NEW METAL N-AMINOGUANIDINATE COMPLEXES FOR USE IN THIN FILM FABRICATION AND CATALYSIS

Abstract

The present patent application relates to new metal complexes having at least one N-aminoguanidinate ligand. The patent application further relates to the preparation of the new metal complexes and also to their use. The new metal complexes are especially suitable as precursors for the preparation of functional layers by means of gas-phase thin-film processes such as CVD, MO-CVD, MOVPE and ALD. Additionally, they are also suitable as catalysts for olefin hydroamination and for olefm polymerization.

##STR00001##

Claims

1. Metal complex having at least one N-aminoguanidinate ligand, wherein this metal complex is of the following formula 1a or 1b ##STR00011## wherein M is a metal selected from the groups 1 to 15 of the Periodic Table of the Elements (PTE), lanthanides or actinides, R.sup.1 is hydrogen or a cyclic, linear or branched alkyl radical having up to 5 carbon atoms, NH.sub.2, NH(CH.sub.3), N(CH.sub.3).sub.2, N(CH.sub.2H.sub.5).sub.2 or N-pyrrolidinyl, or R.sup.1 and R.sup.2 together with the nitrogen atom they are bonded to form a pyrrolidinyl ring; R.sup.2 is hydrogen or a cyclic, linear or branched alkyl radical having up to 5 carbon atoms, or R.sup.2 and R.sup.1 together with the nitrogen atom they are bonded to form a pyrrolidinyl ring; R.sup.3 is hydrogen or a cyclic, linear or branched alkyl radical having up to 8 carbon atoms, NH.sub.2, NH(CH.sub.3), N(CH.sub.3).sub.2, N(C.sub.2H.sub.5).sub.2 or N-pyrrolidinyl or a SiMe.sub.3 group, R.sup.4 and R.sup.5 independently of one another are hydrogen or a linear or branched alkyl radical having up to 4 carbon atoms, or R.sup.4 and R.sup.5 together with the nitrogen atom they are bonded to form a pyrrolidinyl ring; X is a monoanionic co-ligand selected from the hydride anion (H.sup.−), from the group of the halides, from the group of the cyclic, linear or branched alkylides having up to 8 carbon atoms, from the group of substituted or unsubstituted arylides and heteroarylides having up to 10 C atoms, from the group of alkoxylato ligands, from the group of alkylthiolato or alkylselenolato ligands or from the group of secondary amido ligands, Y is a dianionic coligand selected from the oxo group [O].sup.2−, the sulfido group [S].sup.2− or the imido group [NR.sup.6].sup.2−, where R.sup.6 is a cyclic, branched or linear alkyl having up to 8 carbon atoms or is a substituted or unsubstituted aryl having up to 20 carbon atoms, L is a neutral 2-electron donor ligand, a is an integer between 1 and 4 and n, m, and p each independently of one another are 0, 1, 2, 3 or 4.

2. Metal complex according to claim 1, wherein M is a metal selected from the groups 1 to 15 of the Periodic Table of the Elements (PTE), lanthanides or actinides, R.sup.1 is hydrogen or a cyclic, linear or branched alkyl radical having up to 5 carbon atoms, NH.sub.2, N(CH.sub.3).sub.2 or N(C.sub.2H.sub.5).sub.2, R.sup.2 is hydrogen or a cyclic, linear or branched alkyl radical having up to 5 carbon atoms, NH.sub.2, N(CH.sub.3).sub.2 or N(C.sub.2H.sub.5).sub.2, R.sup.3 is hydrogen or a cyclic, linear or branched alkyl radical having up to 8 carbon atoms, NH.sub.2, N(CH.sub.3).sub.2 or N(C.sub.2H.sub.5).sub.2, R.sup.4 and R.sup.5 independently of one another are hydrogen or a linear or branched alkyl radical having up to 4 carbon atoms, X is a monoanionic co-ligand selected from the hydride anion (H.sup.−), from the group of the halides, from the group of the cyclic, linear or branched alkylides haying up to 8 carbon atoms, from the group of substituted or unsubstituted arylides and heteroarylides having up to 10 C atoms, from the group of alkoxylato ligands, from the group of alkylthiolato or alkylselenolato ligands or from the group of secondary amido ligands, Y is a dianionic coligand selected from the oxido group [O].sup.2− or the imido group [NR.sup.6].sup.2−, where R.sup.6 is a cyclic, branched or linear alkyl having up to 8 carbon atoms or is a substituted or unsubstituted aryl having up to 20 carbon atoms, L is a neutral 2-electron donor ligand, a is an integer between 1 and 4 and n, m, and p each independently of one another are 0, 1, 2, 3 or 4.

3. Metal complex according to claim 1, wherein R.sup.1 is hydrogen or a cyclic, linear or branched alkyl radical having up to 5 carbon atoms, R.sup.2 is hydrogen or a cyclic, linear or branched alkyl radical having up to 5 carbon atoms, R.sup.3 is hydrogen or a cyclic, linear or branched alkyl radical having up to 5 carbon atoms, NH.sub.2, N(CH.sub.3).sub.2 or N(C.sub.2H.sub.5).sub.2, R.sup.4 and R.sup.5 are independently of one another hydrogen or a linear or branched alkyl radical having up to 3 carbon atoms, X is the hydride anion (H.sup.−), methylide (CH.sub.3.sup.−), ethylide (C.sub.2H.sub.5.sup.−), isopropylide (iso-C.sub.3H.sub.7.sup.−), tert-butylide (tert-C.sub.4H.sub.9.sup.−), the phenylide anion (C.sub.6H.sub.5.sup.−), the ortho-, meta-, or para-tolylide anion [C.sub.6H.sub.4(CH.sub.3)].sup.−, the thiophen-2-ylide anion (C.sub.4H.sub.3S.sup.−) methylato (MeO.sup.−) ethylato (EtO.sup.−), tert-butylato (tert-BuO.sup.−), MeS.sup.−, MeSe.sup.−, (tert-Bu)S.sup.−, (tert-Bu)Se.sup.−, dimethylamido (NMe.sub.2.sup.−), diethylamido (NEt.sub.2.sup.−), methylethylamido (NMeEt.sup.−), N-pyrrolidido [NC.sub.4C.sub.4H.sub.8].sup.−, chloride (Cl.sup.−) or bromide (Br.sup.−), Y is the oxo group [O].sup.2− or the imido group [NR.sup.6].sup.2−, where R.sup.6 is a cyclic, branched or linear alkyl having up to 6 C atoms or is a substituted or unsubstituted. aryl having up to 12 C atoms.

4. Metal complex according to claim 1, wherein R.sup.1 is hydrogen or a linear or branched alkyl radical having up to 4 carbon atoms, R.sup.2 is hydrogen or a linear or branched alkyl radical haying up to 4 carbon atoms, R.sup.3 is hydrogen, CH.sub.3, C.sub.2H.sub.5, NH.sub.2, N(CH.sub.3).sub.2 or N(C.sub.2H.sub.5).sub.2, R.sup.4 and R.sup.5 independently of one another are hydrogen, CH.sub.3 or C.sub.2H.sub.5, X is the hydride anion (H.sup.−), methylide (CH.sub.3.sup.−), ethylide (C.sub.2H.sub.5.sup.−), the phenylide anion (C.sub.6H.sub.5.sup.−), the ortho- meta-, or para-tolylide anion [C.sub.6H.sub.4(CH.sub.3)].sup.−, methylato (MeO.sup.−), ethylato (EtO.sup.−), MeS.sup.−, MeSe.sup.−, dimethylamido (NMe.sub.2.sup.−), diethylamido (NEt.sub.2.sup.−), methylethylamido (NMeEt.sup.−), chloride (Cl.sup.−) or bromide (Br.sup.−), Y is the oxo group [O].sup.2− or the imido group [NR.sup.6].sup.2−, where R.sup.6 is a branched or linear alkyl having up to 5 C atoms or is a substituted or unsubstituted aryl having up to 8 C atoms.

5. Metal complex according to claim 1, wherein R.sup.1 is hydrogen or a linear or branched alkyl radical having up to 3 carbon atoms, R.sup.2 is hydrogen or a linear or branched alkyl radical having up to 3 carbon atoms, R.sup.3 is CH.sub.3, C.sub.2H.sub.5, N(CH.sub.3).sub.2 or (C.sub.2H.sub.5).sub.2, R.sup.4 and R.sup.5 independently of one another are CH.sub.3 or C.sub.2H.sub.5, X is the hydride anion (H.sup.−), methylide ethylide (C.sub.2H.sub.5.sup.−), the phenylide anion (C.sub.6H.sub.5.sup.−), the ortho-, meta-, or para-tolylide anion [C.sub.6H.sub.4(CH.sub.3)].sup.−, methylato (MeO.sup.−), MeS.sup.−, dimethylamido (NMe2.sup.−) diethylamide (NEt.sub.2.sup.−) or chloride (Cl.sup.−), Y is the imido group [NR.sup.6].sup.2−, where R.sup.6 is a linear or branched alkyl having up to 4 C atoms.

6. Metal complex according to claim 1, wherein R.sup.1 and R.sup.2 are both, independently of one another, a linear alkyl radical having up to 3 carbon atoms. R.sup.3 is CH.sub.3, C.sub.2H.sub.5 or N(CH.sub.3).sub.2, R.sup.4 and R.sup.5 independently of one another are CH.sub.3 or C.sub.2H.sub.5, X is a hydride anion (H.sup.−), methylide (CH.sub.3.sup.−), ethylide (C.sub.2H.sub.5.sup.−), isopropylide (iso-C.sub.3H.sub.7.sup.−). Y is the imido group [N.sup.tBu].sup.2−1,

7. Metal complex according to claim 1, having the formula 2 ##STR00012## wherein M is B, Al, Ga, In, Fe, Zn or Pd, R.sup.3 is CH.sub.3 or N(CH.sub.3).sub.2, X is the hydride anion (H.sup.−) or methylide (CH.sub.3.sup.−), a is I or 2 and n is 0, 1 or 2,

8. Metal complex according to claim 1, wherein the metal complexes have the following formula 3 ##STR00013## wherein M is B, Al, Ga, In, Zn, Fe or Pd, X is the hydride anion (H.sup.−) or methylide (CH.sub.3.sup.−), a is 1 or 2 and n is 0, 1 or 2,

9. Metal complex according to claim 8, wherein the N-aminoguanidinate-ligand is N-dimethylamino-N′,N″-trimethylguanidinate (datg).

10. Metal complex according to claim 8, wherein M is B, Al, Ga, In or Pd.

11. Metal complex according to claim 1, wherein the metal complexes have the following formula 4 ##STR00014## wherein M is B, Al, Ga, Zn, Fe or Pd, X is the hydride anion (H.sup.−) or methylide (CH.sub.3.sup.−), a is 1 or 2 and n is 0, 1 or 2;

12. Metal complex according to claim 11, wherein the N-aminoguarridinate-ligand is N,N′-bisdimethylamino-N″-dimethylguanidinate (bdmg)

13. Metal complex according to claim 11, wherein M is Ga, Zn or Fe.

14. Metal complex according to claim 11, wherein X is methylide, a and n are both 1 or 2.

15. Metal complex according to claim 1, wherein the metal complexes have the following formula 5 ##STR00015## wherein M is La, Ce, Pr, Nd, Sm or Yb; R.sup.3 is CH.sub.3 or N(CH.sub.3).sub.2; X is the hydride anion (H.sup.−) or methylide (CH.sub.3.sup.−); a is 1, 2 or 3; and n is 0, 1 or 2,

16. Metal complex according to claim 1, wherein the metal complexes have the following formula formula 6 ##STR00016## wherein M is Ce, Pr, .Nd, Sm or Yb; X is the hydride anion (H.sup.−) or methylide (CH.sub.3.sup.−); a is 1, 2 or 3; and n is 0, 1 or 2,

17. Metal complex according to claim 16, wherein M is Ce, Pr, Nd, Sm or Yb, n is 0 and a is 3.

18. Metal complex according to claim 1, wherein L is selected from pyridine, dioxane, NH.sub.3, THF, CO, an alkylphosphine or an arylphosphine.

19. Metal complex according to claim 1, wherein L is selected from pyridine, NH.sub.3, CO, PMe.sub.3, PCy.sub.3 and PPh.sub.3.

20. Metal complex according to claim 1, wherein L is selected from NH.sub.3 and CO.

21. Metal complex according to claim 1, wherein M is selected from the group of boron (B), aluminum (Al), gallium (Ga), indium (In), silicon (Si), germanium (Ge), tin (Sn), arsenic (As), antimony (Sb), titanium (Ti), zirconium (Zr), hafnium (Hf), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), ruthenium (Ru), rhodium (Rh), palladium (Pd) and platinum (Pt).

22. Metal complex according to claim 1, wherein M is selected from the group of boron (B), aluminum (Al), gallium (Ga), indium (In) and palladium (Pd).

23. Process for preparing a metal complex according to claim 1, comprising the steps of 1) Preparing an N-aminoguanidine ligand; 2) Preparing the metal complex from the N-aminoguanidine ligand.

24. Process according to claim 23, wherein step 2) comprises the following reaction steps: a) optionally deprotonating the N-aminoguanidine ligand to an N-aminoguanidinate-ligand; b) providing a metal complex preparation mixture, which comprises the N-aminoguanidine ligand or the N-aminoguanidinate ligand obtained from optional step a), at least one metal starting compound and a reaction solvent; c) incubating the obtained metal complex preparation mixture with optional stirring; d) evaporating the reaction solvent; e) optionally purifying the remaining reaction product, preferably by washing with a washing solvent.

25. Process according to claim 23, wherein the reaction solvent is selected from pentane, hexane, heptane, benzene, toluene, dichloromethane, chloroform, diethyl ether, tetrahydrofuran, methanol, ethanol, isopropanol and mixtures thereof.

26. A method comprising utilizing the metal complex according to claims 1 as a precursor in a thin-film process, as a catalyst for olefin hydroamination, as a catalyst for olefin polymerization or combinations thereof.

27. The method according to claim 26, wherein the thin-film process is selected from the group of CND processes, MO-CVD processes and ALD processes.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0126] FIG. 1 shows an ORTEP plot of the crystal structure of Al(datg)Me.sub.2 (example 4). Nitrogen atoms are labelled N1 to N4, respectively. The central carbon atom of the guanidine group is labelled C2. The aluminium atom is labelled Al1. The carbon atoms in the methyl groups are not labelled. Hydrogen atoms are not shown. All bonds are shown as stick representations.

[0127] FIG. 2 shows an ORTEP plot of the crystal structure of Fe(bdmg).sub.2 (example 10). Nitrogen atoms are labelled N1 to N5 or N1′ to N5′, respectively. The central carbon atoms of the guanidine groups are labelled C1 and C1′. The iron atom is labelled Fe1. The carbon atoms in the methyl groups are not labelled. Hydrogen atoms are not shown. All bonds are shown as stick representations.

[0128] FIG. 3 shows an ORTEP plot of the crystal structure of Zn(bdmg).sub.2 (example 11). Nitrogen atoms are labelled N1 to N10, respectively. The central carbon atoms of the guanidine groups are labelled C1 and C8. The zinc atom is labelled Zn1. The carbon atoms in the methyl groups are not labelled. Hydrogen atoms are not shown. All bonds are shown as stick representations.

[0129] FIG. 4 shows an ORTEP plot of the crystal structure of Yb(bdmg).sub.3 (example 12). Nitrogen atoms are labelled N1 to N8 or N1′ to N8′, respectively. The central carbon atoms of the guanidine groups are labelled C1, C1′ and C8. The ytterbium atom is labelled Yb1. The carbon atoms in the methyl groups are not labelled. Hydrogen atoms are not shown. All bonds are shown as stick representations.

EXAMPLES

ABBREVIATIONS

[0130] Me: methyl, —CH.sub.3

[0131] DCM: Dichloromethane

[0132] DEE: Diethyl ether

[0133] MHz: megahertz, 10.sup.6 s.sup.−1

[0134] MeCN: acetonitrile

[0135] ppm: parts per million, unit of chemical shift in NMR spectroscopy

[0136] THF: tetrahydrofuran

[0137] TMS: tetramethylsilane

[0138] For the Multiplicities in the NMR Spectra the Abbreviations are as Follows:

[0139] s: singlet

[0140] bs: broad singlet

[0141] d: doublet

[0142] Intensities in the IR Spectra are Abbreviated as Follows:

[0143] w: weak

[0144] m: moderately strong

[0145] s: strong

[0146] b: broad

General Remarks

[0147] All syntheses have been performed under N.sub.2 inert gas conditions using a common Schlenk line or an inert gas glovebox workstation (Braun). The nitrogen gas used was dried using columns filled with P.sub.4O.sub.10 resin. The vacuum-inert-gas-pipe was connected to a rotary vane pump (Vakuubrand).

[0148] The solvents used were dried by standard procedures (W. L. F. Armarego, D. D. Perrin, Purification of laboratory chemicals, 4. ed., Elsevier, Burlington, 1996) and stored in absorption columns over aluminium oxide/molecular sieve 3 Å/R3-11G-catalyst (BASF).

[0149] The chemical shift δ of the NMR spectra is specified in ppm relative to TMS as internal standard. Residual protons or respectively solvent signals of the respective deuterated solvent are used for calibration of the .sup.1H- and .sup.13C-NMR scales (.sup.1H-NMR: CDCl.sub.3: 7.26 ppm, C.sub.6D.sub.6: 7.16 ppm; .sup.13C-NMR: CDCl.sub.3: 77.16 ppm, C.sub.6D.sub.6: 128.06 ppm).

[0150] Buyable educts were purchased at the companies Sigma Aldrich, TCI Europe, Alfa Aesar and Merck. KHMDS (J. Åhman, P. Somfai, Synth. Commun. 1995, 25, 2301-2303) and dichloromethylethylendimethyl-ammoniumchloride (M. Vilkas, D. Qasmi, Synth. Commun.1990, 20, 2769-2773) were prepared as described in the respective literature instructions.

Examples 1 and 2

Preparation of an N-aminoguanidine ligand

Example 1:

Preparation of N-dimethylamino-N′,N″-trimethylguanidine (Hdatg)

[0151] Trimethylthiourea (11.85 g, 100 mmol, 1.00 equivalent) was suspended in 20 ml DCM at 0° C. Methyl iodide (MeI) (6.40 ml, 103 mmol, 1.03 equivalents) was added drop-wise and the solution was slowly heated to room temperature (RT). After 24 hours the intermediate product was concentrated in vacuum. The clear, yellow and highly viscous oil crystallized slowly. MeI was dissolved with 10 ml THF. All other volatile components were removed in vacuum. The sulfonium salt obtained was dissolved in 8 ml MeCN. N,N-dimethylhydrazine (8.5 ml, 112 mmol, 1.12 equivalents) was added, the solution was stirred for 2 hours at 40° C. and subsequently for 15 minutes at RT. Methanethiol was removed with N.sub.2. MeCN was removed in vacuum. The residues were washed with concentrated KOH.sub.aq and extracted with DCM. DCM was removed in vacuum and the product was distilled (35 mbar, 68° C.-73° C.). 7.64 g (53.0 mmol, 53%) of the clear product were obtained.

[0152] .sup.1H-NMR (300 MHz, C.sub.6D.sub.6): δ=5.73 (s, 1H, NH), 2.55 (s, 6H, NNMe.sub.2), 2.46 (s, 6H, NMe.sub.2), 2.38 (d, 3H, J=5.7 Hz, NHMe).

[0153] .sup.13C-NMR (75 MHz, C.sub.6D.sub.6): δ=164.9 (C.sub.q), 48.8 (NNMe.sub.2), 39.8 (NMe.sub.2), 31.3 (NMe).

[0154] HR-MS (ESI): m/z calculated for [M+H].sup.+: 145.1448, found: 145.1448.

[0155] IR: {tilde over (v)} (cm.sup.−1)=2980 (w), 2948 (m), 2853 (m), 2817 (w), 2772 (w), 1640 (s), 1466 (w), 1449 (w), 1340 (w), 1254 (w), 1157 (m), 1016 (m), 959 (s), 899 (w), 682 (b), 594 (w), 447 (w).

Example 2

Preparation of N,N’-bis(dimethylamino)-N”-dimethylguanidine (Hbdmg):

[0156] N,N-dimethylhydrazine (0.47 ml, 6.16 mmol, 2.0 equivalents) and triethylamine (1.50 ml, 10.80 mmol, 3.5 equivalents) were slowly added drop-wise and under stirring to dichloromethylethylendimethyl-ammoniumchloride (500 mg, 3.08 mmol, 1.0 equivalent) in 5 ml THF at −10° C. After 1 hour the solution was slowly heated to RT. The occurring precipitate was removed by filtering and the volatile components were removed under reduced pressure. The product (517 mg, 2.98 mmol, 97%) was obtained as clear oil.

[0157] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ=2.80 (s, 6H, NMe.sub.2), 2.46 (s, 6H, NNMe.sub.2) 2.33 (s, 6H, NNMe.sub.2), 6.78 (s, 1H, NH).

[0158] .sup.13C-NMR (75 MHz, CDCl.sub.3): δ=162.1 (C.sub.q), 48.2 (NHMe.sub.2), 47.1 (NNMe.sub.2), 38.9 (NMe.sub.2).

[0159] HR-MS (ESI): m/z calculated for [M+H].sup.+: 174.1713, found: 174.1713.

Examples 3 to 9

Preparation of metal complexes from an N-aminoguanidine ligand

[0160] In the examples below, Examples 3 to 5 and 7 to 9 describe complexes with the ligand datg, Example 6 describes a complex with the ligand bdmg.

Example 3

Preparation of [Pd(datg).SUB.2.]

[0161] KHMDS (219 mg, 1.1 mmol, 2.2 equivalents) was dissolved in 5 ml toluene and Hdatg (159 mg, 1.1 mmol, 2.2 equivalents) was added drop-wise under stirring. The reaction mixture was stirred for 15 minutes. Subsequently, the solvent and H-HMDS were removed in vacuum. The Kdatg obtained was dissolved in 3 ml THF and was slowly added drop-wise to [PdCl.sub.2(MeCN).sub.2] (200 mg, 0.77 mmol, 1.0 equivalent) in 3 ml THF. The solution was stirred 30 minutes at room temperature and subsequently 30 minutes at 40° C. KCl was removed by centrifugation and the solvent was removed from the orange supernatant in vacuum. The resulting orange-brown solid was washed with hexane and dried in vacuum. 87 mg (0.22 mmol, 29%) of the desired product were obtained as orange solid.

[0162] .sup.1H-NMR (300 MHz, C.sub.6D.sub.6): δ=2.81 (s, 6H, PdNMe), 2.56 (s, 12H, PdNMe.sub.2), 2.47 (s, 12H, NMe.sub.2).

[0163] .sup.13C-NMR (75 MHz, C.sub.6D.sub.6): δ=160.2 (C.sub.quart), 53.9 (PdNMe.sub.2), 41.9 (NMe.sub.2), 39.4 (PdNMe).

[0164] HR-MS (APCI, MeCN): m/z calculated for [M+H].sup.+: 393.1706, found: 393.1701.

[0165] IR: {tilde over (v)} (cm.sup.−1)=2924 (b), 2862 (b), 1538 (s), 1482 (m), 1444 (m), 1362 (s), 1180 (w), 1117 (s), 1055 (w), 941 (m), 867 (w), 822 (m), 736 (w), 685 (w), 570 (m), 535 (m), 502 (m).

Example 4

[0166] Preparation of [Al(datg)Me.sub.2]

[0167] Hdatg (415 mg, 2.88 mmol, 1.01 equivalents) in 5 ml toluene was slowly added drop-wise to trimethylaluminium (205 mg, 2.84 mmol, 1.00 equivalent) in 5 ml toluene at −78° C. After 1 hour the temperature was raised to 0° C. After 45 minutes it was stirred for 12 hours at RT. Subsequently, the solvent was removed in vacuum and a slightly yellow oil was obtained, which was crystallizing at around 10° C. The product was transferred by vaporization at 40° C. followed by condensation. A colourless crystalline solid (135 mg, 674 pmol, 24%) was obtained, which was easily melted by hand warmth.

[0168] .sup.1H-NMR (300 MHz, C.sub.6D.sub.6): δ=2.72 (s, 3H, NMe), 2.51 (s, 6H, NMe.sub.2), 2.19 (s, 6H, NMe.sub.2), −0.45 (s, 6H, AlMe.sub.2).

[0169] .sup.13C-NMR (75 MHz, C.sub.6D.sub.6): δ=170.5 (CH), 48.7 (NMe.sub.2), 40.6 (NMe.sub.2), 31.8(NMe), −11.2 (AlMe.sub.2).

[0170] IR: {tilde over (v)} (cm.sup.−1)=3005, 2935, 2881, 2815, 2795, 1522, 1492, 1474, 1448, 1416, 1404, 1374, 1267, 1233, 1187, 1164, 1128, 1102, 1093, 1056, 999, 987, 935, 867, 823, 748, 719, 661, 589, 559, 491, 449, 413.

[0171] Melting point: no exact measurement, approximately >20° C.

Example 5

[0172] Preparation of [In(datg)Me.sub.2]

[0173] Hdatg (290 mg, 2.01 mmol, 1.00 equivalent) in 3 ml toluene was slowly added drop-wise to trimethylindium (321 mg, 2.01 mmol, 1.00 equivalent) in 2.5 ml toluene at −78° C. After 45 minutes the temperature was raised to 0° C. After further 45 minutes it was stirred for 12 hours at RT. Subsequently, the solvent was removed in vacuum and a slightly pink oil was obtained. The product was transferred by vaporization at 40° C. followed by condensation. A colourless liquid (233 mg, 809 μmol, 40%) was obtained and identified as [In(datg)Me.sub.2].

[0174] .sup.1H-NMR (300 MHz, C.sub.6D.sub.6): δ=2.90 (d, 3H, J=1.1 Hz, NMe), 2.63 (d, 6H, J=1.5 Hz, NMe.sub.2), 2.20 (s, 6H, NMe.sub.2), −0.09 (d, 6H, J=1.7 Hz, InMe.sub.2).

[0175] .sup.13C-NMR (75 MHz, C.sub.6D.sub.6): δ=170.8 (CH), 50.0 (NMe.sub.2), 41.5 (NMe.sub.2), 35.0(NMe), −8.7 (InMe.sub.2).

[0176] IR: {tilde over (v)} (cm.sup.−1)=2991, 2915, 2862, 2805, 1615, 1590, 1524, 1483, 1444, 1414, 1401, 1360, 1267, 1224, 1182, 1147, 1120, 1054, 1006, 985, 941, 907, 860, 822, 690, 671, 555, 508, 481, 432.

[0177] Melting point: no exact measurement, <0° C.

Example 6

[0178] Preparation of [Ga(bdmg)Me.sub.2]

[0179] Trimethylgallium (184 mg, 1.60 mmol, 1.00 equivalent) in 2 ml toluene at −78° C. was slowly added drop-wise to Hbdmg (275 mg, 1.60 mmol, 1.00 equivalent) in 3 ml toluene. After 1 hour the temperature was raised to 0° C. After further 45 minutes it was stirred for 36 hours at RT. Subsequently, the solvent was removed in vacuum and a slightly yellow oil (167 mg, 0.61 mmol, 38%) was obtained and identified as the desired product.

[0180] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ=2.86 (s, 6H, NMe.sub.2), 2.53 (s, 6H, NNMe.sub.2), 2.48 (s, 6H, NNMe.sub.2), −0.249 (s, 6H, GaMe.sub.2).

[0181] .sup.13C-NMR (75 MHz, CDCl.sub.3): δ=166.1 (C.sub.quart), 48.0 (NNMe.sub.2), 47.8 (NNMe.sub.2), 39.7(NMe.sub.2), −7.1 (GaMe.sub.2).

Example 7

Preparation of [B(datg)H.SUB.2.]

[0182] Lithium borohydride (150 mg, 6.8 mmol, 1 equivalent) was suspended in 10 ml THF. 2.2 ml of a 1 M BCl.sub.3 solution in hexane (2.2 mmol, 0.3 equivalents) was slowly added drop-wise to the suspension at −78° C. The reaction mixture was stirred for 1 hour at RT. Subsequently, the mixture was cooled down to −78° C. and mixed with Hdatg (1.7 ml, 12.7 mmol, 1.8 equivalents). It was heated to RT and stirred overnight. The precipitate was removed from the reaction mixture using Celite™ and the clear filtrate was dried in high vacuum. 636 mg (4.1 mmol, 60%) of the product were obtained as colourless solid.

[0183] .sup.1H-NMR (CDCl.sub.3, 300 MHz): δ/ppm=2.68 (s, 6H, CNMe.sub.2), 2.52 (s, 3H, NMe), 2.51 (s, 6H, BNMe.sub.2).

[0184] .sup.13C-NMR (CDCl.sub.3, 75 MHz): Signal intensity too low due to poor solubility.

[0185] HR-MS(ESI): m/z calculated for [M+H].sup.+: 157.1619, found: 157.1621.

Example 8

Preparation of [Al(datg)H.SUB.2.]

[0186] LiAlH.sub.4 (164 mg, 4.3 mmol, 2.2 equivalents) was dissolved at −78° C. in 20 ml diethyl ether and trimethylamine hydrochloride (392 mg, 4.1 mmol, 2 equivalents) was added in portions. The reaction mixture was stirred for 1 hour at −78° C. Subsequently, it was heated to RT and stirred for another 12 hours at RT. Hdatg (0.26 ml, 2 mmol, 1 equivalent) was added drop-wise under constant stirring at 0° C. The mixture was heated to RT and stirred for 12 hours. The precipitate was removed using Celite™ and the clear filtrate was dried in high vacuum. The residual was suspended in 10 ml hexane and in 5 ml diethyl ether. The turbid solution was filtered and the solvent of the clear filtrate was removed in high vacuum. 165 mg (0.9 mmol, 48%) of a clear solid were obtained as product.

[0187] .sup.1H-NMR (CDCl.sub.3, 300 MHz): δ/ppm=4.02 (bs, 2H, AlH.sub.2), 2.62 (s, 6H, CNMe.sub.2), 2.47 (s, 9H, NMe.sub.2, NMe).

[0188] .sup.13C-NMR (CDCl.sub.3, 75 MHz): Signal intensity too low due to poor solubility.

Example 9

Preparation of [Ga(datg)H.SUB.2.]

[0189] Gallium trichloride (0.55 g, 2.6 mmol, 1 equivalent) was dissolved in 5 ml diethyl ether at −78° C. and added drop-wise to a suspension of lithium hydride (0.40 g, 50.3 mmol, 16 equivalents) in 5 ml diethyl ether cooled to −78° C. The reaction mixture was stirred for another 2 hours at −78° C. Subsequently, it was heated to RT and it was stirred overnight. The precipitate was removed by filtering and the clear filtrate was mixed at −78° C. with a solution of gallium trichloride (0.40 g, 2.3 mmol, 0.7 equivalents) in 4 ml diethyl ether also cooled to −78° C. The resulting suspension was heated to 0° C. and subsequently filtered. The filtrate was cooled to −78° C. and mixed with Hdatg (0.33 ml, 2.5 mmol, 0.8 equivalents). The resulting suspension was slowly heated to 0° C. and was stirred overnight. The reaction mixture was filtered using Celite™ and the clear filtrate was concentrated by evaporation in high vacuum at 0° C. 429 mg (1.9 mmol, 64%) of the product were obtained as white solid.

[0190] .sup.1H-NMR (CDCl.sub.3, 300 MHz): δ/ppm=5.2 (bs, 2H, GaH.sub.2), 2.88 (s, 6H, CNMe.sub.2), 2.67 (s, 9H, NMe.sub.2, NMe).

[0191] .sup.13C-NMR (CDCl.sub.3, 75 MHz): δ/ppm=169.5 (C.sub.quart.) , 49.8 (NNMe), 40.2 (NMe.sub.2), 33.4 (NMe).

Example 10

Synthesis of [Fe(bdmg).SUB.2.]

[0192] Hbdmg (300 mg, 1.73 mmol, 2.2 eq) was added drop wise to KHMDS (345 mg, 1.73 mmol, 2.2 eq) in toluene (10 mL) at room temperature. The mixture was stirred for 1 h during which a white precipitate formed, afterwards the volatile compounds were removed under reduced pressure. FeCl.sub.2 (98.8 mg, 0.78 mmol, 1.0 eq) in toluene (15 mL) was added to the so prepared Kbdmg in toluene (10 mL). The solution was stirred for 48 h at 90° C. during which it turned yellow. The solvent was removed under reduced pressure, the dark yellow residue solved in hexane (25 mL), filtered through celite and the solvent again removed under reduced pressure. This led to the desired product in form of a dark yellow solid (136 mg, 0.34 mmol, 43%).

[0193] .sup.1H-NMR (C.sub.6D.sub.6, 300 MHz): δ/ppm=−25.39 (s, 12 H, C=NNMe.sub.2), −25.18 (s, 12 H, C−NNMe.sub.2), −24.80 (s, 12 H, CNMe.sub.2).

[0194] IR: {tilde over (v)} (cm.sup.−1)=2960 (w), 2940 (w), 2746 (w), 1609 (w), 1507 (w), 1476 (w) 1363 (w), 1257 (s), 1173 (w), 1220 (w) 1143 (m), 1082 (s), 1064 (s), 1052 (s), 1011 (vs), 939 (w), 913 (w), 868 (m), 792 (vs), 732 (m), 664 (w), 558 (w), 523 (m), 488 (m).

Example 11

Synthesis of [Zn(bdmg).SUB.2.]

[0195] Hbdmg (2.2 g, 12.7 mmol, 2.0 eq) was added drop wise to [Zn(HMDS).sub.2] (2.44 g, 6.35 mmol, 1.0 eq) in toluene (10 mL) at room temperature. The solution was stirred for 4 h, afterwards the solvent was removed under reduced pressure. Sublimation of the white solid yielded 2.31 g (5.65 mmol, 89%) of the desired product.

[0196] .sup.1H-NMR (C.sub.6D.sub.6, 300 MHz): δ/ppm=2.35 (s, 6 H, C=NNMeMe), 2.37 (s, 6 H, C=NNMeMe), 2.46 (s, 12 H, C−NNMe.sub.2), 2.96 (s, 12 H, CNMe.sub.2).

[0197] .sup.13C-NMR (C.sub.6D.sub.6, 75 MHz): δ/ppm=41.1 (C−NNMe.sub.2, CNMe.sub.2), 50.2 (C=NNMe.sub.2), 168.6 (C.sub.quart).

[0198] HR-EI-MS: calc. for C.sub.14H.sub.36N.sub.10Zn: 408.2416 m/z, found: 408.2429 m/z.

[0199] IR: {tilde over (v)} (cm.sup.−1)=2999 (m), 2930 (s), 2847 (m), 2804 (m), 2782 (m). 2759 (m), 1510 (vs), 1481 (vs), 1437 (vs), 1370 (vs), 1258 (m), 1222 (m), 1177 (m), 1143 (s), 1077 (m), 1003 (s), 941 (s), 914 (s), 872 (s), 801 (m), 731 (m), 669 (w), 558 (w), 521 (s), 449 (m), 424 (vs).

Example 12

Synthesis of [Yb(bdmg).SUB.3.]

[0200] Hbdmg (0.11 g, 0.65 mmol, 3.2 eq) was added to a solution of KHMDS (0.13 g, 0.65 mmol, 3.2 eq) in 5 mL THF. The mixture was stirred for 1 h, afterwards the volatile compounds were removed under reduced pressure. The residue was solved in 5 mL THF and a slurry of [YbCl.sub.3(thf).sub.3] (0.1 g, 0.20 mmol, 1.0 eq) in THF (3 mL) was added at room temperature. The solution was stirred for 12 h, afterwards the solvent was removed under reduced pressure, toluene was added to the residue and KCl was filtered off. The solution was concentrated and the desired product was obtained as yellow crystals (62 mg, 0.09 mmol, 45%).

[0201] .sup.1H-NMR (C.sub.6D.sub.6, 300MHz): δ/ppm=2.24 (s, 6H, C=NN(CH.sub.3).sub.2), 2.46 (s, 6H, C−NN(CH.sub.3).sub.2), 2.83 (s, 6H, CN(CH.sub.3).sub.2).