Organometallic compounds for the manufacture of a semiconductor element or electronic memory
11643425 · 2023-05-09
Assignee
Inventors
- Nicholas Rau (Marburg, DE)
- Jörg Sundermeyer (Marburg, DE)
- Henrik Schumann (Weinbach, DE)
- Andreas Rivas Nass (Bensheim, DE)
- Annika Frey (Hanau, DE)
- Wolf Schorn (Waldbronn, DE)
- Eileen Woerner (Nidderau, DE)
- Ralf Karch (Kleinostheim, DE)
- Angelino Doppiu (Seligenstadt, DE)
Cpc classification
International classification
C07F15/00
CHEMISTRY; METALLURGY
C23C16/455
CHEMISTRY; METALLURGY
Abstract
The invention relates to compounds in accordance with the general formula [Ru(arene)(R.sup.a—N═CR.sup.1—CR.sup.3═N—R.sup.b)] or [Ru(arene)((R.sup.c,R.sup.d)N—N═CR.sup.H1—CR.sup.H3═N—N(R.sup.e,R.sup.f))]. In this case, arene is selected from the group consisting of mononuclear and polynuclear arenes and heteroarenes. R.sup.1, R.sup.3, RH.sup.1, R.sup.H3 and R.sup.a-R.sup.f are independently selected from the group consisting of H, an alkyl radical (C1-C10) and an aryl radical. It further relates to methods for the production of these compounds, compounds obtainable according to these methods, their use and a substrate having on a surface thereof a ruthenium layer or a layer containing ruthenium. In addition, the invention relates to a method for producing compounds [Ru(arene)X.sub.2]2, wherein arene is selected from the group consisting of mononuclear and polynuclear arenes and X=halogen, compounds of this type obtainable according to this method, and their use. The aforementioned ruthenium(O) compounds can be produced in a simple, cost-effective and reproducible manner with a high degree of purity and good yield. Due to their high degree of purity, they are suitable for use as ruthenium(O) precursors.
Claims
1. Compounds in accordance with the general formula
[Ru(arene)((R.sup.c,R.sup.d)N—N═CR.sup.H1—CR.sup.H3═N—N(R.sup.e,R.sup.f))] (B) wherein i) arene is selected from the group consisting of mononuclear and polynuclear arenes and mononuclear and polynuclear heteroarenes and ii) R.sup.H1, R.sup.H3, R.sup.c, R.sup.d, R.sup.e and R.sup.f are independently selected from the group consisting of H, an alkyl radical (C1-C10) and an aryl radical.
2. Compounds in accordance with the general formula B according to claim 1, wherein R.sup.H1, R.sup.H3 are independently selected from the group consisting of H, an alkyl radical (C1-C10) and an aryl radical and R.sup.c═R.sup.e═H, alkyl radical (C1-C10) or aryl radical and R.sup.d═R.sup.f═H, alkyl radical (C1-C10) or aryl radical.
3. Compounds in accordance with the general formula B according to claim 1, wherein R.sup.H1, R.sup.H3 are independently selected from the group consisting of H, an alkyl radical (C1-C10) and an aryl radical and R.sup.c═R.sup.d═R.sup.e═R.sup.f═H, alkyl radical (C1-C10) or aryl radical.
4. Compounds in accordance with the general formula B according to claim 1, wherein R.sup.H1═R.sup.H3═H, alkyl radical (C1-C10) or aryl radical and R.sup.c═R.sup.e═H, alkyl radical (C1-C10) or aryl radical and R.sup.d═R.sup.f═H, alkyl radical (C1-C10) or aryl radical.
5. Compounds in accordance with the general formula B according to claim 1, wherein R.sup.H1═R.sup.H3═H, alkyl radical (C1-C10) or aryl radical and R.sup.c═R.sup.d═R.sup.e═R.sup.f═H, alkyl radical (C.sub.1-C10) or aryl radical.
6. Method for producing a compound in accordance with the general formula
[Ru(arene)((R.sup.c,R.sup.d)N—N═CR.sup.H1—CR.sup.H3═N—N(R.sup.e,R.sup.f))] (B) wherein i) arene is selected from the group consisting of mononuclear and polynuclear arenes and mononuclear and polynuclear heteroarenes and ii) R.sup.H1, R.sup.H3, R.sup.c, R.sup.d, R.sup.e and R.sup.f are independently selected from the group consisting of H, an alkyl radical (C1-C10) and an aryl radical comprising the following steps: a) providing a compound in accordance with the general formula [Ru(arene)X.sub.2].sub.2 (C), wherein X=halogen and arene is selected from the group consisting of mononuclear and polynuclear arenes and mononuclear and polynuclear heteroarenes, b) reacting [Ru(arene)X.sub.2].sub.2 with M.sup.A.sub.2CO.sub.3 or M.sup.ECO.sub.3, wherein M.sup.A=alkali metal and M.sup.B=alkaline earth metal, and a ligand in accordance with the general formula
(R.sup.c,R.sup.d)N—N═CR.sup.H1—CR.sup.H3═N—N(R.sup.e,R.sup.f) in a polar solvent.
7. Method according to claim 6, wherein M.sup.A.sub.2CO.sub.3 is used, wherein M.sup.A=Li, Na or K, or M.sup.ECO.sub.3 is used, wherein M.sup.E=Mg, Ca, Sr or Ba.
8. Method according to claim 6, wherein the molar ratio [Ru(arene)X.sub.2].sub.2:M.sup.A.sub.2CO.sub.3 or [Ru(arene)X.sub.2].sub.2:M.sup.ECO.sub.3 is between 1:2 and 1:10.
9. Method according to claim 6, wherein the molar ratio [Ru(arene)X.sub.2].sub.2:(R.sup.c,R.sup.d)N—N═CR.sup.H1—CR.sup.H3═N—N(R.sup.e,R.sup.f) is between 1:2 and 1:10.
10. Method according to claim 6, wherein the solvent is an alcohol, an ether, acetonitrile or acetone.
11. Method according to claim 6, wherein the reaction mixture from step b) is heated, wherein a temperature T.sub.1 of the reaction mixture is between 20° C. and 160° C.
12. Method according to claim 6, wherein step b) is followed by step c), which comprises isolating
[Ru(arene)((R.sup.c,R.sup.d)N—N═CR.sup.H1—CR.sup.H3═N—N(R.sup.e,R.sup.f))] (B).
13. Compounds in accordance with the general formula
[Ru(arene)((R.sup.c,R.sup.d)N—N═CR.sup.H1—CR.sup.H3═N—N(R.sup.e,R.sup.f))] (B), wherein ii) arene is selected from the group consisting of mononuclear and polynuclear arenes and mononuclear and polynuclear heteroarenes and ii) R.sup.H1, R.sup.H3, R.sup.c, R.sup.d, and R.sup.f are independently selected from the group consisting of H, an alkyl radical (C1-C10) and an aryl radical, produced according to the method in accordance with claim 6.
14. Compounds according to claim 13, wherein arene is selected from the group consisting of benzene, toluene, ethylbenzene, tert-butylbenzene, sec-butylbenzene, propylbenzene, isopropylbenzene, benzocyclopentane, 4-ethyl-toluene, ortho-xylene, meta-xylene, para-xylene, chlorobenzene, mesitylene, para-cymene, anisole, aniline, pyridine, pyridine derivatives, diazines, diazine derivatives, triazines and triazine derivatives.
15. A method for producing a semiconductor element or an electronic memory comprising utilizing the compound according to claim 1, in the production of the semiconductor element or an electronic memory.
Description
(1) Other characteristics, details, and advantages of the invention follow from the wording of the claims as well as from the following description of the embodiment examples based upon the illustrations. The following are shown:
(2)
(3)
(4)
(5)
(6) The X-ray powder diffractograms (XRPDs, green) shown in
(7) Both for the residue arising from the thermal decomposition of the type A compound, namely [Ru(anisole)(.sup.iPrDAD)] (
Working Instructions for the Synthesis of [Ru(anisole)Cl.SUB.2.].SUB.2., [Ru(anisole)(.SUP.Me2N.DAD)], [Ru(anisole)(.SUP.Me2N.DAD)], [Ru(benzene)(.SUP.iPr.DAD)], [Ru(benzene)(.SUP.Me2N.DAD)], [Ru(mesitylene)(.SUP.iPr.DAD)], [Ru(mesitylene)(.SUP.Me2N.DAD)], [Ru(p-cymene)(.SUP.iPr.DAD)] and [Ru(p-cymene)(.SUP.Me2N.DAD)]
(8) Materials and Methods:
(9) All reactions were performed under a protective gas atmosphere with nitrogen or argon. The work was done with the assistance of common Schlenk techniques. The corresponding vacuum rakes or Schlenk lines were connected to rotary vane pumps made by Vacuubrand. The weighing and storage of educts, reagents and synthesized products took place in glove boxes made by MBraun (model MB 150 BG-1 or Lab Master 130) under a nitrogen atmosphere.
(10) The solvents used were dried according to standard procedures and stored in stainless steel columns over suitable drying agents (molecular sieve, aluminum oxide, copper catalyst). The deuterated solvent C.sub.6D.sub.6 was dehydrated over a K/Na alloy, CDCl.sub.3, over a molecular sieve 3 Å, condensed and once again stored over a molecular sieve 3 Å.
(11) All nuclear magnetic resonance spectroscopic measurements were performed in automated mode on an AV II 300 instrument or in manual mode on an AV III HD 250, AV III HD 300 or AV III 500 instrument. .sup.1H- and .sup.13C-NMR spectra were calibrated to the corresponding residual proton signal of the solvent as an internal standard: .sup.1H:C.sub.6D.sub.6: 7.16 ppm (s), CDCl.sub.3: 7.26 ppm (s). .sup.13C: C.sub.6D.sub.6: 128.0 ppm (tr), CDCl.sub.3: 77.2 ppm (s). The chemical shifts are indicated in ppm and refer to the 6 scale. All signals are provided with the following abbreviations according to their splitting pattern: s (singlet), d (doublet), t (triplet), hept (heptet) or sept (septet). The coupling between two nuclei A and B via n bonds is indicated by the coupling constant of the form .sup.n J.sub.AB in Hertz (Hz).
(12) In substance, the measurements of infrared spectra were usually performed on an Alpha ATR-IR spectrometer made by Bruker. The absorption bands are indicated in wave number (cm.sup.−1), and the intensity is described with the following abbreviations: w (weak), m (medium strong), st (strong), vst (very strong). The spectra were always normalized to the band with the highest intensity.
(13) The elemental analyses were carried out on a vario MICRO cube combustion device made by Elementar. Sample preparation was carried out in a glove box flooded with nitrogen by weighing the substance in tin crucibles, which were cold-welded and stored in a protective gas atmosphere until measurement. The elements of hydrogen, carbon and nitrogen were determined by means of a combustion analysis, wherein the information is always given in mass percent.
(14) All EI mass spectrometric investigations were performed on an AccuTOF GCv spectrometer made by Joel. Air-sensitive and moisture-sensitive samples were prepared in a glove box in crucibles and stored in a protective gas atmosphere until measurement. In the case of high-resolution spectra, the signal with the highest intensity of the isotope pattern is respectively indicated.
(15) The thermogravimetric investigations were performed on a TGA/DSC 3+ STAR system made by Mettler Toledo. In the process, a coupled SDTA measurement was performed for each TGA. The samples were measured in aluminum oxide, aluminum or sapphire crucibles, depending on the method or state of aggregation. The sample was heated at a specific heating rate from 25° C. to the final temperature. The evaluation of the spectra obtained was carried out with STARe software made by Mettler Toledo.
Preparation of glyoxal(bis-isopropylimine) (.SUP.iPr.DAD)
(16) The synthesis was carried out in accordance with E. A. Mistryukov, Mendeleev Communications 2006, 16 (5), 258-259.
(17) .sup.1H-NMR (C.sub.6D.sub.6, 300 MHz, 300 K): δ/ppm=7.94 (s, 2H, CH), 3.16 (hept, 2H, iPrCH), 1.08 (d, 12H, CH.sub.3); .sup.1H-NMR (CDCl.sub.3, 300 MHz, 300 K): δ/ppm=7.87 (s, 2H, CH), 3.46 (hept, 2H, iPrCH), 1.17 (d, 12H, CH.sub.3); .sup.13C-NMR (CDCl.sub.3, 75 MHz, 300 K): δ/ppm=159.8 (CH), 61.2 (iPrCH), 23.8 (CH.sub.3); .sup.13C-NM (C.sub.6D.sub.6, 75 MHz, 300 K): δ/ppm=159.7 (CH), 61.5 (iPrCH), 24.0 (CH.sub.3).
Preparation of glyoxal(bis-dimethylaminoimine) (.SUP.Me2N.DAD)
(18) The synthesis was carried out in accordance with T. Mino, Y. Shirae, Y. Sasai, M. Sakamoto, T. Fujita, J. Org. Chem. 2006, 71, 6834-6839.
(19) .sup.1H-NMR (C.sub.6D.sub.6, 300.2 MHz): δ/ppm=7.29 (s, 2H, CHCH), 3.53 (s, 12H, NMe.sub.2); .sup.1H-NMR (CDCl.sub.3, 300.2 MHz): δ/ppm=7.09 (s, 2H, CHCH), 2.85 (s, 12H, NMe.sub.2); .sup.13C-NMR (C.sub.6D.sub.6, 75.5 MHz): δ/ppm=134.8 (CHCH), 42.5 (NMe.sub.2); HR-ESI(+)-MS: calculated for [M+H].sup.+=143.1291 m/z, found: 143.1295 m/z; elemental analysis: C.sub.6H.sub.14N.sub.4 (142.21 g/mol), calculated: C, 50.68%; H, 9.92%; N, 39.40%, found: C, 49.96%; H, 9.72%; N, 39.86%; IR (substance) {tilde over (v)}/cm.sup.−1=2988 (w), 2952 (w), 2854 (m), 2824 (m), 2784 (m), 1668 (w), 1549 (m), 1465 (m), 1442 (m), 1420 (m), 1259 (m), 1133 (m), 1090 (w), 1009 (vs), 892 (m), 850 (w), 816 (m), 654 (w), 452 (w).
Exemplary Embodiment 1: Preparation of [Ru(Anisole)Cl.SUB.2.].SUB.2 .Via an Autoclave Reaction
(20) A 250 ml glass autoclave was filled with RuCl.sub.3×H.sub.2O (5.0 g, ca. 18.5 mmol, 1 eq), 150 ml methanol (dehydrated) and 1-methoxy-1,4-cyclohexadiene (10 ml, 10.64 g, 96.6 mmol, 5.23 eq). The reaction mixture was stirred at 140° C. and 5 bars for 4 hours. After cooling the reaction mixture to room temperature, the precipitated product was separated by means of filtration and washed with diethyl ether. The product was obtained as an orange crystalline solid with a yield of 47%, wherein it was contaminated with 10-17% of the usual unavoidable by-product [Ru(benzene)Cl.sub.2].sub.2.
(21) .sup.1H-NMR (DMSO-d.sup.6, 300 MHz, 300 K): δ/ppm=6.16 (t, J=5.3 Hz, 2H), 5.53 (d, J=5.9 Hz, 2H), 5.37 (s, 1H), 3.91 (s, 3H).
Exemplary Embodiment 2: Preparation of [Ru(Anisole)(.SUP.iPr.DAD)]
(22) ##STR00002##
(23) Under protective gas conditions, [RuCl.sub.2(anisole)].sub.2 (96.0 mg, 0.17 mmol, 1.0 eq), bis-iso-propyl-diazadiene (48.0 mg, 0.34 mmol, 2.0 eq) and K.sub.2CO.sub.3 (141 mg, 1.02 mmol, 6.0 eq) were absorbed into .sup.iPrOH (10 ml) and stirred for 16 hours under reflux conditions. After removing all volatile components in a vacuum, the residue was absorbed in nhexane (15 ml) and filtered by means of Celite®. In the process, the filter cake was extracted with additional amounts of nhexane (20 ml). The solvent was removed from the filtrate in a vacuum and [Ru(anisole)(.sup.iPrDAD)] was obtained as a red-orange solid (37.0 mg, 0.11 mmol, 65%).
(24) .sup.1H-NMR (C.sub.6D.sub.6, 300.2 MHz): δ/ppm=7.08 (s, 2H, H-1), 4.94 (d, .sup.3J.sub.HH=6.1 Hz, 2H, H-2), 4.87 (t, .sup.3J.sub.HH=5.1 Hz, 1H, H-4), 4.65 (t, .sup.3J.sub.HH=5.7 Hz, 2H, H-3), 4.47 (sept, 2H, .sup.iPr), 3.25 (s, 3H, OMe), 1.43 (d, .sup.3J.sub.HH=6.7 Hz, 12H, .sup.iPr); .sup.13C-NMR (C.sub.6D.sub.6, 75.5 MHz): δ/ppm=131.1 (C-1), 100.4 (C.sub.q), 74.9, 73.6, 71.9, 65.6, 62.8 (.sup.iPr), 56.5 (OMe), 25.0 (.sup.iPr). HR-EI(+)-MS: calculated for [M].sup.+=350.0932 m/z, found: 350.1124 m/z; elemental analysis: calculated for C.sub.15H.sub.24N.sub.2ORu (349.44 g/mol): calculated (found): C, 51.56% (47.04%); H, 6.92% (H, 6.62%); N, 8.02% (8.72%); IR (substance): {tilde over (v)}/cm.sup.−1=3053 (w), 2965 (m), 2918 (m), 2821 (w), 1657 (w), 1559 (w), 1507 (s), 1445 (m), 1427 (m), 1249 (m), 1222 (vs), 1167 (s), 1080 (m), 1040 (m), 1013 (m), 976 (m), 926 (w), 891 (w), 811 (m), 768 (m), 613 (m), 543 (w), 513 (w); TGA (T.sub.S=25° C., T.sub.E=700° C., 10° C./min, m=6.70 mg) steps: 1, T=154.8° C. (3% degradation), T.sub.D(onset)=211.4° C., T.sub.D(max)=252.9° C., total degradation: 5.75 mg (85.8%); SDTA (T.sub.S=25° C., T.sub.E=700° C., 10° C./min, m=6.70 mg) T.sub.M(onset)=91.6° C., T.sub.M(max)=95.4° C. (endothermic), T.sub.D(onset)=not definable, T.sub.D(max.)=not definable; verification of elemental ruthenium (Lit*: M. Cernohorsky, Acta Cryst. 1960, 13, 823-826): XRPD (residue from TGA analysis) 2Θ.sub.Lit*/° (2Θ.sub.obs/°): 38.39 (38.37), 43.72 (42.13), 44.01 (43.99), 58.33 (58.35), 69.41 (69.37), 78.30 (78.36), 82.22 (n/d), 84.71 (84.57), 85.96 (85.77), 92.04 (n/d), 97.09 (n/d).
Exemplary Embodiment 3: Preparation of [Ru(Anisole)(.SUP.Me2N.DAD)]
(25) ##STR00003##
(26) Under protective gas conditions, [RuCl.sub.2(anisole)].sub.2 (500 mg, 0.89 mmol, 1.0 eq), glyoxal(bis-dimethylaminoimine) (254 mg, 1.79 mmol, 2.0 eq) and K.sub.2CO.sub.3 (1.48 g, 10.7 mmol, 6.0 eq) were absorbed into iPrOH (10 ml) and stirred for 16 hours under reflux conditions. After removing all volatile components in a vacuum, the residue was absorbed in nhexane (15 ml) and filtered by means of Celite®. In the process, the filter cake was extracted with additional amounts of nhexane (20 ml). The solvent was removed from the filtrate in a vacuum and volatile impurities were removed by means of sublimation (fine vacuum, 40° C.). [Ru(anisole)(.sup.Me2NDAD)] was obtained as the residue in the form of a red crystalline solid (83.0 mg, 0.24 mmol, 27%).
(27) .sup.1H-NMR (C.sub.6D.sub.6, 300.2 MHz): δ/ppm=7.31 (s, 2H, H-1), 5.33 (d, .sup.3J.sub.HH=5.3 Hz, 2H, H-2), 4.87 (t, .sup.3J.sub.HH=5.1 Hz, 1H, H-4), 4.65 (t, .sup.3J.sub.HH=5.7 Hz, 2H, H-3), 3.29 (s, 3H, OMe), 2.75 (s, 12H, NMe.sub.2); .sup.13C-NMR (C.sub.6D.sub.6, 75.5 MHz): δ/ppm=130.4 (C-1), 73.8 (C-4), 72.4 (C-3), 66.6 (C-2), 56.4 (OMe), 48.1 (NMe.sub.2); HR-EI(+)-MS: calculated for [M]+=352.0827 m/z, found: 352.0845 m/z; elemental analysis: calculated for C.sub.13H.sub.22N.sub.4ORu (351.42 g/mol): calculated (found): C, 44.43% (45.63%); H, 6.31% (H, 6.28%); N, 15.94% (15.39%); IR (substance): {tilde over (v)}/cm.sup.−1=3046 (w), 2973 (w), 2933 (m), 2853 (m), 2812 (m), 2771 (m), 1508 (m), 1435 (s), 1267 (m), 1227 (vs), 1169 (m), 1130 (m), 1009 (s), 919 (m), 886 (m), 858 (m), 814 (m), 769 (m), 738 (m), 637 (w), 614 (w), 553 (w) 473 (w), 447 (w) 417 (w); TGA (T.sub.S=25° C., T.sub.E=700° C., 10° C./min, m=11.5 mg) steps: 2, T=177.1° C. (3% degradation), step 1: T(onset)=182.2° C., T(max)=239.9° C., step 2: T(onset)=460.8° C., T(max)=508.3° C., total degradation: 8.26 mg (71.8%); SDTA (T.sub.S=25° C., T.sub.E=700° C., 10° C./min, m=11.5 mg) T.sub.M(onset)=60.1° C., T.sub.M(max)=70.2° C. (endothermic), T.sub.D1(onset)=217.2° C., T.sub.D1(max)=239.6° C. (exothermic), T.sub.D2(onset)=483.5° C., T.sub.D2(max)=516.2° C. (exothermic);
(28) verification of elemental ruthenium (Lit *: M. Cernohorsky, Acta Cryst. 1960, 13, 823-826): XRPD (residue from TGA analysis) 2Θ.sub.Lit*/° (2Θ.sub.obs/°): 38.39 (38.34), 43.72 (42.09), 44.01 (43.99), 58.33 (58.26), 69.41 (69.37), 78.30 (78.28), 82.22 (n/d), 84.71 (84.68), 85.96 (85.87), 92.04 (n/d), 97.09 (n/d).
Exemplary Embodiment 4: Preparation of [Ru(Benzene)(.SUP.iPr.DAD)]
(29) ##STR00004##
(30) [RuCl.sub.2(benzene)].sub.2 (800 mg, 1.60 mmol, 1.0 eq) and zinc powder (418 mg, 6.40 mmol, 4.0 eq) were provided in THF (30 ml) and mixed with .sup.iPrDAD (673 mg, 4.80 mmol, 3.0 eq) while stirring. The mixture was stirred for 5 hours at 60° C., wherein a dark red color was observed. After removing all volatile components in a vacuum, the residue was absorbed in toluene (15 ml), stirred for one hour at room temperature and then filtered by means of Celite®. In the process, the solid was extracted several times with toluene (40 ml) until reddish filtrate was no longer obtained. After the filtrate had dried in the vacuum, the target compound was condensed out of the resulting residue in a dynamic fine vacuum at an oil bath temperature of 120° C. [Ru(benzene)(.sup.iPrDAD)] was obtained as a dark red liquid (466 mg, 1.46 mmol, 46%), which ultimately completely crystallized and was present as a solid at room temperature.
(31) .sup.1H-NMR (C.sub.6D.sub.6, 300.2 MHz): δ/ppm=7.05 (s, 2H, H-1), 4.83 (s, 6H, benzene), 4.39 (sept, 2H, iPr), 1.41 (d, .sup.3J.sub.HH=6.8 Hz, 12H, iPr); .sup.13C-NMR (C.sub.6D.sub.6, 75.5 MHz): δ/ppm=131.5 (C-1), 74.9 (benzene), 63.4 (Pr), 24.9 (iPr); HR-EI-MS: calculated for [M]+=320.0827 m/z, found: 320.0805 m/z; elemental analysis: C.sub.14H.sub.22N.sub.2Ru (319.41 g/mol), calculated: C, 52.64%; H, 6.94%; N, 8.77%, found: C, 52.65%; H, 6.89%; N, 8.98%; IR (substance): {tilde over (v)}/cm.sup.−1=3047 (w), 2959 (m), 2922 (m), 2859 (m), 1838 (w), 1726 (m), 1641 (w), 1510 (m), 1433 (m), 1353 (m), 1276 (m), 1247 (s), 1216 (vs), 1168 (s), 1118 (s), 1072 (m), 996 (m), 904 (m), 793 (m), 718 (s), 614 (m), 546 (m); TGA (T.sub.S=25° C., T.sub.E=700° C., 10° C./min, m=12.0 mg) steps: 1, T=185.8° C. (3% degradation), T.sub.D(onset)=222.8° C., T.sub.D(max)=268.4° C., total degradation: 11.8 mg (98.0%); SDTA (T.sub.S=25° C., T.sub.E=900° C., 10° C./min, m=12.0 mg): T.sub.M(onset)=101.6° C., T.sub.M(max.)=106.7° C. (endothermic), T.sub.D(onset)=250° C., T.sub.D(max)=271.1° C. (exothermic).
Exemplary Embodiment 5: Preparation of [Ru(benzene)(.SUP.Me2N.DAD)]
(32) ##STR00005##
(33) [RuCl.sub.2(benzene)].sub.2 (400 mg, 0.80 mmol, 1.0 eq) and zinc powder (209 mg, 3.20 mmol, 4.0 eq) were provided in THF (15 ml) and mixed with .sup.Me2NDAD (227 mg, 1.60 mmol, 2.0 eq) in THF (5 ml) while stirring. The mixture was stirred for 5 hours at 60° C., wherein a change of color to dark red was observed. After removing all volatile components in a vacuum, the residue was absorbed in toluene (15 ml), stirred for one hour at room temperature and then filtered by means of Celite®. In the process, the solid was extracted several times with toluene (40 ml) until reddish filtrate was no longer obtained. After the filtrate had dried in the vacuum, the target compound was condensed out of the resulting residue in a dynamic fine vacuum at an oil bath temperature of 120° C. [Ru(benzene)(.sup.Me2NDAD)] was obtained as a dark red liquid (153 mg, 0.48 mmol, 60%), which ultimately completely crystallized and was present as a solid at room temperature.
(34) In the SDTA experiment obtained, two endothermic peaks were found, both of which could indicate a melting point. By means of optical melting point determination, the second peak could be clearly assigned to such a process, whereas no change of the sample was detectable in the temperature range of the first peak.
(35) .sup.1H-NMR (C.sub.6D.sub.6, 300.2 MHz): δ/ppm=7.31 (s, 2H, H-1), 5.19 (s, 6H, H-arom.), 2.71 (s, 12H, NMe.sub.2); .sup.13C-NMR (C.sub.6D.sub.6, 75.5 MHz): δ/ppm=131.2 (C-1), 75.7 (C-arom.), 48.1 (NMe.sub.2); HR-EI-MS: calculated for [M]+=322.0731 m/z, found: 322.0733 m/z; elemental analysis: C.sub.12H.sub.20N.sub.4Ru (321.39 g/mol), calculated: C, 44.85%; H, 6.27%; N, 17.43%, found: C, 44.84%; H, 6.26%; N, 17.85%; IR (substance): {tilde over (v)}/cm.sup.−1=2936 (m), 2829 (m), 2798 (m), 2756 (m), 1648 (w), 1501 (m), 1448 (m), 1429 (s), 1256 (s), 1227 (m), 1205 (m), 1139 (m), 966 (s), 909 (m), 865 (m), 797 (vs), 712 (s), 684 (m), 599 (m), 541 (w), 457 (w), 413 (m); TGA (T.sub.S=25° C., T.sub.E=700° C., 10° C./min, m=12.3 mg) steps: 2, T=1922° C. (3% degradation), step 1: T.sub.D1(onset)=221.2° C., T.sub.D1(max.)=258.5° C., step 2: T.sub.D2(onset)=465.4° C., T.sub.D2(max.)=507.4° C., total degradation: 9.01 mg (81.2%); SDTA (T.sub.S=25° C., T.sub.E=700° C., 10° C./min, m=12.3 mg): T(onset)=56.8° C., T(max.)=60.0° C. (endothermic), T.sub.M(onset)=84.2° C., T.sub.M(max.)=86.5° C. (endothermic), T.sub.D1(onset)=224.7° C., T.sub.D1(max)=246.1° C. (exothermic); melting point determination: (N.sub.2, T.sub.S=50° C., T.sub.E=100° C., 2° C./min): T.sub.M=85.3° C.; verification of elemental ruthenium (Lit *: M. Cernohorsky, Acta Cryst. 1960, 13, 823-826): XRPD (residue from TGA analysis) 2Θ.sub.Lit*/° (2Θobs/°): 38.39 (38.61), 43.72 (42.27), 44.01 (43.89), 58.33 (58.27), 69.41 (69.22), 78.30 (78.36), 82.22 (n/d), 84.71 (84.66), 85.96 (85.41), 92.04 (n/d), 97.09 (n/d).
Exemplary Embodiment 6: Preparation of [Ru(mesitylene)(.SUP.iPr.DAD)]
(36) ##STR00006##
(37) [RuCl.sub.2(mesitylene)].sub.2 (800 mg, 1.37 mmol, 1.0 eq) and zinc powder (358 mg, 5.48 mmol, 4.0 eq) were provided in THF (15 ml) and mixed with iPrDAD (576 mg, 4.11 mmol, 3.0 eq) while stirring. The mixture was stirred for 5 hours at 60° C., wherein a dark red color was observed. After removing all volatile components in a vacuum, the residue was absorbed in toluene (20 ml) and filtered by means of Celite®. In the process, the solid was extracted several times with toluene (40 ml) until reddish filtrate was no longer obtained. After the filtrate had dried in the vacuum, the target compound was condensed out of the resulting residue in a dynamic fine vacuum at an oil bath temperature of 120° C. Ru(mesitylene)(.sup.iPrDAD)] was obtained as an orange-red liquid (305 mg, 0.84 mmol, 31%), which ultimately completely crystallized and was present at room temperature as an orange-colored solid.
(38) .sup.1H-NMR (C.sub.6D.sub.6, 300.2 MHz: δ/ppm=7.06 (s, 2H, CHCH), 4.76 (s, 3H, H-2), 4.53 (sept, 2H, iPr), 2.04 (s, 9H, H-3), 1.44 (d, .sup.3J.sub.HH=6.8 Hz, 12H, iPr); .sup.13C-NMR (C.sub.6D.sub.6, 75.5 MHz): δ/ppm=129.4 (C-1), 85.8 (C-3), 78.1 (C-2), 61.4 (iPr), 24.7 (iPr), 20.3 (C-4); HR-EI-MS: calculated for [M]+=362.1296 m/z, found: 362.1313 m/z; elemental analysis: C.sub.17H.sub.28N.sub.2Ru (361.50 g/mol), calculated: C, 56.48%; H, 7.81%; N, 7.75%, found: C, 56.04%; H, 7.61%; N, 8.23%; IR (substance): {tilde over (v)}/cm.sup.−1=2963 (m), 2917 (w), 2859 (w), 1635 (w), 1516 (m), 1441 (m), 1371 (w), 1244 (s), 1217 (vs), 1166 (m), 1028 (m), 984 (m), 874 (m), 712 (vs), 615 (w), 564 (w), 509 (w), 475 (w).
Exemplary Embodiment 7: Preparation of [Ru(mesitylene)(.SUP.Me2N.DAD)]
(39) ##STR00007##
(40) [RuCl.sub.2(mesitylene)].sub.2 (800 mg, 1.37 mmol, 1.0 eq) and zinc powder (358 mg, 5.48 mmol, 4.0 eq) were provided in THF (15 ml) and mixed with .sup.Me2NDAD (576 mg, 4.11 mmol, 3.0 eq) in THF (5 ml) while stirring. The mixture was stirred for 5 hours at 60° C., wherein a dark red color was observed. After removing all volatile components in a vacuum, the residue was absorbed in toluene (20 ml) and filtered by means of Celite®. In the process, the solid was extracted several times with toluene (30 ml) until reddish filtrate was no longer obtained. After the filtrate had dried in the vacuum, the target compound was condensed out of the residue in a dynamic fine vacuum at an oil bath temperature of 120° C. [Ru(mesitylene)(.sup.Me2NDAD)] was obtained as an orange-red liquid (332 mg, 0.92 mmol, 34%), which ultimately completely crystallized and was present at room temperature as an orange-colored solid.
(41) .sup.1H-NMR (C.sub.6D.sub.6, 300.2 MHz): δ/ppm=7.13 (s, 2H, H-1), 4.95 (s, 3H, H-2), 2.75 (s, 12H, NMe.sub.2), 2.17 (s, 9H, H-4); .sup.13C-NMR (C.sub.6D.sub.6, 75.5 MHz9: δ/ppm=125.7 (C-1), 87.9 (C-3), 79.1 (C-2), 47.2 (NMe.sub.2), 20.5 (C-4); HR-EI-MS: calculated for [M]+=364.1201 m/z, found: 364.1204 m/z; elemental analysis: C.sub.15H.sub.26N.sub.4Ru (363.47 g/mol), calculated: C, 49.57%; H, 7.21%; N, 15.41%; found: C, 48.51%; H, 7.13%; N, 16.10%; IR (substance): {tilde over (v)}/cm.sup.−1=2972 (m), 2934 (m), 2862 (m), 2832 (m), 2799 (m), 2761 (m), 1504 (m), 1445 (s), 1371 (m), 1235 (m), 1199 (m), 1150 (m), 1031 (m), 995 (m), 853 (s), 678 (vs), 567 (w), 567 (m), 510 (m).
Exemplary Embodiment 8: Preparation of [Ru(p-cymene)(.SUP.iPr.DAD)]
(42) ##STR00008##
(43) [RuCl.sub.2(p-cymene)].sub.2 (1.00 g, 1.63 mmol, 1.0 eq) and zinc powder (426 mg, 6.53 mmol, 4.0 eq) were provided in a protective gas flask and mixed with THF (30 ml). iPrDAD (916 mg, 6.53 mmol, 4.0 eq) was added while stirring and the mixture was stirred for five hours at 60° C., wherein a dark red color was observed. After removing all volatile components in a vacuum, the residue was absorbed in toluene (20 ml), stirred for one hour at room temperature and then filtered by means of Celite®. In the process, the solid was extracted several times with toluene (50 ml) until reddish filtrate was no longer obtained. After the filtrate had dried in the vacuum, the target compound was isolated from the residue by means of recondensation in a fine vacuum at an oil bath temperature of 120° C. [Ru(p-cymene)(.sup.iPrDAD)] was obtained as a dark red liquid (413 mg, 1.13 mmol, 35%), which ultimately completely crystallized and was present as a solid at room temperature.
(44) .sup.1H-NMR (C.sub.6D.sub.6, 300.2 MHz): δ/ppm=7.03 (s, 2H, H-3), 4.62 (s, 4H, H-4, H-5), 4.49 (sept, 2H, H-1), 2.43 (sept, 1H, H-8), 2.10 (s, 3H, H-10), 1.45 (d, .sup.3J.sub.HH=6.7 Hz, 12H, H-2), 1.15 (d, .sup.3J.sub.HH=6.7 Hz, 6H, H-9); .sup.13C-NMR (C.sub.6D.sub.6, 75.5 MHz): δ/ppm=130.5 (C-3), 100.5 (C-7), 88.6 (C-6), 75.4 (C-5), 73.4 (C-4), 62.9 (C-1), 32.6 (C-8), 24.8 (C-2), 21.1 (C-10); HR-EI(+)-MS: calculated for [M]+=376.1453 m/z, found: 376.1443 m/z; elemental analysis: C.sub.16H.sub.28N.sub.4Ru (377.50 g/mol), calculated: C, 57.57%; H, 8.05%; N, 7.46%, found: C, 57.48%; H, 7.87%; N, 7.99%; IR (substance): {tilde over (v)}/cm.sup.−1=3077 (w), 3049 (w), 2959 (s), 2921 (m), 2860 (m), 1815 (w), 1632 (w), 1517 (m), 1439 (m), 1372 (m), 1354 (m), 1319 (m), 1243 (s), 1216 (vs), 1164 (s), 1140 (m), 1114 (m), 1081 (m), 1044 (m), 905 (m), 859 (m), 834 (m), 795 (m), 717b (vs), 636 (m), 613 (m), 544 (m), 420 (w); TGA (T.sub.S=25° C., T.sub.E=700° C., 10° C./min, m=11.8 mg) steps: 1, T=185.6° C. (3% degradation), T.sub.D(onset)=229.4° C., T.sub.D(max.)=266.9° C., total degradation: 11.5 mg (97.1%); SDTA (T.sub.S=25° C., T.sub.E=700° C., 10° C./min, m=11.8 mg): T.sub.M(onset)=38.0° C., T.sub.M(max.)=42.3° C. (endothermic), T.sub.D(onset)=n/d, T.sub.D(max)=168.3° C. (exothermic).
Exemplary Embodiment 9: Preparation of [Ru(p-cymene)(.SUP.Me2N.DAD)]
(45) ##STR00009##
(46) [RuCl.sub.2(p-cymene)].sub.2 (40.0 g, 65.3 mmol, 1.0 eq) and zinc (20.0 g, 306 mmol, 4.7 eq) were provided in a protective gas flask and mixed with THF (200 ml). .sup.Me2NDAD (37.15 g, 261 mmol, 4.0 eq) was added while stirring and the mixture was stirred for five hours at 60° C., wherein a dark red color was observed. After removing all volatile components in a vacuum, the residue was absorbed in toluene (100 ml), stirred for one hour at room temperature and then filtered by means of Celite®. In the process, the solid was extracted several times with toluene (600 ml) until reddish filtrate was no longer obtained. After the filtrate had dried in a vacuum, the target compound was isolated by means of an ether bridge in a fine vacuum at an oil bath temperature of 120° C. [Ru(p-cymene)(.sup.Me2NDAD)] was obtained as a dark red liquid (30.8 g, 81.6 mmol, 62%), which ultimately completely crystallized and was present as a solid at room temperature.
(47) .sup.1H-NMR (C.sub.6D.sub.6, 300.2 MHz): δ/ppm=7.22 (s, 2H, H-1), 5.08 (s, 4H, H-2, H-3), 2.78 (s, 12H, NMe.sub.2), 2.52 (sept, 1H, iPr), 2.13 (s, 3H, Me), 1.15 (d, .sup.3J.sub.HH=7.1 Hz, 6H, iPr); .sup.13C-NMR (C.sub.6D.sub.6, 75.5 MHz: δ/ppm=129.5 (C-1), 101.9 (Cq), 90.2 (Cq), 76.5 (C-3), 74.5 (C-2), 48.0 (NMe.sub.2), 32.8 (iPr), 24.8 (iPr), 21.2 (Me); HR-EI(+)-MS: calculated for [M]+=378.1357 m/z, found: 378.1352 m/z; elemental analysis: C.sub.16H.sub.28N.sub.4Ru (377.50 g/mol), calculated: C, 50.91%; H, 7.48%; N, 14.84%, found: C, 50.94%; H, 7.27%; N, 15.05%; IR (substance) {tilde over (v)}/cm.sup.−1=2959 (m), 2926 (m), 2840 (m), 2804 (m), 2759 (m), 1727 (w), 1648 (w), 1507 (m), 1435 (s), 1379 (m), 1355 (m), 1355 (m), 1316 (m), 1269 (vs), 1192 (m), 1141 (m), 1081 (m), 1026 (m), 924 (m), 865 (m), 840 (s), 796 (m), 720 (vs), 689 (m), 655 (w), 639 (w), 470 (w); TGA (T.sub.S=25° C., T.sub.E=600° C., 10° C./min, m=12.3 mg) steps: 2, T=186.8° C. (3% degradation), T.sub.D1(onset)=217.0° C., T.sub.D1(max.)=245.0° C. (71.0%), T.sub.D2(onset)=456.0° C., T.sub.D2(max.)=502.5° C. (5.89%), total degradation: 9.45 mg (76.9%), SDTA (T.sub.S=25° C., T.sub.E=600° C., 10° C./min, m=12.3 mg): T.sub.M(onset)=54.7° C., T.sub.M(max.)=59.1° C. (endothermic), T.sub.D1(onset)=214.2° C., T.sub.D1(max)=237.2° C. (exothermic);
(48) verification of elemental ruthenium (Lit *: M. Cernohorsky, Acta Cryst. 1960, 13, 823-826): XRPD (residue from TGA analysis) 2Θ.sub.Lit*)(2Θobs/°): 38.39 (38.38), 43.72 (42.15), 44.01 (43.99), 58.33 (58.30), 69.41 (69.37), 78.30 (78.34), 82.22 (n/d), 84.71 (84.65), 85.96 (85.92), 92.04 (n/d), 97.09 (n/d).
(49) The invention is not limited to one of the embodiments described above but may be modified in many ways.
(50) It is recognized that the invention relates to compounds in accordance with the general formula [Ru(arene)(R.sup.a—N═CR.sup.1—CR.sup.3═N—R.sup.b)] or [Ru(arene)((R.sup.c,R.sup.d)N—N═CR.sup.H1—CR.sup.H3═N—N(R.sup.e,R.sup.f))]. In this case, arene is selected from the group consisting of mononuclear and polynuclear arenes and mononuclear and polynuclear heteroarenes. R.sup.1, R.sup.3, R.sup.H1, R.sup.H3 and R.sup.a-R.sup.f are independently selected from the group consisting of H, an alkyl radical (C1-C10) and an aryl radical. It further relates to methods for the production of these compounds, compounds obtainable according to these methods, their use and a substrate having on a surface thereof a ruthenium layer or a layer containing ruthenium. In addition, the invention relates to a method for producing compounds [Ru(arene)X.sub.2].sub.2, wherein arene is selected from the group consisting of mononuclear and polynuclear arenes and X=halogen, compounds of this type obtainable according to this method, and their use.
(51) Using the method described above, the aforementioned ruthenium(0) compounds can be prepared in a simple, cost-effective and reproducible manner with a high degree of purity and a good yield. The production methods can also be carried out on an industrial scale. Due to their high degree of purity, the aforementioned embodiments of the ruthenium(0) complexes claimed are suitable for use as ruthenium(0) precursors. Advantageously, only a small amount of material is required to deposit a ruthenium(0) layer or a layer containing ruthenium(0).
(52) All features and advantages resulting from the claims, the description and the figures, including constructive details, spatial arrangements and method steps, can be essential to the invention, both in and of themselves and in the most diverse combinations.