CH.sub.arom), 5.83 (s, 1H, CH.sub.arom), 5.77 (s, 1H, CH.sub.arom), 3.58 (s, 3H, NCH.sub.3), 2.35 (s, 3H, CCH.sub.3), 2.33 (s, 3H, CCH.sub.3), 2.30 (s, 3H, CCH.sub.3), 2.29 (s, 3H, CCH.sub.3). .sup.13C NMR in CDCl.sub.3 (75 MHz): =158.4 (C.sub.i), 155.8 (C.sub.i), 147.9 (C.sub.i), 147.8 (C.sub.i), 145.3 (C.sub.i), 145.0 (C.sub.i), 142.8 (C.sub.i), 131.2 (C.sub.i & CH.sub.arom), 130.4 (C.sub.i), 126.3 (CH.sub.arom), 125.0 (C.sub.i), 122.9 (CH.sub.arom), 122.3 (C.sub.i), 121.1 (CH.sub.arom), 120.4 (CH.sub.arom), 118.6 (CH.sub.arom), 115.9 (CH.sub.arom), 111.4 (CH.sub.arom), 105.7 (CH.sub.arom), 105.2 (CH.sub.arom), 35.8 (NCH.sub.3), 15.4 (CCH.sub.3), 14.6 (CCH.sub.3), 13.0 (CCH.sub.3), 12.9 (CCH.sub.3). .sup.195Pt NMR in CDCl.sub.3 (64 MHz): =3837.5 (s). MS (ESI): m/z=646.4 [MH].sup.+. Elemental analysis: calculated C, 48.38%; H, 4.22%; N, 13.02%; found C, 48.06%; H, 4.03%; N, 12.84%.
[Dihydrobis(pyrazol-1-yl-N.SUP.2.)borate][3-phenyl-1-(phenyl-C.SUP.2.)-1H-benzimidazolin-2-ylidene-C.SUP.2.]platinum(II) (C)
[0094] ##STR00015##
[0095] Synthesis analogous to the general synthesis procedure. 0.287 g (0.8 mmol) 1,3-diphenyl-1H-benzimidazolium tetrafluoroborate.sup.2 and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=45 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 0.298 g (1.6 mmol, 2 eq) potassium dihydrobis(pyrazol-1-yl)borate is added. Eluent mixture: iso-hexane/DCM (5:4). Yield: 154 mg (58%); melting point: 258 C.; molecular formula: C.sub.25H.sub.21BN.sub.6Pt; molar mass: 611.37 g/mol. 1H NMR in DMSO-d.sub.6 (300 MHz): =8.47 (d, J=8.2 Hz, 1H, CH.sub.arom), 7.96 (d, J=7.8 HZ, 1H, CH.sub.arom), 7.83-7.67 (m, 3H, CH.sub.arom), 7.61-7.51 (m, 2H, CH.sub.arom), 7.50-7.37 (m, 3H, CH.sub.arom), 7.37-7.31 (m, 2H, CH.sub.arom), 7.31-7.20 (m, 3H, CH.sub.arom), 7.04 (t, J=7.4 Hz, 1H, CH.sub.arom), 6.86 (d, J=2.1 HZ, 1H, CH.sub.arom), 6.36 (t, J=2.2 Hz, 1H, CH.sub.arom), 5.52 (t, J=2.2 Hz, 1H, CH.sub.arom). .sup.13C NMR in DMSO-d.sub.6 (75 MHz): =166.2 (C.sub.i), 148.5 (C.sub.i), 141.2 (CH.sub.arom), 141.1 (CH.sub.arom), 136.2 (CH.sub.arom), 135.5 (C.sub.i), 135.1 (C.sub.i), 134.1 (CH.sub.arom), 134.0 (CH.sub.arom), 131.3 (C.sub.i), 130.4 (C.sub.i), 128.8 (CH.sub.arom), 128.6 (2CH.sub.arom) 125.4 (CH.sub.arom), 124.2 (2CH.sub.arom), 124.1 (CH.sub.arom), 112.7 (CH.sub.arom), 112.1 (CH.sub.arom), 112.0 (CH.sub.arom), 105.5 (CH.sub.arom), 105.0 (CH.sub.arom). .sup.195Pt NMR in DMSO-d.sub.6 (64 MHz): =3783.2 (s). MS (ESI): m/z=612.4 [MH]+, 1240.4 [2M+NH.sub.4].sup.+. Elemental analysis: calculated C, 49.11%; H, 3.46%; N, 13.75%; found C, 49.12%; H, 3.56%; N, 13.66%.
[Dihydrobis(3,5-dimethylpyrazol-1-yl-N.SUP.2.)borate][3-phenyl-1-(phenyl-C.SUP.2.)-1/benzimidazolin-2-ylidene-C.SUP.2.]platinum(II) (D)
[0096] ##STR00016##
[0097] Synthesis analogous to the general synthesis procedure. 0.287 g (0.8 mmol) 1,3-diphenyl-1H-benzimidazolium tetrafluoroborate.sup.2 and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=45 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 0.387 g (1.6 mmol, 2 eq) potassium dihydrobis(3,5-dimethylpyrazol-1-yl)borate is added. Eluent mixture: iso-hexane/DCM (5:4). Yield: 54 mg (10%); melting point: 269 C.; molecular formula: C.sub.29H.sub.29BN.sub.6Pt; molar mass: 667.48 g/mol. .sup.1H NMR in CD.sub.2Cl.sub.2 (300 MHz): =8.13 (d, J=8.2 Hz, 1H, CH.sub.arom), 7.78-7.65 (m, 1H, CH.sub.arom), 7.62 (dd, J=8.3, 1.4 HZ, 2H, CH.sub.arom), 7.48 (m, 1H, CH.sub.arom), 7.44-7.28 (m, 4H, CH.sub.arom), 7.28-7.03 (m, 3H, CH.sub.arom), 6.97 (td, J=7.4, 1.1 Hz, 1H, CH.sub.arom), 5.84 (s, 1H, CH.sub.arom), 5.07 (s, 1H, CH.sub.arom), 2.31 (s, 3H, CCH.sub.3), 2.25 (s, 3H, CCH.sub.3), 2.19 (s, 3H, CCH.sub.3), 1.75 (s, 3H, CCH3). .sup.13C NMR in CD.sub.2Cl.sub.2 (75 MHz): =169.0 (C.sub.i), 149.6 (C.sub.i), 148.2 (C.sub.i), 147.2 (C.sub.i), 145.8 (C.sub.i), 144.5 (C.sub.i), 136.9 (CH.sub.arom), 136.2 (C.sub.i), 136.0 (C.sub.i), 132.6 (C.sub.i), 132.1 (C.sub.i), 129.0 (CH.sub.arom), 125.4 (CH.sub.arom), 124.4 (CH.sub.arom), 124.2 (CH.sub.arom), 124.0 (CCH.sub.arom), 112.4 (CH.sub.arom), 112.4 (CH.sub.arom), 112.1 (CH.sub.arom), 106.1 (CH.sub.arom), 105.3 (CH.sub.arom), 15.5 (CCH.sub.3), 14.7 (CCH.sub.3), 13.2 (CCH.sub.3), 12.6 (CCH.sub.3). .sup.195Pt NMR in CD.sub.2Cl.sub.2 (64 MHz): =3790.6 (s). MS (ESI): m/z=668.5 [MH]+, 685.4 [M+NH.sub.4].sup.+. Elemental analysis: calculated C, 52.18%; H, 4.38%; N, 12.59%; found C, 51.90%; H, 4.38%; N, 12.44%.
[Dihydrobis(pyrazol-1-yl-N.SUP.2.)borate][4-methyl-1-(phenyl-C.SUP.2.)-1H-1,2,4-triazol-5-ylideneC.SUP.5.]platinum(II) (E)
[0098] ##STR00017##
[0099] Synthesis analogous to the general synthesis procedure. 230 mg (0.8 mmol) 4-methyl-1-phenyl-1H-1,2,4-triazolium iodide.sup.3 and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=45 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 298 mg (1.6 mmol, 2 eq) potassium dihydrobis(pyrazol-1-yl)borate is added. Eluent mixture: iso-hexane/DCM (1:6). Yield: 206 mg (52%); melting point: 231 C.; molecular formula: C.sub.15H.sub.16BN.sub.7Pt; molar mass: 500.23 g/mol. 1H NMR in DMSO-d.sub.6 (300 MHz, DMSO-d.sub.6): =8.78 (s, 1H), 8.09 (dd, J=2.1, 0.7 Hz, 1H), 7.79 (d, J=2.2 Hz, 1H), 7.76 (d, J=2.4 Hz, 2H), 7.31 (dd, J=7.6, 1.4 Hz, 1H), 7.23 (dd, J=7.5, 1.3 Hz, 1H), 7.13 (td, J=7.5, 1.3 Hz, 1H), 7.00 (td, J=7.4, 1.4 Hz, 1H), 6.38 (t, J=2.2 Hz, 1H), 6.30 (t, J=2.2 Hz, 1H), 3.64 (s, 3H). .sup.13C NMR in DMSO-d.sub.6 (75 MHz): =158.2 (C.sub.i), 145.6 (C.sub.i), 144.8 (CH.sub.arom), 143.4 (CH.sub.arom), 141.3 (CH.sub.arom), 136.2 (CH.sub.arom), 136.1 (CH.sub.arom), 133.9 (CH.sub.arom), 126.3 (C.sub.i), 125.2 (CH.sub.arom), 124.1 (CH.sub.arom), 111.5 (CH.sub.arom), 105.6 (CH.sub.arom), 105.4 (CH.sub.arom), 34.6 (NCH.sub.3). .sup.195Pt NMR in DMSO-d.sub.6 (64 MHz): =3868.3 (s). MS (ESI): m/z=499.3 [MH].sup.+. Elemental analysis: calculated C, 36.02%; H, 3.22%; N, 19.60%; found C, 36.39%; H, 3.20%; N, 19.23%.
[Dihydrobis(3,5-dimethylpyrazol-1-yl-N.SUP.2.)borate][4-methyl-1-(phenyl-C.SUP.2.)-1H-1,2,4-triazol-5-ylidene-C.SUP.5.]platinum(II) (F)
[0100] ##STR00018##
[0101] Synthesis analogous to the general synthesis procedure. 0.230 g (0.8 mmol) 4-methyl-1-phenyl-1H-1,2,4-triazolium iodide.sup.3 and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=45 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 0.387 g (1.6 mmol, 2 eq) potassium dihydrobis(3,5-dimethylpyrazol-1-yl)borate is added. Eluent: DCM. Yield: 85 mg (19%); melting point: 241 C.; molecular formula: C.sub.19H.sub.24BN.sub.7Pt; molar mass: 556.34 g/mol. .sup.1H NMR in CDCl.sub.3 (300 MHz): =7.84 (s, 1H, CH.sub.arom), 7.34 (dd, J=7.7, 1.4 Hz, 1H, CH.sub.arom), 7.28 (dd, J=7.6, 1.4 Hz, 1H, CH.sub.arom), 7.09 (td, J=7.5, 1.4 Hz, 1H, CH.sub.arom), 6.96 (td, J=7.4, 1.4 Hz, 1H, CH.sub.arom), 5.81 (s, 1H, CH.sub.arom), 5.77 (s, 1H, CH.sub.arom), 3.57 (s, 3H, NCH.sub.3), 2.32 (s, 3H, CCH.sub.3), 2.31 (s, 3H, CCH.sub.3), 2.29 (s, 3H, CCH3), 2.25 (s, 3H, CCH.sub.3). .sup.13C NMR in CDCl.sub.3 (151 MHz): =161.2 (C.sub.i), 147.7 (C.sub.i), 147.6 (C.sub.i), 145.9 (C.sub.i), 145.4 (C.sub.i), 145.0 (C.sub.i), 141.9 (CH.sub.arom), 136.4 (CH.sub.arom), 126.64, 125.4 (CH.sub.arom), 123.9 (CH.sub.arom), 111.8 (CH.sub.arom), 105.6 (CH.sub.arom), 105.1 (CH.sub.arom), 33.2 (NCH.sub.3), 15.2 (CCH.sub.3), 14.6 (CCH.sub.3), 12.8 (2CCH.sub.3). .sup.195Pt NMR in CDCl.sub.3 (64 MHz): =3884.4 (s). MS (ESI): m/z=555.4 [MH].sup.+, 1130.6 [2M+NH.sub.4].sup.+. Elemental analysis: calculated C, 41.02%; H, 4.35%; N, 17.62%; found C, 40.83%; H, 4.51%; N, 17.36%.
[Dihydrobis(4-methylpyrazol-1-yl-N.SUP.2.)borate][4-methyl-1-(phenyl-C.SUP.2.)-1H-1,2,4-triazol-5-ylidene-C.SUP.5.]platinum(II) (G)
[0102] ##STR00019##
[0103] Synthesis analogous to the general synthesis procedure. 0.230 g (0.8 mmol) 4-methyl-1-phenyl-1H-1,2,4-triazolium iodide.sup.3 and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=45 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 0.343 g (1.6 mmol, 2 eq) potassium dihydrobis(4-methylpyrazol-1-yl)borate is added. Eluent mixture: iso-hexane/DCM (1:5). Yield: 164 mg (39%); melting point: 248 C.; molecular formula: C.sub.17H.sub.20BN.sub.7Pt; molar mass: 528.28 g/mol. 1H NMR in CDCl.sub.3 (600 MHz): =7.85 (s, 1H, CH.sub.arom), 7.54 (s, 1H, CH.sub.arom), 7.47 (s, 1H, CH.sub.arom), 7.43-7.40 (m, 2H, CH.sub.arom), 7.39 (s, 1H, CH.sub.arom), 7.37 (dd, J=7.7, 1.3 Hz, 1H, CH.sub.arom), 7.14 (td, J=7.5, 1.3 Hz, 1H, CH.sub.arom), 7.06 (td, J=7.4, 1.4 Hz, 1H, CH.sub.arom), 3.70 (s, 3H, NCH3), 2.10 (s, 3H, CCH3), 2.03 (s, 3H, CCH.sub.3 .sup.13C NMR in CDCl.sub.3 (151 MHz): =160.8 (C), 146.1 (C.sub.i), 142.2 (CH.sub.arom), 141.8 (CH.sub.arom), 140.9 (CH.sub.arom), 135.8 (CH.sub.arom), 135.6 (CH.sub.arom), 134.8 (CH.sub.arom), 126.2 (C.sub.i), 125.8 (CH.sub.arom), 124.4 (CH.sub.arom), 115.5 (C.sub.i), 115.4 (C.sub.i), 112.3 (CH.sub.arom), 35.0 (NCH.sub.3), 9.1 (CCH.sub.3), 9.0 (CCH.sub.3). .sup.195Pt NMR in CDCl.sub.3 (64 MHz): =3857.2 (s). MS (ESI): m/z=529.3 [M+H].sup.+, 546.3 [M+NH.sub.4].sup.+. Elemental analysis: calculated C, 38.65%; H, 3.82%; N, 18.56%; found C, 38.62%; H, 3.81%; N, 18.45%.
[Cycloocta-1,5-diylbis(pyrazol-1-yl-N.SUP.2.)borate][4-methyl-1-(phenyl-C.SUP.2.)-1H-1,2,4-triazol-5-ylidene-C.SUP.5.]platinum(II) (H)
[0104] ##STR00020##
[0105] Synthesis analogous to the general synthesis procedure. 0.230 g (0.8 mmol) 4-methyl-1-phenyl-1H-1,2,4-triazolium iodide.sup.3 and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=45 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 0.471 g (1.6 mmol, 2 eq) potassium cycloocta-1,5-diylbis(pyrazol-1-yl)borate is added. Eluent mixture: iso-hexane/DCM (2:5). Yield: 80 mg (16%); melting point: 301 C.; molecular formula: C.sub.23H.sub.28BN.sub.7Pt; molar mass: 608.41 g/mol. .sup.1H NMR in CDCl.sub.3 (600 MHz): =7.89 (s, 1H, CH.sub.arom), 7.81-7.74 (m, 3H, CH.sub.arom), 7.70 (dd, J=2.0, 0.7 Hz, 1H, CH.sub.arom), 7.56-7.41 (m, 1H, CH.sub.arom), 7.39 (dd, J=7.7, 1.3 Hz, 1H), 7.15 (td, J=7.6, 1.3 HZ, 1H, CH.sub.arom), 7.06 (td, J=7.4, 1.4 Hz, 1H, CH.sub.arom), 6.24 (t, J=2.2 Hz, 1H, CH.sub.arom), 6.19 (t, J=2.2 Hz, 1H, CH.sub.arom), 3.76 (s, 3H, NCH.sub.3), 3.58-3.51 (m, 1H, CH.sub.9-BBN), 2.29-2.20 (m, 2H, CH.sub.2, 9-BBN), 2.06-1.85 (m, 4H, CH.sub.2, 9-BBN), 1.75-1.58 (m, 2H, CH.sub.2, 9-BBN), 1.52-1.40 (m, 5H, C/2, 9-BBN & C-BBN). .sup.13C NMR in CDCl.sub.3 (151 MHz): =161.1 (C.sub.i), 145.8 (C.sub.i), 142.1 (CH.sub.arom), 141.5 (CH.sub.arom), 141.2 (CH.sub.arom), 134.5 (CH.sub.arom), 134.3 (CH.sub.arom), 134.2 (CH.sub.arom), 126.4 (C.sub.i), 125.9 (CH.sub.arom), 124.2 (CH.sub.arom), 112.4 (CH.sub.arom), 105.1 (CH.sub.arom), 104.8 (CH.sub.arom), 34.8 (NCH.sub.3), 32.5 (CH.sub.2, 9-BBN), 32.3 (CH.sub.2, 9-BBN), 31.3 (CH.sub.2, 9-BBN), 30.3 (CH.sub.2, 9-BBN), 24.7 (CH.sub.2, 9-BBN), 24.6 (CH.sub.2, 9-BBN). .sup.195Pt NMR in CDCl.sub.3 (129 MHz): =3766.3 (s). MS (ESI): m/z=609.3 [MH].sup.+, 1234.4 [2M+NH.sub.4].sup.+. Elemental analysis: calculated C, 45.40%; H, 4.64%; N, 16.11%; found C, 45.43%; H, 4.63%; N, 16.03%.
[Cycloocta-1,5-diylbis(4-methylpyrazol-1-yl-N.SUP.2.)borate][4-methyl-1-(phenyl-C.SUP.2.)-1H-1,2,4-triazol-5-ylidene-C.SUP.5.]platinum(II) (I)
[0106] ##STR00021##
[0107] Synthesis analogous to the general synthesis procedure. 0.230 g (0.8 mmol) 4-methyl-1-phenyl-1H-1,2,4-triazolium iodide.sup.3 and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=45 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 0.516 g (1.6 mmol, 2 eq) potassium cycloocta-1,5-diylbis(4-methylpyrazol-1-yl)borate is added. Eluent mixture: iso-hexane/DCM (2:5).
[0108] Yield: 235 mg (46%); melting point: 241 C. (dec.); molecular formula: C.sub.25H.sub.32BN.sub.7Pt; molar mass: 636.47 g/mol. .sup.1H NMR in CDCl.sub.3 (600 MHz): =7.87 (s, 1H, CH.sub.arom), 7.55 (s, 1H, CH.sub.arom), 7.53 (s, 1H, CH.sub.arom), 7.53 (s, 1H, CH.sub.arom), 7.50 (dd, J=7.5, 1.3 Hz, 1H, CH.sub.arom), 7.48 (s, 1H, CH.sub.arom), 7.38 (dd, J=7.7, 1.3 Hz, 1H, CH.sub.arom), 7.14 (td, J=7.5, 1.3 Hz, 1H, CH.sub.arom), 7.06 (td, J=7.4, 1.4 Hz, 1H, CH.sub.arom), 3.76 (s, 3H, NCH3), 3.45 (bs, 1H, CH.sub.9-BBN), 2.28-2.19 (m, 2H, CH.sub.2,9-BBN), 2.07 (s, 3H, CCH.sub.3), 2.02 (s, 3H, CCH.sub.3), 2.01-1.91 (m, 2H, CH.sub.2, 9-BBN), 1.91-1.84 (n, 2H, CH.sub.2, 2, 9-BBN), 1.73-1.66 (n, 1H, CH.sub.2, 9-BBN), 1.63-1.58 (m, 1H, CH.sub.2, 9-BBN), 1.52-1.42 (m, 4H, CH.sub.2, 9-BBN), 1.35 (bs, 1H, CH.sub.9-BBN). .sup.13C NMR in CDCl.sub.3 (151 MHz): =161.5 (C.sub.i), 145.8 (C.sub.i), 142.0 (CH.sub.arom), 141.2 (CH.sub.arom), 140.8 (CH.sub.arom), 134.4 (CH.sub.arom), 133.9 (CH.sub.arom), 133.6 (CH.sub.arom), 126.8 (C.sub.i), 125.8 (CH.sub.arom), 124.1 (CH.sub.arom), 115.1 (C.sub.i), 114.8 (C.sub.i), 112.3 (CH.sub.arom), 34.8 (NCH.sub.3), 32.6 (CH.sub.2), 32.4 (CH.sub.2), 31.3 (CH.sub.2), 30.4 (CH.sub.2), 24.7 (CH.sub.2), 24.7 (CH.sub.2), 9.2 (2CCH.sub.3). .sup.195Pt NMR in CDCl.sub.3 (129 MHz): =3757.1 (s). MS (ESI): m/z=637.4 [M+H].sup.+. Elemental analysis: calculated C, 47.18%; H, 5.07%; N, 15.40%; found C, 47.09%; H, 5.19%; N, 15.08%.
[Dihydrobis(pyrazol-1-yl-N.SUP.2.)borate][3,4-diphenyl-1-(phenyl-C.SUP.2.)-1H-1,2,4-triazol-5-ylidene-C.SUP.5.]platinum(II) (3)
[0109] ##STR00022##
[0110] Synthesis analogous to the general synthesis procedure. 0.340 g (0.8 mmol) 1,3,4-triphenyl-1H-1,2,4-triazolium iodide.sup.4 and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=55 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 0.298 g (1.6 mmol, 2 eq) potassium dihydrobis(pyrazol-1-yl)borate is added. Eluent mixture: iso-hexane/DCM (1:1). Yield: 161 mg (32%); melting point: 270 C.; molecular formula: C.sub.26H.sub.22BN.sub.7Pt; molar mass: 638.4 g/mol. 1H NMR in CD.sub.2Cl.sub.2 (600 MHz): =7.76 (dd, J=2.2, 0.7 HZ, 1H, CH.sub.arom), 7.59 (dd, J=2.3, 0.8 Hz, 1H, CH.sub.arom), 7.51-7.47 (m, 1H, CH.sub.arom), 7.47-7.41 (m, 2H, CH.sub.arom), 7.39 (dd, J=7.5, 1.2 Hz, 1H, CH.sub.arom), 7.35-7.31 (m, 2H, CH.sub.arom), 7.31-7.28 (m, 3H, CH.sub.arom), 7.26-7.15 (m, 3H, CH.sub.arom), 7.11-6.97 (m, 3H, CH.sub.arom), 6.44 (dd, J=2.1, 0.7 Hz, 1H, CH.sub.arom), 6.28 (t, J=2.2 Hz, 1H, CH.sub.arom), 5.47 (t, J=2.2 Hz, 1H, CH.sub.arom). .sup.13C NMR in CD.sub.2Cl.sub.2 (151 MHz): =161.0 (C.sub.i), 152.9 (C.sub.i), 146.6 (C.sub.i), 141.7 (CH.sub.arom), 141.1 (CH.sub.arom), 136.5 (CH.sub.arom), 135.3 (C.sub.i), 134.9 (CH.sub.arom), 134.8 (CH.sub.arom), 131.1 (CH.sub.arom), 130.3 (CH.sub.arom), 129.7 (CH.sub.arom), 129.1 (CH.sub.arom), 127.6 (C.sub.i), 126.2 (CH.sub.arom), 125.6 (C.sub.i), 124.8 (CH.sub.arom), 112.9 (CH.sub.arom), 105.7 (CH.sub.arom), 105.6 (CH.sub.arom). .sup.195Pt NMR in CD.sub.2Cl.sub.2 (129 MHz): =3837.2 (s). MS (ESI): m/z=637.4 [M+H].sup.+, 1294.5 [2M+NH.sub.4].sup.+. Elemental analysis: calculated C, 48.92%; H, 3.47%; N, 15.38%; found C, 48.67%; H, 3.44%; N, 15.24%.
[Dihydrobis(pyrazol-1-yl-N.SUP.2.)borate][1-methyl-3-(phenyl-C.SUP.2.)-1H-imidazo[4,5-b]pyridin-2-ylidene-C.SUP.2.]platinum(II) (K)
[0111] ##STR00023##
[0112] Synthesis analogous to the general synthesis procedure. 0.270 g (0.8 mmol) 1-methyl-3-phenyl-1H-imidazo[4,5-b]pyridinium iodide.sup.5 and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=45 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 0.298 g (1.6 mmol, 2 eq) potassium dihydrobis(pyrazol-1-yl)borate is added. Eluent mixture: iso-hexane/DCM (2:5). Yield: 124 mg (28%); melting point: 244 C.; molecular formula: C.sub.19H.sub.18BN.sub.7Pt; molar mass: 550.29 g/mol. 1H NMR in CDCl.sub.3 (600 MHz): =8.52 (dd, J=4.9, 1.4 HZ, 1H, CH.sub.arom), 8.50 (dd, J=7.8, 1.3 Hz, 1H, CH.sub.arom), 7.79 (d, J=1.4 HZ, 1H, CH.sub.arom), 7.70 (d, J=2.0 HZ, 1H, CH.sub.arom), 7.69 (d, J=2.3 Hz, 1H, CH.sub.arom), 7.67 (dd, J=8.0, 1.4 Hz, 1H, CH.sub.arom), 7.64 (d, J=1.6 Hz, 1H, CH.sub.arom), 7.43 (dd, J=7.5, 1.4 Hz, 1H, CH.sub.arom), 7.31 (dd, J=8.0, 4.9 Hz, 1H, CH.sub.arom), 7.23 (td, J=7.6, 1.4 Hz, 1H, CH.sub.arom), 7.06 (td, J=7.4, 1.4 Hz, 1H, CH.sub.arom), 6.29 (t, J=2.2 Hz, 1H, CH.sub.arom), 6.24 (t, J=2.2 Hz, 1H, CH.sub.arom), 3.75 (s, 3H, NCH3). .sup.13C NMR in CDCl.sub.3 (151 MHz): =171.5 (C.sub.i), 148.0 (C.sub.i), 145.4 (C.sub.i), 145.3 (CH.sub.arom), 142.0 (CH.sub.arom), 141.6 (CH.sub.arom), 136.4 (CH.sub.arom), 136.4 (CH.sub.arom), 134.7 (CH.sub.arom), 129.3 (C.sub.i), 128.3 (C.sub.i), 124.7 (CH.sub.arom), 124.6 (CH.sub.arom), 118.6 (CH.sub.arom), 118.0 (CH.sub.arom), 114.7 (CH.sub.arom), 105.5 (CH.sub.arom), 105.2 (CH.sub.arom), 34.8 (NCH.sub.3). .sup.195Pt NMR in CDCl.sub.3 (64 MHz): =3748.6 (s). MS (ESI): m/z=551.3 [M+H].sup.+. Elemental analysis: calculated C, 41.47%; H, 3.30%; N, 17.82%; found C, 41.11%; H, 3.32%; N, 17.52%.
[Dihydrobis(3,5-dimethylpyrazol-1-yl-N.SUP.2.)borate][1-methyl-3-(phenyl-C.SUP.2.)_1H-imidazo[4,5-b]pyridin-2-ylidene-C.SUP.2.]platinum(II) (L)
[0113] ##STR00024##
[0114] Synthesis analogous to the general synthesis procedure. 0.270 g (0.8 mmol) 1-methyl-3-phenyl-1H-imidazo[4,5-b]pyridinium iodide.sup.5 and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=45 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 0.387 g (1.6 mmol, 2 eq) potassium dihydrobis(3,5-dimethylpyrazol-1-yl)borate is added. Eluent mixture: iso-hexane/DCM (1:1). Yield: 99 mg (20%); melting point: 257 C.; molecular formula: C.sub.23H.sub.26BN.sub.7Pt; molar mass: 606.40 g/mol. .sup.1H NMR in CDCl.sub.3 (600 MHz): =8.49 (dd, J=4.9, 1.4 Hz, 1H, CH.sub.arom), 8.43 (dd, J=7.8, 1.3 Hz, 1H, CH.sub.arom), 7.63 (dd, J=8.1, 1.4 Hz, 1H, CH.sub.arom), 7.39-7.28 (m, 1H, CH.sub.arom), 7.29-7.26 (m, 1H, CH.sub.arom), 7.17 (td, J=7.6, 1.4 Hz, 1H, CH.sub.arom), 6.96 (td, J=7.4, 1.3 Hz, 1H, CH.sub.arom), 5.82 (s, 1H, CH.sub.arom), 5.79 (s, 1H, CH.sub.arom), 3.69 (s, 3H, NCH3), 2.34 (s, 6H, CCH.sub.3), 2.29 (s, 3H, CCH.sub.3), 2.25 (s, 3H, CCH.sub.3). .sup.13C NMR in CDCl.sub.3 (151 MHz): =171.8 (C.sub.i), 148.0 (C.sub.i), 147.9 (C.sub.i), 147.8 (C.sub.i), 145.5 (C.sub.i), 145.2 (C.sub.i), 145.1 (CH.sub.arom), 136.4 (CH.sub.arom), 129.7 (C.sub.i), 128.3 (C.sub.i), 124.3 (CH.sub.arom), 124.1 (CH.sub.arom), 118.3 (CH.sub.arom), 117.8 (CH.sub.arom), 114.2 (CH.sub.arom), 105.9 (CH.sub.arom), 105.3 (CH.sub.arom), 33.0 (NCH.sub.3), 15.5 (CCH.sub.3), 14.5 (CCH.sub.3), 12.9 (CCH.sub.3), 12.9 (CCH.sub.3). .sup.195Pt NMR in CDCl.sub.3 (129 MHz): =3749.8 (s). MS (ESI): m/z=607.5 [M+H].sup.+, 624.4 [M+NH.sub.4].sup.+. Elemental analysis: calculated C, 45.56%; H, 4.32%; N, 16.17%; found C, 45.19%; H, 4.24%; N, 16.02%.
[Cycloocta-1,5-diylbis(4-methylpyrazol-1-yl-N.SUP.2.)borate][1-methyl-3-(phenyl-C.SUP.2.)-1/imidazo[4,5-b]pyridin-2-ylidene-C.SUP.2.]platinum(II) (M)
[0115] ##STR00025##
[0116] Synthesis analogous to the general synthesis procedure. 0.270 g (0.8 mmol) 1-methyl-3-phenyl-1H-imidazo[4,5-b]pyridinium iodide.sup.5 and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=45 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 0.516 g (1.6 mmol, 2 eq) potassium cycloocta-1,5-diylbis(4-methylpyrazol-1-yl)borate is added. Eluent mixture: iso-hexane/DCM (3:5). Yield: 82 mg (15%); decomposition point>310 C.; molecular formula: C.sub.29H.sub.34BN.sub.7Pt; molar mass: 686.53 g/mol. 1H NMR in CDCl.sub.3 (600 MHz): =8.50 (dd, J=4.9, 1.4 Hz, 1H, CH.sub.arom), 8.47 (dd, J=7.8, 1.3 Hz, 1H, CH.sub.arom), 7.66 (dd, J=8.0, 1.4 Hz, 1H, CH.sub.arom), 7.57 (s, 1H, CH.sub.arom), 7.55 (s, 1H, CH.sub.arom), 7.54 (s, 1H, CH.sub.arom), 7.52 (dd, J=7.5, 1.3 Hz, 1H, CH.sub.arom), 7.49 (s, 1H, CH.sub.arom), 7.29 (dd, J=8.0, 4.9 Hz, 1H, CH.sub.arom), 7.23 (td, J=7.6, 1.4 Hz, 1H, CH.sub.arom), 7.06 (td, J=7.4, 1.4 Hz, 1H, CH.sub.arom), 3.89 (s, 3H, NCH.sub.3), 3.54 (bs, 1H, CH.sub.9-BBN), 2.31-2.22 (m, 2H, C/2, 9-BBN), 2.08 (s, 3H, CCH.sub.3), 2.04 (s, 3H, CCH.sub.3), 2.02-1.85 (m, 4H, CH.sub.2, 9-BBN), 1.76-1.60 (m, 2H, CH.sub.2, 9-BBN), 1.60-1.47 (m, 4H, CH.sub.2, 9-BBN), 1.39 (s, 1H, CH.sub.9-BBN). .sup.13C NMR in CDCl.sub.3 (151 MHz): =172.3 (C.sub.i), 147.7 (C.sub.i), 145.5 (C.sub.i), 145.0 (CH.sub.arom), 141.2 (CH.sub.arom), 141.1 (CH.sub.arom), 134.3 (CH.sub.arom), 133.9 (CH.sub.arom), 133.7 (CH.sub.arom), 129.9 (C.sub.i), 128.3 (C.sub.i), 124.6 (CH.sub.arom), 124.2 (CH.sub.arom), 118.3 (CH.sub.arom), 117.8 (CH.sub.arom), 115.3 (C.sub.i), 114.8 (C.sub.i), 114.6 (CH.sub.arom), 34.7 (NCH.sub.3), 32.6 (CH.sub.2, 9-BBN), 32.3 (CH.sub.2, 9-BBN), 31.4 (CH.sub.2, 9-BBN), 30.4 (CH.sub.2, 9-BBN), 24.8 (CH.sub.2, 9-BBN), 24.7 (CH.sub.2, 9-BBN), 9.3 (CCH.sub.3), 9.2 (CCH.sub.3). .sup.195Pt NMR in CDCl.sub.3 (129 MHz): =3636.7 (s). MS (ESI): m/z=687.4 [M+H].sup.+. Elemental analysis: calculated C, 50.74%; H, 4.99%; N, 14.28%; found C, 50.92%; H, 5.24%; N, 13.96%.
[Dihydrobis(pyrazol-1-yl-N.SUP.2.][3-(4-fluorophenyl-C.SUP.2.)-1-methyl-1,2,3-triazol-4-ylidene-C.SUP.4.]platinum(II) (N)
[0117] ##STR00026##
[0118] Synthesis analogous to the general synthesis procedure. 0.244 g (0.8 mmol) 1-(4-fluorophenyl)-3-methyl-1H-1,2,3-triazolium iodide.sup.6 and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=85 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the last step of the reaction, 0.262 g (1.41 mmol, 1.76 eq) potassium dihydrobis(pyrazol-1-yl)borate is added, deviating from the general prescription. Eluent: DCM. Yield: 114 mg (28%); melting point: 219 C.; molecular formula: C.sub.15H.sub.15BFN.sub.7Pt; molar mass: 518.22 g/mol. .sup.1H NMR in DMSO-d.sub.6 (600 MHz): =8.19 (s, 1H, CH.sub.arom), 7.87 (dd, J=2.1, 0.7 Hz, 1H, CH.sub.arom), 7.86 (dd, J=2.1, 0.7 Hz, 1H, CH.sub.arom), 7.80 (dd, J=2.3, 0.7 Hz, 1H, CH.sub.arom), 7.75 (dd, J=2.3, 0.7 Hz, 1H, CH.sub.arom), 7.56 (dd, J=8.6, 5.0 Hz, 1H, CH.sub.arom), 7.06 (dd, J=9.8, 2.7 Hz, 1H, CH.sub.arom), 7.00 (td, J=8.6, 2.7 Hz, 1H, CH.sub.arom), 6.43 (t, J=2.2 Hz, 1H, CH.sub.arom), 6.39 (t, J=2.2 Hz, 1H, CH.sub.arom), 4.25 (s, 3H, NCH.sub.3), 3.57 (bs, 2H, BH.sub.2). .sup.13C NMR in DMSO-d.sub.6 (151 MHz): =161.0 (d, J=246.9 Hz, C.sub.i), 142.0 (C.sub.i), 141.4 (CH.sub.arom), 141.1 (CH.sub.arom, C.sub.i), 136.1 (CH.sub.arom), 135.6 (CH.sub.arom), 134.9 (d, J=5.7 Hz, C.sub.i), 131.6 (CH.sub.arom), 120.7 (d, J=19.8 Hz, CH.sub.arom), 114.7 (d, J=9.1 Hz, CH.sub.arom), 110.0 (d, J=24.4 Hz, CH.sub.arom), 105.8 (CH.sub.arom), 105.6 (CH.sub.arom), 38.6 (NCH.sub.3). .sup.19F NMR in DMSO-d.sub.6 (282 MHz): =113.7 (s). MS: (ESI, m/z)=517.3 (MH).sup.+, 1035.4 (2MH).sup.+. Elemental analysis: calculated C, 34.77%; H, 2.92%; N, 18.92%; found C, 34.51%; H, 2.79%; N, 18.74%.
[Dihydrobis(3,5-dimethylpyrazol-1-yl-N.SUP.2.)borate][3-(4-fluorophenyl-C.SUP.2.)-1-methyl-1,2,3-triazol-4-ylidene-C.SUP.4.]platinum(II) (O)
[0119] ##STR00027##
[0120] Synthesis analogous to the general synthesis procedure. 0.244 g (0.8 mmol) 1-(4-fluorophenyl)-3-methyl-1H-1,2,3-triazolium iodide.sup.6 and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=85 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 0.387 g (1.6 mmol, 2 eq) potassium dihydrobis(3,5-dimethylpyrazol-1-yl)borate is added. Eluent: DCM. Yield: 74 mg (16%); melting point: 264 C.; molecular formula: C.sub.19H.sub.23BFN.sub.7Pt; molar mass: 574.33 g/mol. 1H NMR in CDCl.sub.3 (600 MHz): =7.42 (dd, J=8.6, 4.9 HZ, 1H, CH.sub.arom), 7.27 (s, 1H, CH.sub.arom), 7.15 6.96 (m, 1H, CH.sub.arom), 6.79 (td, J=8.5, 2.7 Hz, 1H, CH.sub.arom), 5.85 (s, 1H, CH.sub.arom), 5.77 (s, 1H, CH.sub.arom), 4.08 (s, 3H, NCH.sub.3), 2.34 (s, 3H, CCH.sub.3), 2.32 (s, 3H, CCH.sub.3), 2.30 (s, 3H, CCH.sub.3), 2.28 (s, 3H, CCH.sub.3). .sup.13C NMR in CDCl.sub.3 (151 MHz): =162.24 (d, J=248.6 Hz, C.sub.i), 147.4 (C.sub.i), 147.3 (C.sub.i), 144.8 (C.sub.i), 144.7 (C.sub.i), 143.4 (C.sub.i), 142.01 (d, J=1.9 Hz, G), 134.9 (d, J=6.0 Hz, G), 131.6 (CH.sub.arom), 123.46 (d, J=19.9 Hz, CH.sub.arom), 114.61 (d, J=9.2 Hz, CH.sub.arom), 109.89 (d, J=25.0 Hz, CH.sub.arom), 105.8 (CH.sub.arom), 105.0 (CH.sub.arom), 38.5 (NCH.sub.3), 15.0 (CCH.sub.3), 14.7 (CCH.sub.3), 13.0 (2CCH.sub.3). .sup.19F NMR in CDCl.sub.3 (282 MHz): =113.8 (s). .sup.195Pt NMR in CDCl.sub.3 (129 MHz): =3851.0 (s). MS (ESI): m/z=575.4 [MH].sup.+. Elemental analysis: calculated C, 39.73%; H, 4.04%; N, 17.07%; found C, 39.58%; H, 4.05%; N, 16.89%.
[3-(2,4-difluorophenyl-C.SUP.6.)-1-methyl-1,2,3-triazol-4-ylidene-C.SUP.4.][dihydrobis(pyrazol-1-yl-N.SUP.2.)borate]platinum(II) (P)
[0121] ##STR00028##
[0122] Synthesis analogous to the general synthesis procedure. 0.258 g (0.8 mmol) 1-(2,4-difluorophenyl)-3-methyl-1H-1,2,3-triazolium iodide and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=85 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 0.298 g (1.6 mmol, 2 eq) potassium dihydrobis(pyrazol-1-yl)borate is added. Eluent mixture: iso-hexane/DCM (1:5). Yield: 153 mg (36%); melting point: 286 C.; molecular formula: C.sub.15H.sub.14BF.sub.2N.sub.7Pt; molar mass: 536.21 g/mol. 1H NMR in DMSO-d.sub.6 (600 MHz): =8.22 (s, 1H), 7.87 (dd, J=2.1, 0.7 Hz, 1H), 7.86 (dd, J=2.1, 0.7 Hz, 1H), 7.81 (dd, J=2.3, 0.7 Hz, 1H), 7.76 (dd, J=2.3, 0.7 Hz, 1H), 7.14 (ddd, J=11.4, 9.1, 2.5 Hz, 1H), 6.91 (dd, J=9, 0, 2.5 Hz, 1H), 6.43 (t, J=2.2 Hz, 1H), 6.40 (t, J=2.2 Hz, 1H), 4.27 (s, 3H). .sup.13C NMR in DMSO-d.sub.6 (151 MHz): =160.7 (dd, J=250.4, 9.7 Hz, C.sub.i), 150.2 (dd, J=258.0, 13.4 Hz, C.sub.i), 141.8 (C.sub.i), 141.4 (CH.sub.arom), 141.1 (CH.sub.arom), 137.1 (C.sub.i), 136.2 (CH.sub.arom), 135.8 (CH.sub.arom), 131.0 (CH.sub.arom), 128.9 (C.sub.i), 116.7 (d, J=19.1 Hz, CH.sub.arom), 105.9 (CH.sub.arom), 105.7 (CH.sub.arom), 99.8 (dd, J=28.0, 22.8 Hz, CH.sub.arom), 38.8 (NCH.sub.3). .sup.19F NMR in DMSO-d.sub.6 (282 MHz): =108.5-112.1 (m), 120.1-123.1 (m). .sup.195Pt NMR in DMSO-d.sub.6 (64 MHz): =3829.4 (s). MS (ESI): m/z=535.2 (MH)+. Elemental analysis: calculated C, 33.60%; H, 2.63%; N, 18.29%; found C, 34.00%; H, 2.50%; N, 17.93%.
[3-(2,4-difluorophenyl-C.SUP.6.)-1-methyl-1,2,3-triazol-4-ylidene-C.SUP.4.][dihydrobis(3,5-dimethylpyrazol-1-yl-N.SUP.2.)borate]platinum(II) (Q)
[0123] ##STR00029##
[0124] Synthesis analogous to the general synthesis procedure. 0.258 g (0.8 mmol) 1-(2,4-difluorophenyl)-3-methyl-1H-1,2,3-triazolium iodide and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=85 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 0.387 g (1.6 mmol, 2 eq) potassium dihydrobis(3,5-dimethylpyrazol-1-yl)borate is added. Eluent mixture: iso-hexane/DCM (2:5).
[0125] Yield: 83 mg (18%); melting point: 235 C.; molecular formula: C.sub.19H.sub.22BF.sub.2N.sub.7Pt; molar mass: 592.32 g/mol. 1H NMR in DMSO-d.sub.6 (600 MHz): =8.05 (s, 1H, CH.sub.arom), 7.08 (ddd, J=11.4, 9.1, 2.5 Hz, 1H, CH.sub.arom), 6.64 (dd, J=8.8, 2.5 Hz, 1H, CH.sub.arom), 5.96 (s, 1H, CH.sub.arom), 5.90 (s, 1H, CH.sub.arom), 4.24 (s, 3H, NCH.sub.3), 2.28 (s, 3H, CCH.sub.3), 2.25 (s, 3H, CCH.sub.3), 2.22 (s, 3H, CCH.sub.3), 2.21 (s, 3H, CCH3). .sup.13C NMR in DMSO-d.sub.6 (151 MHz): =160.6 (dd, J=249.8, 9.7 Hz, C.sub.i), 150.0 (dd, J=257.8, 13.3 Hz, C.sub.i), 147.6 (C.sub.i), 146.4 (C.sub.i), 144.0 (2C.sub.i), 141.6 (C.sub.i), 137.2 (d, J=6.5 Hz, C.sub.i), 132.4 (CH.sub.arom), 128.8 (dd, J=4.6, 2.8 Hz, C), 117.7 (d, J=18.9 Hz, CH.sub.arom), 105.8 (CH.sub.arom), 105.1 (CH.sub.arom), 99.41 (dd, J=28.1, 22.7 Hz, CH.sub.arom), 38.7 (NCH.sub.3), 14.6 (CCH.sub.3), 14.3 (CCH.sub.3), 12.5 (CCH.sub.3), 12.4 (CCH.sub.3). .sup.19F NMR in DMSO-d.sub.6 (282 MHz): =111.84 (d, J=5.9 Hz, CF), 122.86 (d, J=5.8 Hz, CF). .sup.195Pt NMR in DMSO-d.sub.6 (129 MHz): =3844.3 (s). MS (ESI): m/z=591.2 [MH].sup.+. Elemental analysis: calculated C, 38.53%; H, 3.74%; N, 16.55%; found C, 38.20%; H, 3.64%; N, 16.16%.
[dihydrobis(3,5-dimethylpyrazol-1-yl-N.SUP.2.)borate][1-methyl-3-(phenyl-C.SUP.2.)-1/imidazolin-2-ylidene-C.SUP.2.]platinum(II) R
[0126] ##STR00030##
[0127] Synthesis analogous to the general synthesis procedure. 0.229 g (0.8 mmol) 1-methyl-3-phenyl-1H-imidazolium iodide.sup.7 and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=45 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 0.387 g (1.6 mmol, 2 eq) potassium dihydrobis(3,5-dimethylpyrazol-1-yl)borate is added. Eluent mixture: iso-hexane/DCM (3:5). Yield: 79 mg (18%); melting point: 243 C. (dec.); molecular formula: C.sub.20H.sub.25BN.sub.6Pt; molar mass: 555.35 g/mol. 1H NMR in CDCl.sub.3 (600 MHz): =7.27 (d, J=2.1 Hz, 1H, CH.sub.arom), 7.27 7.24 (m, 1H, CH.sub.arom), 7.03 (td, J=7.5, 1.3 Hz, 1H, CH.sub.arom), 6.97 (dd, J=7.8, 1.3 Hz, 1H, CH.sub.arom), 6.88 (td, J=7.4, 1.3 HZ, 1H, CH.sub.arom), 6.80 (d, J=2.1 Hz, 1H, CH.sub.arom), 5.79 (s, 1H, CH.sub.arom), 5.74 (s, 1H, CH.sub.arom), 3.52 (s, 3H), 2.32 (s, 3H, CCH.sub.3), 2.31 (s, 3H, CCH.sub.3), 2.26 (s, 3H, CCH.sub.3), 2.25 (s, 3H, CCH.sub.3). .sup.13C NMR in CDCl.sub.3 (151 MHz): =158.5 (f), 147.7 (C.sub.i), 147.6 (C.sub.i), 147.5 (C.sub.i), 145.2 (C.sub.i), 144.8 (C.sub.i), 137.0 (CH.sub.arom), 129.9 (C.sub.i), 124.4 (CH.sub.arom), 123.5 (CH.sub.arom), 121.2 (CH.sub.arom), 115.1 (CH.sub.arom), 110.1 (CH.sub.arom), 105.6 (CH.sub.arom), 105.1 (CH.sub.arom), 35.8 (NCH.sub.3), 15.3 (CCH.sub.3), 14.6 (CCH.sub.3), 13.0 (CCH.sub.3), 12.9 (CCH.sub.3). .sup.195Pt NMR in CDCl.sub.3 (64 MHz): =3864.2 (s). MS (ESI): m/z=556.4 [M+H].sup.+, 1128.7 [2M+NH.sub.4].sup.+. Elemental analysis: calculated C, 43.25%; H, 4.54%; N, 15.13%; found C, 42.95%; H, 4.36%; N, 14.82%.
[Dihydrobis(3,5-dimethylpyrazol-1-yl-N.SUP.2.)borate][1-methyl-3-(5-methylphenyl-C.SUP.2.)-1H-imidazolin-2-ylidene-C.SUP.2.]platinum(II) (S)
[0128] ##STR00031##
[0129] Synthesis analogous to the general synthesis procedure. 0.240 g (0.8 mmol) 1-methyl-3-(3-methylphenyl)-1H-imidazolium iodide and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=45 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 0.387 g (1.6 mmol, 2 eq) potassium dihydrobis(3,5-dimethylpyrazol-1-yl)borate is added. Eluent mixture: iso-hexane/DCM (3:5). Yield: 147 mg (33%); melting point: 227 C.; molecular formula: C.sub.21H.sub.27BN.sub.6Pt; molar mass: 569.38 g/mol. 1H NMR in CDCl.sub.3 (300 MHz): =7.25 (d, J=2.1 Hz, 1H, CH.sub.arom), 7.23-7.00 (m, 1H, CH.sub.arom), 6.84-6.74 (m, 2H, CH.sub.arom), 6.75-6.67 (m, 1H, CH.sub.arom), 5.78 (s, 1H, CH.sub.arom), 5.74 (s, 1H, CH.sub.arom), 3.50 (s, 3H, NCH.sub.3), 2.32 (s, 3H, CCH.sub.3), 2.31 (s, 3H, CCH.sub.3), 2.28 (s, 3H, CCH.sub.3), 2.25 (s, 3H, CCH.sub.3), 2.25 (s, 3H, CCH.sub.3). .sup.13C NMR in CDCl.sub.3 (75 MHz): =158.7 (C.sub.i), 147.7 (C.sub.i), 147.6 (2 C.sub.i), 145.2 (C.sub.i), 144.8 (C.sub.i), 136.8 (CH.sub.arom), 133.1 (C.sub.i), 125.8 (C.sub.i), 125.0 (CH.sub.arom), 121.0 (CH.sub.arom), 115.0 (CH.sub.arom), 111.2 (CH.sub.arom), 105.5 (CH.sub.arom), 105.0 (CH.sub.arom), 35.8 (NCH.sub.3), 21.4 (CCH.sub.3), 15.3 (CCH.sub.3), 14.6 (CCH.sub.3), 13.0 (CCH.sub.3), 12.9 (CCH.sub.3) .sup.195Pt NMR in CDCl.sub.3 (64 MHz): =3871.3 (s). MS (ESI): m/z=570.5 [M+H].sup.+, 1156.5 [2M+NH.sub.4].sup.+. Elemental analysis: calculated C, 44.30%; H, 4.78%; N, 14.76%; found C, 44.46%; H, 4.66%; N, 14.56%.
[Dihydrobis(3,5-dimethylpyrazol-1-yl-N.SUP.2.)borate][1-(phenyl-C.SUP.2.)-3-(2,4,6-trimethylphenyl)-1H-imidazolin-2-ylidene-C.SUP.2.]platinum(II) (T)
[0130] ##STR00032##
[0131] Synthesis analogous to the general synthesis procedure. 0.280 g (0.8 mmol) 1-phenyl-3-(2,4,6-trimethyphenyl)-1H-imidazolium tetrafluoroborate8 and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=45 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 0.387 g (1.6 mmol, 2 eq) potassium dihydrobis(3,5-dimethylpyrazol-1-yl)borate is added. Eluent mixture: iso-hexane/DCM (3:5). Yield: 84 mg (16%); melting point: 245 C.; molecular formula: C.sub.28H.sub.33BN.sub.6Pt; molar mass: 659.50 g/mol. 1H NMR in CDCl.sub.3 (300 MHz): =7.46 (d, J=2.1 Hz, 1H, CH.sub.arom), 7.42-7.17 (m, 1H, CH.sub.arom), 7.09 (d, J=3.8 Hz, 2H, CH.sub.arom), 7.01-6.86 (m, 1H, CH.sub.arom), 6.85-6.73 (m, 2H, CH.sub.arom), 6.46 (s, 1H, CH.sub.arom), 5.73 (s, 1H, CH.sub.Pz), 5.11 (s, 1H, CH.sub.Pz), 2.27 (s, 3H, CCH.sub.3), 2.24 (s, 6H, CCH.sub.3), 2.22 (s, 3H, CCH.sub.3), 2.19 (s, 3H, CCH.sub.3), 2.19 (s, 3H, CCH.sub.3), 1.67 (s, 3H, CCH.sub.3). .sup.13C NMR in CDCl.sub.3 (75 MHz): =157.7 (C.sub.i), 147.6 (C.sub.i), 147.3 (C.sub.i), 146.9 (C.sub.i), 144.5 (C.sub.i), 144.3 (C.sub.i), 138.7 (C.sub.i), 136.9 (CH.sub.arom), 136.5 (C.sub.i), 134.3 (C.sub.i), 133.3 (C.sub.i), 130.3 (C.sub.i), 129.0 (CH.sub.arom), 128.3 (CH.sub.arom), 124.9 (CH.sub.arom), 123.6 (CH.sub.arom), 122.0 (CH.sub.arom), 114.7 (CH.sub.arom), 110.4 (CH.sub.arom), 105.4 (CH.sub.arom), 103.7 (CH.sub.arom), 20.9 (CCH.sub.3), 19.0 (CCH.sub.3), 18.9 (CCH.sub.3), 15.5 (CCH.sub.3), 15.0 (CCH.sub.3), 13.0 (CCH.sub.3), 12.6 (CCH.sub.3). .sup.195Pt NMR in CDCl.sub.3 (64 MHz): =3859.5 (s). MS (ESI): m/z=660.5 [M+H].sup.+. Elemental analysis: calculated C, 50.99%; H, 5.04%; N, 12.74%; found C, 51.35%; H, 5.21%; N, 12.52%.
[cycloocta-1,5-diylbis(pyrazol-1-yl-N.SUP.2.)borate][1-(phenyl-C.SUP.2.)-3-(2,4,6-trimethylphenyl)-1/imidazolin-2-ylidene-C.SUP.2.]platinum(II) (U)
[0132] ##STR00033##
[0133] Synthesis analogous to the general synthesis procedure. 0.280 g (0.8 mmol) 1-phenyl-3-(2,4,6-trimethyphenyl)-1H-imidazolium tetrafluoroborate8 and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are added to 20 ml DMF (T.sub.1=45 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=115 C.). For the final step of the reaction, 0.516 g (1.6 mmol, 2 eq) potassium cycloocta-1,5-diylbis(4-methylpyrazol-1-yl)borate is added. Eluent mixture: iso-hexane/DCM (5:3). Yield: 245 mg (43%); melting point: 268 C.; molecular formula: C.sub.32H.sub.37BN.sub.6Pt; molar mass: 711.58 g/mol. 1H NMR in CDCl.sub.3 (600 MHz): =7.69 (d, J=2.1 Hz, 1H, CH.sub.arom), 7.68 (d, J=2.4 HZ, 1H, CH.sub.arom), 7.53 (d, J=2.1 HZ, 1H, CH.sub.arom), 7.51-7.41 (m, 2H, CH.sub.arom), 7.18-7.11 (m, 2H, CH.sub.arom), 7.03-6.98 (m, 1H, CH.sub.arom), 6.96 (s, 1H, CH.sub.arom), 6.81 (d, J=2.1 Hz, 1H, CH.sub.arom), 6.65 (d, J=2.0 Hz, 1H, CH.sub.arom), 6.45 (d, J=2.1 Hz, 1H, CH.sub.arom), 6.16 (t, J=2.2 Hz, 1H, CH.sub.arom), 5.54 (t, J=2.2 Hz, 1H, CH.sub.arom), 3.37 (bs, 1H, CH.sub.9-BBN), 2.31 (s, 3H, CCH.sub.3), 2.25 (s, 3H, CCH.sub.3), 2.24-2.13 (m, 2H, CH.sub.2, 9-BBN), 2.08 (s, 3H, CCH.sub.3), 2.02-1.88 (m, 2H, CH.sub.9-BBN), 1.88-1.79 (in, 2H, CH.sub.2, 9-BBN), 1.66-1.56 (m, 2H, CH.sub.2, 9-BBN), 1.53-1.35 (m, 4H, CH.sub.2, 9-BBN), 1.32-1.29 (bs, 1H, CH.sub.9-BBN). .sup.13C NMR in CDCl.sub.3 (151 MHz): =156.6 (C.sub.i), 146.6 (C.sub.i), 141.0 (CH.sub.arom), 141.0 (C.sub.i), 139.5 (C.sub.i), 136.4 (C.sub.i), 135.1 (CH.sub.arom), 134.9 (C.sub.i), 134.3 (CH.sub.arom), 133.6 (CH.sub.arom), 133.0 (CH.sub.arom), 129.8 (C.sub.i), 129.4 (CH.sub.arom), 128.8 (CH.sub.arom), 125.1 (CH.sub.arom), 123.7 (CH.sub.arom), 121.8 (CH.sub.arom), 114.9 (CH.sub.arom), 110.6 (CH.sub.arom), 104.5 (CH.sub.arom), 103.0 (CH.sub.arom), 32.8 (CCH.sub.2), 32.6 (CCH.sub.2), 31.5 (CCH.sub.2), 30.2 (CCH.sub.2), 26.4 (CH), 24.7 (CCH.sub.2), 24.3 (CCH.sub.2), 22.1 (CH), 21.0 (CCH.sub.3), 18.7 (CCH.sub.3), 18.1 (CCH.sub.3). .sup.195Pt NMR in CDCl.sub.3 (64 MHz): =3736.1 (s). MS (ESI): m/z=712.5 [M+H].sup.+. Elemental analysis: calculated C, 54.01%; H, 5.24%; N, 11.81%; found C, 54.39%; H, 5.43%; N, 11.54%.
[Cycloocta-1,5-diylbis(4-methylpyrazol-1-yl-N.SUP.2.)borate][1-(phenyl-C.SUP.2.)-3-(2,4,6-trimethylphenyl)-1H-imidazolin-2-ylidene-C.SUP.2.]platinum(II) (V)
[0134] ##STR00034##
[0135] According to the general synthesis instruction, 280 mg (0.8 mmol) of 1-phenyl-3-(2,4,6-trimethylphenyl)-1H-imidazolium tetrafluoroborate8 and 93 mg (0.4 mmol, 0.5 eq) are added to 20 ml DMF. Following the synthesis procedure, 299 mg (0.8 mmol, 1 eq) of Pt(COD)Cl.sub.2 is added. For the final step of the reaction, 516 mg (1.6 mmol, 2 eq) potassium cycloocta-1,5-diylbis(4-methylpyrazol-1-yl)borate is added. The product is then isolated by column chromatography with the eluent mixture iso-hexane/DCM (1:1). Yield: 326 mg (55%); melting point: 283 C.; molecular formula: C.sub.34H.sub.41BN.sub.6Pt; molar mass: 739.63 g/mol. .sup.1H NMR in CDCl.sub.3 (600 MHz): =7.52 (d, J=2.1 HZ, 1H, CH.sub.arom), 7.51-7.43 (m, 3H, CH.sub.arom), 7.23 (s, 1H, CH.sub.arom), 7.17-7.09 (m, 2H, CH.sub.arom), 7.01 (td, J=7.2, 1.8 Hz, 1H, CH.sub.arom), 6.99 (s, 1H, CH.sub.arom), 6.79 (d, J=2.1 HZ, 1H, CH.sub.arom), 6.68 (s, 1H, CH.sub.arom), 6.20 (s, 1H, CH.sub.arom), 3.27 (bs, 1H, CH.sub.9-BBN), 2.30 (s, 3H, CCH.sub.3), 2.28 (s, 3H, CCH.sub.3), 2.26-2.13 (m, 2H, CH.sub.2, 9-BBN), 2.06 (s, 3H, CCH.sub.3), 2.02 (s, 3H, CCH.sub.3), 1.99-1.85 (m, 2H, C/2, 9-BBN), 1.85-1.74 (m, 2H, CH.sub.2, 9-BBN), 1.68 (s, 3H, CCH.sub.3), 1.63-1.53 (m, 2H, CH.sub.2, 9-BBN), 1.52-1.33 (m, 4H, CH.sub.2, 9-BBN), 1.22 (bs, 1H, CH.sub.9-BBN). .sup.13C NMR in CDCl.sub.3 (151 MHz): =157.0 (C.sub.i), 146.6 (C.sub.i), 141.0 (CH.sub.arom), 140.7 (CH.sub.arom), 139.3 (C.sub.i), 136.6 (C.sub.i), 135.2 (CH.sub.arom), 135.1 (C.sub.i), 134.5 (C.sub.i), 133.1 (CH.sub.arom), 132.3 (CH.sub.arom), 130.3 (C.sub.i), 129.4 (CH.sub.arom), 128.5 (CH.sub.arom), 125.0 (CH.sub.arom), 123.6 (CH.sub.arom), 121.7 (CH.sub.arom), 114.9 (CH.sub.arom), 114.5 (C.sub.i), 112.8 (C.sub.i), 110.5 (CH.sub.arom), 32.8 (CH2), 32.6 (CH.sub.2), 31.5 (CH.sub.2), 30.2 (CH.sub.2), 24.8 (CH.sub.2), 24.4 (CH.sub.2), 21.2 (CCH.sub.3), 18.7 (CCH.sub.3), 18.1 (CCH.sub.3), 9.2 (CCH.sub.3), 8.8 (CCH.sub.3). .sup.195Pt NMR in CDCl.sub.3 (129 MHz): =3726.2 (s). MS (ESI): m/z=740.5 [M+H].sup.+. Elemental analysis: calculated C, 55.21%; H, 5.59%; N, 11.36%; found C, 55.41%; H, 5.60%; N, 11.38%.
[0136] Furthermore, the following compounds W, X and 3 to 12 were generated and measured:
##STR00035## ##STR00036##
[0137] [Dihydrobis(3,5-dimethylpyrazol-1-yl-N.sup.2)borate][4-methyl-1-(5-methylphenyl-C.sup.2-1H-1,2,4-triazol-5-ylidene-C.sup.5]platinum(II) (W): synthesis analogous to the general synthesis procedure. 0.301 g (0.8 mmol) 4-methyl-1-(5-methylphenyl)-1H-1,2,4-triazolium iodide and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are placed in 20 ml DMF (T.sub.1=45 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=125 C.). For the final step of the reaction, 0.387 g (1.6 mmol, 2 eq) potassium dihydrobis(3,5-dimethylpyrazol-1-yl)borate is added. The product is isolated by column chromatography with an eluent mixture matched for polarity. Yield: 112 mg (25%); melting point: 265 C.; molecular formula: C.sub.20H.sub.26BN.sub.7Pt; molar mass: 570.36 g/mol. 1H NMR in CDCl.sub.3 (300 MHz) =7.83 (s, 1H, CH.sub.arom), 7.22-7.08 (M, 2H, CH.sub.arom), 6.88-6.71 (m, 1H, CH.sub.arom), 5.80 (s, 1H, CH.sub.arom), 5.76 (s, 1H, CH.sub.arom), 3.56 (s, 3H, NCH.sub.3), 2.33-2.30 (m, 9H, CCH.sub.3), 2.28 (s, 3H, CCH.sub.3), 2.24 (s, 3H, CCH.sub.3). .sup.13C NMR in CDCl.sub.3 (75 MHz) =161.4 (C.sub.i), 147.8 (C.sub.i), 147.7 (C.sub.i), 146.1 (C.sub.i), 145.5 (C.sub.i), 145.0 (C.sub.i), 141.9 (CH.sub.arom), 136.4 (CH.sub.arom), 133.8 (C.sub.i), 126.2 (CH.sub.arom), 122.5 (C.sub.i), 112.9 (CH.sub.arom), 105.7 (CH.sub.arom), 105.1 (CH.sub.arom), 33.3 (NCH.sub.3), 21.3 (CCH.sub.3), 15.4 (CCH.sub.3), 14.8 (CCH.sub.3), 13.0 (CCH.sub.3), 12.9 (CCH3). .sup.195Pt NMR in CDCl.sub.3 (64 MHz) =3889.8 (s). MS (ESI): m/z=571.5 [M+H].sup.+, 588.4 [M+NH.sub.4].sup.+, 1157.6 [2M+NH.sub.4].sup.+. Elemental analysis: calculated C, 42.12%; H, 4.59%; N, 17.19%; found C, 42.10%; H, 4.86%; 16.84%.
[0138] [Cycloocta-1,5-diylbis(3-methylpyrazol-1-yl-N.sup.2)borate][4-methyl-1-(phenyl-C.sup.2)-1H-1,2,4-triazol-5-ylidene-C.sup.5]platinum(II) (X): synthesis analogous to the general synthesis procedure. 0.230 g (0.8 mmol) 4-methyl-1-phenyl-1H-1,2,4-triazolium iodide and 0.093 g (0.4 mmol, 0.5 eq) silver(I) oxide are placed in 20 ml DMF (T.sub.1=45 C.). Subsequently, 0.299 g (0.8 mmol, 1 eq) Pt(COD)Cl.sub.2 is added (T.sub.2=125 C.). For the final step of the reaction, 0.561 g (1.6 mmol, 2 eq) potassium cycloocta-1,5-diylbis(3-methylpyrazol-1-yl)borate is added. The product is isolated by column chromatography with an eluent mixture matched for polarity. Yield: 151 mg (30%); melting point: 254 C.; molecular formula: C.sub.25H.sub.32BN.sub.7Pt; molar mass: 636.47 g/mol. 1H NMR in CDCl.sub.3 (600 MHz) =7.88 (s, 1H, CH.sub.arom), 7.64 (s, 2H, CH.sub.arom), 7.36 (dd, J=7.7, 1.3 HZ, 1H, CH.sub.arom), 7.33 (dd, J=7.4, 1.3 HZ, 1H, CH.sub.arom), 7.11 (td, J=7.5, 1.3 Hz, 1H, CH.sub.arom), 6.97 (td, J=7.4, 1.4 HZ, 1H, CH.sub.arom), 5.98 (d, J=2.3 Hz, 1H, CH.sub.arom), 5.97 (d, J=2.3 Hz, 1H, CH.sub.arom), 3.76-3.71 (m, 1H, CH.sub.9-BBN), 3.64 (S, 3H, NCH.sub.3), 2.31 (s, 6H, 2 CCH.sub.3), 2.30-2.19 (m, 2H, CH.sub.2, 9-BBN), 2.05-1.84 (m, 4H, CH.sub.2, 9-BBN), 1.70-1.45 (m, 6H, CH.sub.2.9-BBN), 1.37-1.31 (n, 1H, CH.sub.9-BBN). .sup.13C NMR in CDCl.sub.3 (151 MHz) =161.6 (C.sub.i), 148.6 (C.sub.i), 148.3 (C.sub.i), 145.8 (C.sub.i), 142.0 (CH.sub.arom), 136.3 (CH.sub.arom), 135.4 (CH.sub.arom), 135.0 (CH.sub.arom), 127.0 (C.sub.i), 125.5 (CH.sub.arom), 123.8 (CH.sub.arom), 111.9 (CH.sub.arom), 104.8 (CH.sub.arom), 104.5 (CH.sub.arom), 33.4 (NCH.sub.3), 32.6 (CH.sub.2, 9-BBN), 32.4 (CH.sub.2, 9-BBN), 31.5 (CH.sub.2, 9-BBN), 30.4 (CH.sub.2, 9-BBN), 24.7 (CH.sub.2, 9-BBN), 24.6 (CH.sub.2, 9-BBN), 16.2 (CCH.sub.3), 15.6 (CCH.sub.3). .sup.195Pt NMR in CDCl.sub.3 (64 MHz) =3806.20 (s). Elemental analysis: calculated C, 47.18%; H, 5.07%; N, 15.40%; found C, 47.09%; H, 4.99%; N, 15.40%.
[0139] [Dihydrobis(pyrazol-1-yl-N.sup.2)borate][1-methyl-4-(phenyl-C.sup.2)-1H-1,2,4-triazol-5-ylidene-C.sup.5]platinum(II) (3): synthesis analogous to the general synthetic procedure (see Chapter 2,2,1). 230 mg (0.8 mmol, 1 eq.) of 1-methyl-4-phenyl-1H-1,2,4-triazolium iodide and 93 mg (0.4 mmol, 0.5 eq.) of silver(I) oxide are placed in 20 ml DMF. Subsequently, 299 mg (0.8 mmol, 1 eq.) of Pt(COD)Cl.sub.2 is added. For the final step of the reaction, 298 mg (1.6 mmol, 2 eq.) potassium dihydrobis(pyrazol-1-yl)borate (11) is added. The product is isolated by column chromatography with a mixture of eluents adjusted for polarity. Yield: 115 mg (29%); melting point: 179 C.; molecular formula: C.sub.15H.sub.16BN.sub.7Pt; Molar mass: 500.23 g/mol; 1H-NMR (500 MHz, CDCl.sub.3): =8.30 (s, 1H, CH.sub.Triaz), 7.71 (dd, J=15.4, 1.5 Hz, 2H, CH.sub.Pyr), 7.64 (ddd, J=14.9, 2.3, 0.6 Hz, 2H, CH.sub.Pyr), 7.42 (dd, J=7.5, 1.1 Hz, 1H, CH.sub.Ph), 7.15 (dtd, J=9.0, 7.7, 1.4 Hz, 2H, CH.sub.Ph), 7.07 (td, J=7.3, 1.6 Hz, 1H, CH.sub.Ph), 6.26 (dt, J=24.2, 2.2 Hz, 2H, CH.sub.Pyr), 3.83 (s, 3H, NCH) ppm. .sup.13C-NMR (151 MHz, CDCl.sub.3): =159.58 (C.sub.i), 143.96 (C.sub.i, Ph), 141.98 (CH.sub.Pyr), 141.22 (CH.sub.Pyr), 136.36 (CH.sub.Pyr), 136.33 (CH.sub.Pyr), 136.13 (CH.sub.Ph), 135.88 (CH.sub.Ph), 128.73 (C.sub.i,Ph), 125.89 (CH.sub.Ph), 124.31 (CH.sub.Ph), 111.07 (CH.sub.Triaz), 105.26 (CH.sub.Pyr), 105.16 (CH.sub.Pyr), 39.70 (NCH.sub.3) ppm. .sup.195Pt-NMR (129 MHz, CDCl.sub.3): =3787.4 ppm. MS (ESI): m/z=501.1 [M+H].sup.+, 1017.4 [2M+NH.sub.4].sup.+, 1022.3 [2M+Na].sup.+, 1039.2 [2M+K].sup.+. Elemental analysis: calculated: C, 36.02%; H, 3.22%; N, 19.60%; found: C, 35.95%; H, 3.09%; N, 19.51%.
[0140] [Dihydrobis(4-methylpyrazol-1-yl-N.sup.2)borate][1-methyl-4-(phenyl-C.sup.2)-1H-1,2,4-triazol-5-ylidene-C.sup.5]platinum(II) (4): synthesis analogous to the general synthetic procedure (see Chapter 2.2.1). 230 mg (0.8 mmol, 1 eq.) of 1-methyl-4-phenyl-1H-1,2,4-triazolium iodide and 93 mg (0.4 mmol, 0.5 eq.) of silver(I) oxide are placed in 20 ml DMF. Subsequently, 299 mg (0.8 mmol, 1 eq.) of Pt(COD)Cl.sub.2 is added. For the final step of the reaction, 345 mg (1.6 mmol, 2 eq.) potassium dihydrobis(4-methylpyrazol-1-yl)borate is added. The product is isolated by column chromatography with a mixture of eluents matched for polarity. Yield: 113 mg (27%); melting point: 206 C.; molecular formula: C.sub.17H.sub.20BN.sub.7Pt; Molar mass: 528.28 g/mol; 1H-NMR (500 MHz, CDCl.sub.3): =8.28 (s, 1H, CH.sub.Triaz), 7.48 (d, J=12.8 Hz, 2H, CH.sub.Pyr), 7.44 (dd, J=5.9, 4.8 Hz, 1H, CH.sub.Ph), 7.41 (d, J=13.1 Hz, 2H, CH.sub.Pyr), 7.17-7.10 (m, 2H, CH.sub.Ph), 7.10-7.04 (m, 1H, CH.sub.Ph), 3.84 (s, 3H, NCH.sub.3), 2.10 (s, 3H, CCH.sub.3), 2.04 (s, 3H, CCH.sub.3) ppm. .sup.13C-NMR (151 MHz, CDCl.sub.3): =159.88 (C.sub.i), 143.99 (CH.sub.Ph), 141.65 (CH.sub.Pyr), 140.80 (CH.sub.Pyr), 136.31 (CH.sub.Ph), 135.96 (CH.sub.Ph), 135.70 (CH.sub.Pyr), 135.51 (CH.sub.Pyr), 129.07 (C.sub.i,Ph), 125.83 (CH.sub.Ph), 124.16 (CH.sub.Ph), 115.48 (C.sub.i,Pyr), 115.33 (C.sub.i,pyr), 111.00 (CH.sub.triaz), 39.70 (NCH.sub.3), 8.98 (CCH.sub.3), 8.91 (CCH.sub.3) ppm. .sup.195Pt-NMR (129 MHz, CDCl.sub.3): =3778.6 ppm. MS (ESI): m/z=529.3 [M+H].sup.+, 1074.3 [2M+NH.sub.4].sup.+, 1079.3 [2M+Na].sup.+, 1095.3 [2M+K].sup.+. Elemental analysis: calculated: C, 38.65%; H, 3.82%; N, 18.56%; found: C, 38.67%; H, 3.75%; N, 18.51%. [Dihydrobis(3,5-dimethylpyrazol-1-yl-N.sup.2)borate][1-methyl-4-(phenyl-C.sup.2)-1H-1,2,4-triazol-5-ylidene-C.sup.5]platinum(II) (5): synthesis analogous to the general synthetic procedure. 230 mg (0.8 mmol, 1 eq.) of 1-methyl-4-phenyl-1H-1,2,4-triazolium iodide and 93 mg (0.4 mmol, 0.5 eq.) of silver(I) oxide are placed in 20 ml DMF. Subsequently, 299 mg (0.8 mmol, 1 eq.) of Pt(COD)Cl.sub.2 is added. For the final step of the reaction, 391 mg (1.6 mmol, 2 eq.) potassium dihydrobis(3,5-dimethylpyrazol-1-yl)borate is added. The product is isolated by column chromatography with an eluent mixture matched for polarity. Yield: 145 mg (33%); melting point: 239 C.; molecular formula: C.sub.19H.sub.24BN.sub.7Pt; Molar mass: 556.34 g/mol; .sup.1H-NMR (300 MHz, CDCl.sub.3): =8.27 (s, 1H, CH.sub.Triaz), 7.30 (dd, J=7.5, 1.0 Hz, 1H, CH.sub.Ph), 7.10 (dtd, J=9.0, 7.7, 1.4 Hz, 2H, CH.sub.Ph), 6.97 (td, J=7.2, 1.7 Hz, 1H, CH.sub.Ph), 5.85-5.74 (m, 2H, CH.sub.Pyr), 3.73 (s, 3H, NCH.sub.3), 2.32 (d, J=2.0 Hz, 6H, CCH.sub.3), 2.26 (d, J=2.7 Hz, 6H, CCH.sub.3) ppm. .sup.13C-NMR (151 MHz, CDCl.sub.3): =160.19 (C.sub.i), 147.62 (CH.sub.Pyr), 147.55 (CH.sub.Pyr), 145.40 (CH.sub.Pyr), 145.00 (CH.sub.Pyr), 143.97 (CH.sub.Ph), 137.63 (CH.sub.Ph), 136.45 (CH.sub.Ph), 129.52 (CH.sub.Ph), 125.56 (CH.sub.Ph), 123.83 (CH.sub.Ph), 110.69 (CH.sub.Triaz), 105.69 (CH.sub.Pyr), 105.19 (CH.sub.Pyr), 38.08 (NCH.sub.3), 15.12 (CCH.sub.3), 14.43 (CCH.sub.3), 12.82 (CCH.sub.3), 12.76 (CCH.sub.3) ppm. .sup.195Pt-NMR (129 MHz, CDCl.sub.3): =3804.8 ppm. MS (ESI): m/z=557.4 [M+H].sup.+, 1129.6 [2M+NH.sub.4].sup.+, 1134.4 [2M+Na].sup.+, 1152.3 [2M+K].sup.+. Elemental analysis: calculated: C, 41.02%; H, 4.35%; N, 17.62%; found: C, 41.03%; H, 4.37%; N, 17.69%.
[0141] [Cycloocta-1,5-diylbis(pyrazol-1-yl-N.sup.2)borate][1-methyl-4-(phenyl-C.sup.2)-1H-1,2,4-triazol-5-ylidene-C.sup.5]platinum(II) (6): synthesis analogous to the general synthetic procedure. 230 mg (0.8 mmol, 1 eq.) of 1-methyl-4-phenyl-1H-1,2,4-triazolium iodide and 93 mg (0.4 mmol, 0.5 eq.) of silver(I) oxide are placed in 20 ml DMF. Subsequently, 299 mg (0.8 mmol, 1 eq.) of Pt(COD)Cl.sub.2 is added. For the final step of the reaction, 471 mg (1.6 mmol, 2 eq.) potassium cycloocta-1,5-diylbis(pyrazol-1-yl)borate is added. The product is isolated by column chromatography with an eluent mixture matched for polarity. Yield: 97 mg (20%); melting point: 294 C.; molecular formula: C.sub.23H.sub.28BN.sub.7Pt; Molar mass: 608.41 g/mol; 1H-NMR (300 MHz, CDCl.sub.3): =8.31 (s, 1H, CH.sub.Triaz), 7.81-7.75 (m, 2H, CH.sub.Pyr), 7.71 (t, J=2.1 Hz, 2H, CH.sub.Pyr), 7.50 (d, J=7.2 Hz, 1H, CH.sub.Ph), 7.20-7.02 (m, 3H, CH.sub.Ph), 6.22 (dt, J=9.3, 2.0 Hz, 2H, CH.sub.Pyr), 3.90 (s, 3H, NCH.sub.3), 3.55 (s, 1H, CH.sub.9-BBN), 2.35-2.18 (m, 2H, CH.sub.9-BBN), 2.08 1.85 (m, 4H, CH.sub.9-BBN), 1.78-1.59 (m, 2H, CH.sub.9-BBN), 1.57-1.39 (m, 5H, CH.sub.2, 9-BBN& CH.sub.9-BBN) ppm. .sup.13C-NMR (151 MHz, CDCl.sub.3): =160.12 (C.sub.i), 143.78 (CH.sub.Ph), 141.43 (CH.sub.Pyr), 141.10 (CH.sub.Pyr), 136.40 (CH.sub.Ph), 135.43 (CH.sub.Ph), 134.34 (CH.sub.Pyr), 134.15 (CH.sub.Pyr), 129.19 (CH.sub.Ph), 125.92 (CH.sub.Ph), 124.04 (CH.sub.Ph), 111.15 (CH.sub.Triaz), 105.03 (CH.sub.Pyr), 104.69 (CH.sub.Pyr), 39.41 (NCH.sub.3), 32.43 (CH.sub.2-9BBN), 32.24 (CH.sub.2-9BBN), 31.07 (CH.sub.2-9BBN), 30.24 (CH.sub.2-9BBN), 24.51 (s), 24.46 (CH.sub.2-9BBN) ppm. .sup.195Pt-NMR (129 MHz, CDCl.sub.3): =3692.1 ppm.
[0142] MS (ESI): m/z=609.3 [M+H].sup.+, 631.3 [M+Na].sup.+, 1239.4 [2M+Na].sup.+. Elemental analysis: calculated: C, 45.41%; H, 4.64%; N, 16.12%; found: C, 45.05%; H, 4.58%; N, 15.83%.
[0143] [Cycloocta-1,5-diylbis(4-methylpyrazol-1-yl-N.sup.2)borate]-[1-methyl-4-(phenyl-C.sup.2)-1H-1,2-triazol-5-ylidene-C.sup.5]platinum(II) (7): synthesis analogous to the general synthetic procedure. 230 mg (0.8 mmol, 1 eq.) of 1-methyl-4-phenyl-1H-1,2,4-triazolium iodide and 93 mg (0.4 mmol, 0.5 eq.) of silver(I) oxide are placed in 20 ml DMF. Subsequently, 299 mg (0.8 mmol, 1 eq.) of Pt(COD)Cl.sub.2 is added. For the final step of the reaction, 516 mg (1.6 mmol, 2 eq.) potassium cycloocta-1,5-diylbis(4-methylpyrazol-1-yl)borate is added. The product is isolated by column chromatography with an eluent mixture matched for polarity. Yield: 111 mg (22%); melting point: 302 C.; molecular formula: C.sub.25H.sub.32BN.sub.7Pt; Molar mass: 636.47 g/mol; 1H-NMR (500 MHz, CDCl.sub.3): =8.28 (s, 1H, CH.sub.Triaz), 7.54 (d, J=4.1 Hz, 2H, CH.sub.Pyr), 7.52 (dd, J=7.5, 1.1 Hz, 1H, CH.sub.Ph), 7.47 (d, J=3.1 Hz, 2H, CH.sub.Pyr), 7.14 (dtd, J=9.0, 7.7, 1.4 Hz, 2H, CH.sub.Ph), 7.07 (td, J=7.3, 1.7 Hz, 1H, CH.sub.Ph), 3.91 (s, 3H, NCH.sub.3), 3.47 (s, 1H, CH.sub.9-BBN), 2.29-2.19 (m, 2H, CH.sub.2, 9-BBN), 2.07 (s, 3H, CCH.sub.3), 2.03 (s, 3H, CCH.sub.3), 2.01-1.83 (m, 4H, CH.sub.2, 9-BBN), 1.73-1.57 (m, 2H, CH.sub.2, 9-BBN), 1.53-1.41 (m, 4H, CH.sub.2, 9-BBN), 1.36 (d, J=1.5 Hz, 1H, CH.sub.9-BBN) ppm. .sup.13C-NMR (151 MHz, CDCl.sub.3): =160.44 (C.sub.i), 143.81 (C.sub.i,Ph), 141.09 (CH.sub.Pyr), 140.70 (CH.sub.Pyr), 136.36 (CH.sub.Ph), 135.50 (CH.sub.Ph), 133.73 (CH.sub.Pyr), 133.54 (CH.sub.Pyr), 129.58 (C.sub.i,Ph), 125.82 (CH.sub.Ph), 123.86 (CH.sub.Ph), 115.09 (C.sub.i,Pyr), 114.70 (C.sub.i,Pyr), 111.07 (CH.sub.Triaz), 39.44 (NCH.sub.3), 32.45 (CH.sub.2-9BBN), 32.26 (CH.sub.2-9 BBN), 31.09 (CH.sub.2-9 BBN), 30.28 (CH.sub.2-9 BBN), 24.60 (CH.sub.2- 9 BBN), 24.55 (CH.sub.2-9BBN), 9.12 (CCH.sub.3), 9.08 (CCH.sub.3) ppm. .sup.195Pt-NMR (129 MHz, CDCl.sub.3): =3683.6 ppm. MS (ESI): m/z=637.4 [M+H].sup.+, 1290.5 [2M+NH.sub.4].sup.+. Elemental analysis: calculated: C, 47.18%; H, 5.07%; N, 15.40%; found: C, 46.90%; H, 4.86%; N, 15.12%.
[0144] [Cycloocta-1,5-diylbis(3-methylpyrazol-1-yl-N.sup.2)borate]-[1-methyl-4-(phenyl-C.sup.2)-1H-1,2,4-triazol-5-ylidene-C.sup.5]platinum(II) (8): synthesis analogous to the general synthetic procedure (see Chapter 2,2,1). 230 mg (0.8 mmol, 1 eq.) of 1-methyl-4-phenyl-1H-1,2,4-triazolium iodide and 93 mg (0.4 mmol, 0.5 eq.) of silver(I) oxide are placed in 20 ml DMF. Subsequently, 299 mg (0.8 mmol, 1 eq.) of Pt(COD)Cl.sub.2 is added. For the final step of the reaction, 516 mg (1.6 mmol, 2 eq.) potassium cycloocta-1,5-diylbis(3-methylpyrazol-1-yl)borate is added. The product is isolated by column chromatography with an eluent mixture matched for polarity. Yield: 159 mg (31%); melting point: 275 C.; molecular formula: C.sub.25H.sub.32BN.sub.7Pt; Molar mass: 636.47 g/mol; 1H-NMR (300 MHz, CDCl.sub.3): =8.29 (s, 1H, CH.sub.Triaz), 7.64 (t, J=2.1 Hz, 2H, CH.sub.Pyr), 7.34 (dd, J=7.5, 1.0 Hz, 1H, CH.sub.Ph), 7.12 (dtd, J=9.0, 7.7, 1.4 Hz, 2H, CH.sub.Ph), 6.97 (td, J=7.3, 1.6 Hz, 1H, CH.sub.Ph), 5.98 (t, J=2.0 Hz, 2H, CH.sub.Pyr), 3.79 (s, 3H, NCH.sub.3), 3.75 (d, J=2.3 Hz, 1H, CH.sub.9-BBN), 2.32 (s, 3H, CCH.sub.3), 2.28 (s, 3H, CCH.sub.3), 2.25-2.17 (m, 2H, CH.sub.2, 9-BBN), 2.03-1.81 (m, 4H, CH.sub.2, 9-BBN), 1.72-1.44 (m, 6H, CH.sub.2, 9-BBN), 1.34 (d, J=1.5 Hz, 1H, CH.sub.9-BBN) ppm. .sup.13C-NMR (151 MHz, CDCl.sub.3): =160.42 (C.sub.i), 148.41 (CH.sub.Pyr), 148.27 (C.sub.i,Pyr), 143.76 (C.sub.i,Ph), 137.31 (CH.sub.Ph), 136.58 (CH.sub.Ph), 135.29 (CH.sub.Pyr), 134.94 (CH.sub.Pyr), 129.68 (C.sub.i,Ph), 125.53 (CH.sub.Ph), 123.67 (CH.sub.Ph), 110.79 (CH.sub.Triaz), 104.76 (CH.sub.Pyr), 104.49 (CH.sub.Pyr), 37.96 (NCH.sub.3), 32.51 (CH.sub.2.9BBN), 32.32 (CH.sub.2.9 BBN), 31.32 (CH.sub.2.9BBN), 30.32 (CH.sub.2.9BBN), 24.55 (CH.sub.2.9BBN), 24.47 (CH.sub.2.9BBN), 15.96 (CCH.sub.3), 15.23 (CCH.sub.3) ppm. .sup.195Pt-NMR (129 MHz, CDCl.sub.3): =3733.7 ppm. MS (ESI): m/z=637.3 [M+H].sup.+, 659.4 [M+Na].sup.+, 1295.4 [2M+Na].sup.+. MS (ESI): m/z=637.3 [M+H].sup.+, 659.4 [M+Na].sup.+, 1295.4 [2M+Na].sup.+. Elemental analysis: calculated: C, 47.18%; H, 5.07%; N, 15.40%; found: C, 47.04%; H, 4.92%; N, 15.31%.
[0145] [Cycloocta-1,5-diylbis(4-methylpyrazol-1-yl-N.sup.2)borate]-[1-methyl-4-(3-methylphenyl-C.sup.2)-1H-1,2,4-triazol-5-ylidene-C.sup.5]platinum(II) (9): synthesis analogous to the general synthetic procedure. 243 mg (0.8 mmol, 1 eq.) of 1-methyl-4-(3-methylphenyl)-1H-1,2,4-triazolium iodide and 93 mg (0.4 mmol, 0.5 eq.) of silver(I) oxide are placed in 20 ml DMF. Subsequently, 302 mg (0.8 mmol, 1 eq.) of Pt(COD)Cl.sub.2 is added. For the final step of the reaction, 437 mg (1.36 mmol, 1.7 eq.) potassium cycloocta-1,5-diylbis(4-methylpyrazol-1-yl)borate is added. The product is then isolated by column chromatography with an eluent mixture matched for polarity. Yield: 76 mg (15%); melting point: 293 C.; molecular formula: C.sub.26H.sub.34BN.sub.7Pt; molar mass: 650.49 g/mol. 1H-NMR (600 MHz, CDCl.sub.3): =8.27 (s, 1H, CH.sub.Triaz), 7.54 (d, J=6.1 Hz, 2H, CH.sub.Pyr), 7.47 (s, 2H, CH.sub.Pyr), 7.38 (d, J=7.7 Hz, 1H, CH.sub.Ph), 6.99 (s, 1H, CH.sub.Ph), 6.92-6.88 (m, 1H, CH.sub.Ph), 3.90 (s, 3H, NCH.sub.3), 3.46 (s, 1H, CH.sub.9-BBN), 2.34 (s, 3H, CCH.sub.3,Ph), 2.28-2.19 (m, 2H, CH.sub.2, 9-BBN), 2.07 (s, 3H, CCH.sub.3,Pyr), 2.03 (s, 3H, CCH.sub.3,Pyr), 2.00 1.83 (m, 4H, CH.sub.2, 9-BBN), 1.73-1.57 (m, 2H, CH.sub.2.9-BBN), 1.53-1.40 (m, 4H, CH.sub.2, 9-BBN), 1.35 (s, 1H, CH.sub.9-BBN) ppm. .sup.195Pt-NMR (129 MHz, CDCl.sub.3): =3688.3 ppm. MS (ESI): m/z=649.0 [MH].sup.+, 651.5 [M+H].sup.+, 673.4 [M+Na].sup.+, 690.4 [M+K].sup.+, 1317.6 [2M+NH.sub.4].sup.+, 1323.4 [2M+Na].sup.+. Elemental analysis: calculated C, 48.01%; H, 5.27%; N, 15.07%; found C, 48.03%; H, 5.50%; N, 14.76%.
[0146] [Cycloocta-1,5-diylbis(3-methylpyrazol-1-yl-N.sup.2)borate]-[1-methyl-4-(3-methylphenyl-C.sup.2)-1/+1,2,4-triazol-5-ylidene-C.sup.5]platinum(II) (10): synthesis analogous to the general synthesis procedure II with slight modification of the purification. 243 mg (0.8 mmol, 1 eq.) of 1-methyl-4-(3-methylphenyl)-1H-1,2,4-triazolium iodide and 93 mg (0.4 mmol, 0.5 eq.) of silver(I) oxide are placed in 20 ml DMF. Subsequently, 300 mg (0.8 mmol, 1 eq.) of Pt(COD)Cl.sub.2 is added. For the final step of the reaction, 517 mg (1.6 mmol, 2 eq.) potassium cycloocta-1,5-diylbis(3-methylpyrazol-1-yl)borate is added. The product is then isolated by column chromatography with an eluent mixture matched for polarity. Yield: 125 mg (24%); melting point: 289 C.; molecular formula: C.sub.26H.sub.34BN.sub.7Pt; molar mass: 650.49 g/mol. .sup.1H-NMR (600 MHz, CDCl.sub.3): =8.27 (s, 1H, CH.sub.Triaz), 7.66-7.62 (m, 2H, CH.sub.Pyr), 7.21 (d, J=7.6 Hz, 1H, CH.sub.Ph), 6.98 (s, 1H, C/A-h), 6.81 (d, J=7.6 Hz, 1H, CH.sub.Ph), 5.97 (dd, J=4.0, 2.2 Hz, 2H, CH.sub.Pyr), 3.78 (s, 3H, NCH.sub.3), 3.75 (s, 1H, CH.sub.9-BBN), 2.32 (S, 3H, CCH.sub.3,Pyr), 2.31 (s, 3H, CCH.sub.3,Pyr), 2.28 (s, 3H, CCH.sub.3,Ph), 2.27-2.20 (m, 2H, CH.sub.2, 9-BBN), 2.01-1.83 (m, 4H, CH.sub.2, 9-BBN), 1.69 1.46 (m, 6H, CH.sub.2, 9-BBN), 1.33 (d, J=1.8 Hz, 1H, CH.sub.9-BBN) ppm. .sup.195Pt-NMR (129 MHz, CDCl.sub.3): =3739.2 ppm. MS (ESI): m/z=649.0 [MH].sup.+, 651.4 [M+H].sup.+, 673.4 [M+Na].sup.+, 689.4 [M+K].sup.+, 1322.5 [2M+Na].sup.+; elemental analysis: calculated C, 48.01%; H, 5.27%; N, 15.07%; found: C, 47.74%; H, 5.46%; N, 14.87%.
[0147] [Cycloocta-1,5-diylbis(4-methylpyrazol-1-yl-N.sup.2)borate]-[3-methyl-1-(3-methylphenyl-C.sup.2)-1H-imidazolin-2-ylidene-C.sup.2]platinum(II) (11): synthesis analogous to general synthesis procedure II. 240 mg (0.8 mmol, 1 eq.) of 3-methyl-1-phenyl-1H-imidazolium iodide and 94 mg (0.4 mmol, 0.5 eq.) of silver(I) oxide are placed in 20 ml DMF. Subsequently, 299 mg (0.8 mmol, 1 eq.) of Pt(COD)Cl.sub.2 is added. For the final step of the reaction, 516 mg (1.6 mmol, 2 eq.) potassium cycloocta-1,5-diylbis(4-methylpyrazol-1-yl)borate is added. The product is then isolated by column chromatography with a mixture of eluents matched for polarity.
[0148] Yield: 132 mg (25%); melting point: 291 C.; molecular formula: C.sub.27H.sub.35BN.sub.6Pt; molar mass: 649.51 g/mol. 1H-NMR (600 MHz, CDCl.sub.3): =7.52 (s, 2H, CH.sub.Im), 7.49 (d, J=6.1 Hz, 2H, CH.sub.Pyr), 7.34 (d, J=7.6 Hz, 1H, CH.sub.Pyr), 7.28 (d, J=2.0 Hz, 1H, CH.sub.Pyr), 6.84 (s, 1H, CH.sub.Ph), 6.83-6.80 (m, 2H, CH.sub.Ph), 3.71 (s, 3H, NCH.sub.3), 3.58 (s, 1H, CH.sub.9-BBN), 2.32 (S, 3H, CCH.sub.3,Ph), 2.30-2.20 (m, 2H, CH.sub.2, 9-BBN), 2.06 (s, 3H, CCH.sub.3,Pyr), 2.01 (s, 3H, CCH.sub.3,Pyr), 2.00-1.83 (m, 4H, CH.sub.2, 9-BBN), 1.73-1.59 (m, 2H, CH.sub.2, 9-BBN), 1.54-1.44 (m, 4H, CH.sub.2, 9-BBN), 1.35 (s, 1H, CH.sub.9-BBN) ppm. .sup.13C-NMR (151 MHz, CDCl.sub.3): =158.95 (C.sub.i), 147.35 (C.sub.i,Ph), 141.17 (CH.sub.Pyr), 140.66 (CH.sub.Pyr), 134.52 (CH.sub.Ph), 133.43 (CH.sub.Pyr), 133.20 (CH.sub.Pyr), 133.14 (C.sub.i,Ph), 125.76 (C.sub.i,Ph), 125.15 (CH.sub.Ph), 121.01 (CH.sub.Ph), 114.85 (CH.sub.Im), 114.75 (C.sub.i,Pyr), 114.35 (C.sub.i,Pyr), 111.53 (CH.sub.Im), 37.29 (NCH.sub.3), 32.55 (CH.sub.2-9 BBN), 32.32 (CH.sub.2-9 BBN), 31.21 (CH.sub.2-9 BBN), 30.35 (CH.sub.2-9 BBN), 24.68 (CH.sub.2-9 BBN), 24.60 (CH.sub.2-9 BBN), 21.19 (CCH.sub.3,Ph), 9.13 (CCH.sub.3,Pyr), 9.09 (CCH.sub.3,Pyr) ppm. .sup.195Pt-NMR (129 MHz, CDCl.sub.3): =3724.6 ppm. MS (ESI): m/z=650.4 [M+H].sup.+, 672.4 [M+Na].sup.+, 1298.5 [2M+H].sup.+, 1316.4 [2M+NH.sub.4].sup.+. Elemental analysis: calculated C, 49.93%; H, 5.43%; N, 12.94%; C, 50.05%; H, 5.62%; N, 12.61%.
[0149] [Cycloocta-1,5-diylbis(3-methylpyrazol-1-yl-N.sup.2)borate]-[3-methyl-1-(3-methylphenyl-C.sup.2)-1H-imidazolin-2-ylidene-C.sup.2]platinum(II) (12): synthesis analogous to the general synthetic procedure (see Chapter 1). 240 mg (0.8 mmol, 1 eq.) of 3-methyl-1-phenyl-1H-imidazolium iodide and 94 mg (0.4 mmol, 0.5 eq.) of silver(I) oxide are placed in 20 ml DMF. Subsequently, 299 mg (0.8 mmol, 1 eq.) of Pt(COD)Cl.sub.2 is added. For the final step of the reaction, 516 mg (1.6 mmol, 2 eq.) potassium cycloocta-1,5-diylbis(3-methylpyrazol-1-yl)borate is added. The product is isolated by column chromatography with an eluent mixture matched to polarity. After washing and drying, a white, slightly yellowish solid is obtained. Yield: 142 mg (27%); melting point: 260 C.; molecular formula: C.sub.27H.sub.35BN.sub.6Pt; molar mass: 649.51 g/mol. 1H-NMR (600 MHz, CDCl.sub.3): =7.63 (dd, J=8.9, 2.2 Hz, 2H, CH.sub.Im), 7.29 (d, J=2.1 Hz, 1H, C.sub.i,Pyr), 7.23-7.10 (m, 1H, C.sub.i,Pyr), 6.89-6.76 (m, 2H, CH.sub.Ph), 6.72 (dd, J=7.5, 0.7 Hz, 1H, CH.sub.Ph), 5.95 (dd, J=9.0, 2.1 Hz, 2H, C.sub.i,Pyr), 3.89 (s, 1H, CH.sub.9-BBN), 3.58 (s, 3H, NCH.sub.3), 2.32 (s, J=5.4 Hz, 3H, CCH.sub.3,Ph), 2.30 (s, J=5.2 Hz, 3H, CCH.sub.3,Pyr), 2.29 (s, 3H, CCH.sub.3,Pyr), 2.28-2.17 (m, 2H, CH.sub.2,9-BBN), 2.03-1.83 (n, 4H, CH.sub.2,9-BBN), 1.70-1.46 (n, 6H, CH.sub.2, 9-BBN), 1.33 (s, 1H, CH.sub.9-BBN) ppm. .sup.13C-NMR (151 MHz, CDCl.sub.3): =158.96 (C.sub.i), 148.40 (C.sub.i,Pyr), 148.22 (C.sub.i,Pyr), 147.20 (C.sub.i,Ph), 136.38 (CH.sub.Ph), 134.99 (CH.sub.Pyr), 134.63 (CH.sub.Pyr), 132.88 (C.sub.i,Ph), 125.84 (C.sub.i,Ph), 124.89 (CH.sub.Ph), 120.81 (CH.sub.Ph), 114.98 (CH.sub.Im), 111.27 (CH.sub.Im), 104.49 (CH.sub.Pyr), 104.20 (CH.sub.Pyr), 35.65 (NCH.sub.3), 32.61 (CH.sub.2-9 BBN), 32.38 (CH.sub.2-9 BBN), 31.43 (CH.sub.2-9 BBN), 30.38 (CH.sub.2-9 BBN), 24.64 (CH.sub.2-9 BBN), 24.53 (CH.sub.2-9 BBN), 21.24 (CCH.sub.3,Ph), 16.01 (CCH.sub.3,Pyr), 15.29 (CCH.sub.3,Pyr) ppm. .sup.195Pt-NMR (129 MHz, CDCl.sub.3): =3783.7 ppm. MS (ESI): m/z=650.4 [M+H].sup.+, 672.4 [M+Na].sup.+, 688.4, [M+K].sup.+, 1321.5 [2M+Na].sup.+. Elemental analysis: calculated C, 49.93%; H, 5.43%; N, 12.94%; found C, 49.63%; H, 5.34%; N, 12.86%.
[0150] Photophysical Characterization and Structures
[0151] Emission spectra for compounds A to V are shown in
[0152]
TABLE-US-00003 TABLE 2 Photoluminescence data of complexes A to X and 3 to 12, measured at room temperature in PMMA films each containing 2 wt. % of the respective complex, and melting or decomposition temperatures of complexes A-X and 3 to 12: Complex .sub.exc PLQY .sub.em CIE x CIE y T.sub.v T.sub.0 mp ( C.) A 370 84 469 0.173 0.378 15.4 18.3 239 B 370 92 470 0.175 0.383 16.1 17.4 279 C 330 58 468 0.159 0.198 6.2 10.7 258 D 330 78 472 0.160 0.214 6.3 8.1 269 E 310 42 463 0.161 0.180 8.0 19.1 231 F 310 70 461 0.159 0.175 9.1 13.1 241 G 310 61 462 0.160 0.176 8.2 13.4 248 H 310 69 458 0.159 0.163 8.7 12.7 301 I 310 80 458 0.158 0.156 8.7 10.9 241 J 310 60 471 0.164 0.214 9.4 15.6 270 K 330 44 466 0.155 0.165 4.9 11.1 244 L 330 71 465 0.155 0.172 4.9 6.9 257 M 330 80 461 0.154 0.146 5.1 6.4 >310 N 340 79 484 0.198 0.348 10.9 13.8 219 0 340 79 484 0.197 0.349 10.5 13.3 264 P 340 80 470 0.167 0.231 8.8 10.9 286 Q 340 79 470 0.166 0.231 7.8 9.8 235 R 320 59 449 0.154 0.112 7.7 13.0 243 S 320 76 461 0.155 0.156 9.1 11.9 227 T 320 77 452 0.154 0.118 8.4 10.9 245 U 320 87 449 0.154 0.109 8.5 9.8 268 V 320 91 449 0.154 0.107 8.3 9.1 283 W 310 69 476 0.170 0.253 9.6 14.1 265 X 310 79 457 0.159 0.160 9.6 12.2 254 3 310 13 434 0.160 0.081 81.0 642.9 179 4 310 31 434 0.159 0.078 7.0 22.2 206 5 310 33 435 0.155 0.069 5.8 17.8 239 6 310 46 431 0.158 0.071 4.6 10.0 294 7 310 62 430 0.157 0.066 8.3 13.4 302 8 310 76 431 0.156 0.067 7.7 10.2 275 9 310 82 445 0.156 0.096 9.2 11.3 293 10 310 93 443 0.155 0.095 9.9 10.6 289 11 310 86 458 0.156 0.138 37.9 44.3 291 12 310 92 457 0.156 0.141 10.4 11.3 260 .sub.exc = excitation wavelength; PLQY = photoluminescence quantum yield .sub.em = emission wavelength of highest intensity at room temperature, CIE x, CIE y = CIE coordinates at room temperature, T.sub.v = measured phosphorescence lifetime T.sub.0 = phosphorescence lifetime given as T.sub.0 = 100 T.sub.v/PLQY mp = melting or decomposition point
[0153] The compounds A to X and 3 to 12 according to the invention exhibit clear luminescence in the blue region of the visible spectrum with emission wavelength em highest intensity at room temperature starting at 430 nm (compound 7) through about 450 (compounds U, V: 449 nm each) and well below 500 nm (compounds N, O: 484 nm each) and thus in the blue region of the spectrum. The melting or decomposition temperatures are almost all located well above 200 C., with peak values above 300 C. with simultaneous highest intensity of the emission wavelength around about 460 nm, thus clearly in the blue region of the spectrum (compounds H, M) or 430 nm (compound 7). At the same time, the complexes according to the invention exhibit comparatively low CIE x and CIE y values. Thus, the CIE x values of the measured compounds are <0.2, in many cases <0.16 (preferred). Further photophysical characteristics of compounds A to V, W, X and 3 to 12 can be taken from Table 2.
[0154]