METAL COMPLEXES HAVING TRIAZENIDO LIGANDS AND USES THEREOF FOR DEPOSITING METALS FROM THE GAS PHASE

Abstract

The invention relates to the use of a metal complex, which has at least one ligand of the formula R.sup.1N.sub.3R.sup.2, wherein R.sup.1 and R.sup.2 are hydrocarbon moieties, for depositing the metal or a compound of the metal from the gas phase. The invention further relates to methods for depositing metals from the metal complexes, and to metal complexes, substituted triazene compounds and to methods for the production thereof.

Claims

1. Use of a metal complex that has at least one ligand L with the formula R.sup.1N.sub.3R.sup.2, wherein R.sup.1 and R.sup.2 are hydrocarbon radicals, for depositing the metal or a compound of the metal from the gas phase.

2. Use according to claim 1, wherein the metal complex has at least one ligand L with the formula R.sup.1N.sub.3R.sup.2 and at least one further ligand X that is selected from H, halogen, CO and hydrocarbon ligands.

3. Use according to at least one of the preceding claims, wherein the metal complex has at least one ligand L with the formula R.sup.1N.sub.3R.sup.2, in which R.sup.1 and R.sup.2 are alkyl radicals.

4. Use according to at least one of the preceding claims, wherein the metal complex has the formula (1):
M.sub.x[(L.sup.1).sub.a(L.sup.2).sub.b(L.sup.3).sub.cX.sub.d](1) wherein the ligands L, that is L.sup.1, L.sup.2 and L.sup.3, are independently of one another selected from radicals of the formula R.sup.1N.sub.3R.sup.2, wherein R.sup.1 and R.sup.2 are hydrocarbon radicals, wherein at least for L.sup.1 the radicals R.sup.1 and R.sup.2 are alkyl radicals, X is independently selected from H, halogen, CO and hydrocarbon ligands, X is an integer between 1 and 4, a, b, c and d are integers, wherein the sum a+b+c+d is at least x and is not greater than 12, a is at least 1, and b, c and d may equal 0.

5. Use according to at least one of the preceding claims, wherein the metal complex is homoleptic and only has ligands L of the formula R.sup.1N.sub.3R.sup.2.

6. Use according to at least one of the preceding claims, wherein the metal complex is heteroleptic.

7. Use according to at least one of the preceding claims, wherein the radicals R.sup.1 and R.sup.2 have 1 to 30 C atoms independently of one another.

8. Use according to at least one of the preceding claims, wherein all the R.sup.1 and R.sup.2 radicals of the metal complex are alkyl radicals.

9. Use according to claim 8, wherein the R.sup.1 and R.sup.2 radicals independently have 1 to 15 C atoms.

10. Use according to claim 8 or 9, wherein all or part of the R.sup.1 and/or R.sup.2 radicals are branched and/or cyclic alkyl radicals.

11. Use according to claim 10, wherein all or part of the R.sup.1 and/or R.sup.2 radicals are tert-butyl.

12. Use according to at least one of the preceding claims, wherein the metal complex has at least one ligand L that is tert-butyl-N.sub.3-tert-butyl or tert-Butyl-N.sub.3-Methyl.

13. Use according to claim 12, wherein all ligands L of the metal complex are tert-Butyl-N.sub.3-tert-Butyl or tert-Butyl-N.sub.3-Methyl.

14. Use according to at least one of the preceding claims 2 to 13, wherein at least one X is a hydrocarbon ligand selected from alkyl or alkenyl of 1 to 12 carbon atoms and aromatic hydrocarbons having 5 to 30 C atoms.

15. Use according to at least one of the preceding claims, wherein the metal M is selected from In, Co, Cu, Ru, Al, Ga, Tl, and La.

16. Use according to claim 15, wherein the metal M is selected from In, Co, Cu, La and Ru.

17. Use according to at least one of the preceding claims, wherein the metal complex has the formula (2):
M[(L.sup.1).sub.aX.sub.d](2) wherein L.sup.1 has the formula R.sup.1N.sub.3R.sup.2, wherein R.sup.1 and R.sup.2 are alkyl radicals with 1 to 12 C atoms, X is selected from H, halogen, CO and alkyl having 1 to 12 C atoms, a=2 or 3, d=0 or 1, and M is selected from In, Co, Cu, Al, Ga, Tl, and La.

18. Use according to claim 17, wherein the metal complex has one of formulas (3) to (5):
M[(L.sup.1).sub.2X](3) wherein L.sup.1 has the formula R.sup.1N.sub.3R.sup.2, wherein R.sup.1 and R.sup.2 are alkyl radicals with 1 to 12 C atoms, X is selected from H and alkyl with 1 to 12 C atoms, and M=Al or Ga;
M[(L.sup.1).sub.3](4) wherein L.sup.1 has the formula R.sup.1N.sub.3R.sup.2, wherein R.sup.1 and R.sup.2 are alkyl radicals with 1 to 12 C atoms, and M=In, TI or La;
M.sub.x(L.sup.1).sub.a(5) wherein L.sup.1 has the formula R.sup.1N.sub.3R.sup.2, wherein R.sup.1 and R.sup.2 are alkyl radicals with 1 to 12 C atoms, x is an integer between 1 and 4, and a is an integer between 2 and 8, with the proviso that a/x=1 or 2, and M=Co or Cu.

19. Use according to at least one of the claims 1 to 16, wherein the metal complex has the formula (6):
(Ru[(L.sup.1)X.sup.1X.sup.2](6) wherein L.sup.1 has the formula R.sup.1N.sub.3R.sup.2, wherein R.sup.1 and R.sup.2 are alkyl radicals with 1 to 12 C atoms, X.sup.1 is an aromatic hydrocarbon ligand having from 5 to 30 C atoms, and X.sup.2 is selected not from any radical, H, halogen, CO and alkyl having 1 to 6 C atoms.

20. Use according to at least one of the preceding claims, wherein the metal complex is sublimable or vaporizable without decomposition taking place.

21. Use according to at least one of the preceding claims, wherein the molecular weight of the metal complex is less than less than 600 g/mol.

22. Use according to at least one of the preceding claims, wherein the metal complex is thermally stable at 100 C. and/or decomposes in a temperature range from 100 C. to 400 C., wherein the temperature is determined at atmospheric pressure or at reduced pressure in the range from 10.sup.3 to 900 mbar.

23. Use according to at least one of the preceding claims, wherein the deposition of the metal or of the compound of the metal from the gas phase is effected at reduced pressure in the range from 10.sup.3 to 900 mbar, preferably in the range from 10.sup.2 to 1 mbar, and in particular 10.sup.2 mbar.

24. Method for the production of coated substrates, comprising the steps of: (a) providing a metal complex according to at least one of the preceding claims, and (b) depositing the metal or a compound of the metal on the surface of the substrate by metal-organic vapor deposition.

25. Method or use according to at least one of the preceding claims, wherein the method is a metal-organic chemical vapor deposition (MOCVD).

26. Method or use according to at least one of the preceding claims, wherein the method is a metal-organic gas phase epitaxy (MOVPE).

27. Method or use according to at least one of the preceding claims, wherein the compound of the metal is selected from semiconductor compounds, alloys, nitrides, phosphides, arsenids and silicides.

28. Method or use according to at least one of the preceding claims, wherein the metal complex is sublimated or evaporated without decomposition taking place.

29. Method or use according to at least one of the preceding claims, wherein the metal complex decomposes in the gas phase at a temperature which is not more than 100 C. above the sublimation temperature or evaporation temperature.

30. Method for the production of a metal complex, wherein the metal complex is such according to least one of claims 1 to 23, comprising the steps of (A) providing a compound of the formula R.sup.1(N.sub.3)A-R.sup.2, wherein A is selected from H or an alkaline metal, in particular Li, Na or K, and (B) bringing into contact with a compound of the metal.

31. Method according to claim 30, wherein the compound of the metal in step (B) is selected from a metal salt, a metal-organic compound or a metal complex of the metal which does not have a ligand L.

32. Method for the production of a compound of the formula R.sup.1(N.sub.3)A-R.sup.2 in a reaction mixture that contains the compounds R.sup.1N.sub.3 and AR.sup.2, wherein A is an alkaline metal.

33. Method according to claim 30 or 31, wherein in a preceding step the compound of the formula R.sup.1(N.sub.3)A-R.sup.2, wherein A is an alkaline metal, is prepared with a method according to claim 32.

34. Method according to at least one of claims 30 to 33, wherein A=Li.

35. Metal complex of formula (1):
M.sub.x[(L.sup.1).sub.a(L.sup.2).sub.b(L.sup.3).sub.cX.sub.d](1) wherein the ligands L, that is L.sup.1, L.sup.2 and L.sup.3, are independently of one another selected from radicals of the formula R.sup.1N.sub.3R.sup.2, wherein R.sup.1 and R.sup.2 are hydrocarbon radicals, wherein at least for L.sup.1 the radicals R.sup.1 and R.sup.2 are alkyl radicals, The ligand X is selected from halogen, H, CO and hydrocarbon ligands, X is an integer between 1 and 4, a, b, c and d are integers, wherein the sum a+b+c+d is at least x and is not greater than 12, a is at least 1, and b, c and d may equal 0, wherein at least one of the following conditions (i) to (ii) is satisfied: (i) M is selected from metals of the VIIIth subgroup and the lanthanides of the Periodic Table of the Elements, (ii) at least one ligand L has at least one radical R.sup.1 or R.sup.2 that is tert-butyl.

36. Metal complex according to claim 35 having one of formulas (7) to (20) or (102) to (115): ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055##

37. Compound selected from tert-Butyl-(N.sub.3)HCH.sub.3 and organo-alkaline metal salts of the formula R.sup.1(N.sub.3)A-R.sup.2, wherein R.sup.1 and R.sup.2 are alkyl radicals and A is an alkaline metal, especially Li, Na or K.

38. Organo-alkaline metal salt according to claim 37 which has one of formulas (21) to (23) or (116) to (117): ##STR00056##

Description

EXEMPLARY EMBODIMENTS

Overview of the Compounds Produced:

[0150] ##STR00007## ##STR00008## ##STR00009## ##STR00010## ##STR00011## ##STR00012##

Example 1: Tert-Butyl Azide

[0151] In general, organic azides are classified as explosive on the basis of two criteria, both conditions being empirical limits of explosivity. [0152] 1) [(quantity (N atoms)+quantity (O atoms))/quantity (C atoms)]<3 [0153] 2) Percentage by weight of acidic nitrogen >25 w %

[0154] According to both criteria, the tert-butyl azide described here should be classified as explosive material. However, accidents in representation or handling are not known. In addition, it is a liquid that can be distilled at 79 C. for purification and has an N.sub.2 separation temperature of approximately 550 C., which is comparatively high for organic azides.

[0155] There are several synthetic approaches that have been reported since the end of the 1960s. For example, one approach starts out from tertbutyl chloride that is converted with NaN.sub.3 and ZnCl.sub.2 as the catalyst in CS.sub.2..sup.[34] Moreover, in another synthetic access, tertbutyl nitrate is converted with LiN.sub.3 in DMF..sup.[35,36] Both approaches may lead to various complications due to incomplete reactions or incomplete separation of the by-products. Furthermore, the use of carbon disulfide should be avoided due to the high toxicity. Therefore, an approach starting with tert-butanol was investigated, in which the alcohol is reacted with NaN.sub.3 in a mixture of water and sulfuric acid..sup.[37] Upscaling of the reaction to the tert-butyl azide up to several 100 g according to the literature is possible without problems and safely. Nevertheless, it should always be borne in mind with this synthesis route that HN.sub.3 is formed in the reaction mixture, which should absolutely be handled in generously diluted form.

1.1 Synthesis of Tertbutyl Azide

[0156] ##STR00013##

[0157] 75 mL H.sub.2O and 50 mL concentrated H.sub.2SO.sub.4 were submitted at 5 C. NaN.sub.3 (9.80 g, 151 mmol, 1.10 eq) was slowly added with a solids dispenser. The colorless suspension was stirred for 15 min and allowed to warm to 0 C. tBuOH (10.2 g, 137 mmol, 1.00 eq) was slowly added in drops via a dropping funnel. The solid present in the reaction mixture dissolved slowly in the process. The reaction solution was stirred at RT for 16 h and transferred to a separating funnel in order to achieve separation of the phases. The aqueous phase was separated and immediately neutralized with NaOH (2 m). The organic phase was washed twice with 20 mL of NaOH (2 m) each, then dried over Na.sub.2SO.sub.4. The desired product was recondensed and could be obtained with a yield of 69% (9.40 g, 94.8 mmol) in the form of a colorless liquid.

Example 2: Synthesis of H(dbt) and Li(dbt)

2.1 Synthesis of Li(dbt)Method 1

[0158] ##STR00014##

[0159] tBuN.sub.3 (10.17 g, 102.6 mmol, 1.00 eq) was placed in 100 mL pentane and cooled to 5 C. Within one hour, a solution of tBuLi in pentane (60 mL, 1.83 m, 110 mmol, 1.07 eq) was added in drops. The dropping funnel was purged twice with 10 ml of pentane. The reaction mixture was slowly heated and stirred for 1 h at RT. 180 mL H.sub.2O were added to the slightly yellow suspension, which decolorized the mixture. The aqueous phase was separated and the organic phase was washed once more with 180 mL H.sub.2O. The organic phase was dried over Na.sub.2SO.sub.4, filtered, and the volatiles were removed in FV. The crude product was purified by distillation at 60 mbar and 70 C. The yield of the desired product in the form of a colorless, clear liquid was 32% (5.15 g, 32.7 mmol).

##STR00015##

[0160] H(dbt) (700 mg, 4.45 mmol, 1.00 eq) was submitted in 10 mL Et.sub.2O and cooled to 0 C. A solution of nBuLi in hexane (1.8 mL, 2.5 m, 4.45 mmol, 1.00 eq) was slowly added in drops. The slightly yellow solution was stirred for 1 h at RT, then brought to RT and stirred for a further 24 hours. The solvent of the clear solution was removed in FV to give a slightly yellow solid. The desired product was dried in FV and could be isolated with a yield of 95% (687 mg, 4.21 mmol).

2.2 Synthesis of Li(dbt)Method 2 (Optimized Synthesis)

[0161] ##STR00016##

[0162] tBuN.sub.3 (1.27 g, 12.8 mmol, 1.00 eq) was submitted in 10 mL pentane and cooled to 5 C. A solution of tBuLi in hexane (7.4 mL, 1.83 m, 13.7 mmol, 1.07 eq) was slowly added in drops, with a slight yellow coloration of the reaction mixture resulting from this. The reaction mixture was stirred at 5 C. for 1 h, then slowly warmed to RT and stirred for 1 hour. The slightly turbid solution was filtered through a syringe filter and the solvent of the slightly yellow filtrate was removed in FV. The desired product could be obtained with a yield of 83% (1.64 g, 10.0 mmol).

[0163] No differences between the two batches of Li(dbt) could be observed with the analytical examinations carried out. The optimized synthesis of Li(dbt) is a single-stage synthesis without by-products. While the neutral ligand was initially assumed, the optimization leads both to savings in reagents and in various working steps, etc. a distillation.

Example 3: Synthesis of K(dbt)

[0164] ##STR00017##

[0165] BnK (700 mg, 4.45 mmol, 1.00 eq) was taken up in 10 mL Et.sub.2O and dropwise blended with H(dbt) (582 mg, 4.47 mmol, 1.00 eq) at 0 C. The colorless suspension was warmed to RT and stirred for 16 h. The slightly turbid solution was filtered, and the solvent of the colorless filtrate was completely removed at negative pressure. 85% (510 mg, 2.61 mmol) of the desired product could be obtained in the form of a colorless solid.

Example 4: Synthesis of Li(mbt)

[0166] ##STR00018##

[0167] tBuN.sub.3 (1.00 g, 10.7 mmol, 1.00 eq) was submitted in 15 mL pentane and cooled to 4 C. A solution of MeLi in Et.sub.2O (6.8 mL, 1.60 m, 10.7 mmol, 1.07 eq) was slowly added to the reaction solution dropwise, which yielded a colorless solid. The reaction mixture was warmed to RT, the resulting colorless precipitate was filtered off and dried in an FV for several hours. The desired product was obtained as a colorless solid with a yield of 87% (1.13 g, 9.31 mmol). Upscaling of the reaction is possible.

Example 5: Synthesis of H(mbt)

[0168] ##STR00019##

[0169] Li(mbt) (143 mg, 1.18 mmol, 1.00 eq) was placed in pentane and cooled to 0 C. While stirring, F.sub.3CCOOH (135 mg, 1.18 mmol, 1.00 eq) was slowly added dropwise, with a slight foaming of the reaction solution being observed. The Li(mbt) used went into solution on warming the reaction mixture to RT, and the slightly turbid suspension was stirred for 16 h at RT. After the suspension was filtered through a syringe filter and the pentane removed in FV, the desired product could be obtained in the form of a colorless liquid.

Example 6: Synthesis of [Al(dbt).SUB.2.(Me)]

[0170] ##STR00020##

[0171] A toluene solution of AlMe.sub.3 (33 mg, 0.46 mmol, 1.00 eq) was submitted and dropwise blended with H(dbt) (300 mg, 1.91 mmol, 3.00 eq) at RT. A gas evolution could be immediately observed. The colorless reaction mixture was stirred for 72 h at RT and filtered via syringe filter. The solvent of the filtrate was removed in FV to give a colorless oil. After repeated freeze-drying, the desired product was obtained in a yield of 87% (276 mg, 0.56 mmol) as a colorless solid (melting point: 46 C.).

Thermogravimetric Analysis of [Al(dbt).SUB.2.(Me)]

[0172] The crude product was analyzed by thermogravimetric analysis up to 700 C. at 10 K/min (FIG. 1). The thermogravimetric analysis shows a one-step process with an overall mass degradation of approximately 91.2%. A weight decrease of 3% of the starting material was observed at 127.2 C.

Example 7: Synthesis of [Ga(dbt).SUB.2.(H)]

[0173] ##STR00021##

[0174] A solution of GaCl.sub.3 (440 mg, 2.50 mmol, 1.00 eq) in 5 mL Et.sub.2O cooled down to 78 C. was added dropwise to a suspension of LiH (260 mg, 32.8 mmol, 13.1 eq) in 5 mL Et.sub.2O. A slightly gray precipitate immediately formed. The reaction mixture was stirred for 2 h at 78 C., then stirred for 16 h at RT. The slightly gray suspension was filtered into a pre-cooled flask. To the clear filtrate, a solution of GaCl.sub.3 (176 mg, 1.00 mmol, 0.40 eq) in 5 mL Et.sub.2O that was cooled down to 78 C. was added dropwise at 78 C. The suspension was heated to 0 C. while stirred and then filtered in a flask pre-cooled to 78 C. The clear filtrate was added dropwise at 0 C. to a solution of H(dbt) (786 mg, 5.00 mmol, 2.00 eq) in 5 mL Et.sub.2O. Gas evolution was immediately observed. The suspension was slowly warmed to RT and stirred for 16 h. The mixture was filtered through a syringe filter and all volatiles were removed in FV. A colorless solid remained, which was taken up in 5 mL of hexane and filtered again through a syringe filter. The solvent of the filtrate was removed in FV to obtain the product with a yield of 53% (508 mg, 1.33 mmol, melting point: 46 C.). Single crystals for structural analysis could be obtained by sublimation in FV at 60 C.

[0175] The corresponding dihydrido gallium complex [Ga(dbt)H.sub.2] could not be obtained by the 1:1 conversion of H(dbt) and [GaH.sub.3(OEt.sub.2)].

Thermogravimetric Analysis of [Ga(dbt).SUB.2.(H)]

[0176] The crude product was examined through thermogravimetric analysis to 900 C. at 10 K/min (FIG. 2). A total of 86.6% of the starting material was converted into the gas phase.

Example 8: Synthesis of [In(dbt)Me.SUB.2.]

[0177] ##STR00022##

[0178] H(dbt) (250 mg, 1.59 mmol, 1.00 eq) was provided in 8 mL pentane and cooled to 0 C. A toluene solution of InMe.sub.3 (254 mg, 1.59 mmol, 1.00 eq) was added dropwise to observe slight gas evolution. The reaction mixture was stirred for 1 h at 0 C. and for 16 h at RT. The solvent of the clear solution was removed in FV, allowing the desired product to be isolated as a colorless liquid. For purification, the product can be recondensed at 40 C. in a slight vacuum.

[0179] The reaction can also be carried out in an analogous manner in toluene, but this leads to difficulties in the isolation of the indium complex owing to the high volatility of the product.

Example 9: Synthesis of [In(dbt).SUB.3.]

[0180] ##STR00023##

[0181] InMe.sub.3 (150 mg, 0.94 mmol, 1.00 eq) was provided in 5 mL toluene, cooled to 0 C., and dropwise blended with H(dbt) (444 mg, 2.83 mmol, 3.00 eq). The reaction mixture was slowly warmed to RT and stirred for 16 h. The solvent of the clear solution was removed in FV. The desired product was obtained in the form of a colorless solid with a yield of 73% (403 mg, 0.69 mmol) and can be sublimated in FV at 80 C.

Thermogravimetric Analysis of [In(dbt).SUB.3.]

[0182] The crude product was examined through thermogravimetric analysis to 900 C. at 10 K/min (FIG. 3). The analysis shows a one-step process with an overall mass degradation of about 92.8%. A weight decrease of 3% of the starting material was observed at 196.7 C.

Example 10: Synthesis of [La(dbt).SUB.3.]

[0183] ##STR00024##

[0184] [La(hmds).sub.3] (225 mg, 0.36 mmol, 1.00 eq) was provided in 10 mL toluene and cooled to 0 C. H(dbt) (171 mg, 1.09 mmol, 3.00 eq) was dropwise added to the colorless solution. The clear, colorless reaction mixture was warmed to RT and stirred for 16 h. With the aid of a .sup.1H NMR reaction control, it was confirmed that no [La(hmds).sub.3] was present in the reaction mixture anymore. All volatile components of the reaction solution were removed in FV and the resulting colorless solid was dried at 60 C. in FV. The desired product was obtained in a 72% (158 mg, 0.26 mmol) yield.

Thermogravimetric Analysis of [La(dbt).SUB.3.]

[0185] The crude product was examined through thermogravimetric analysis to 800 C. at 10 K/min (FIG. 4). The thermogravimetric analysis shows a one-step process with an overall mass degradation of approximately 85%. A weight decrease of 3% of the starting material was observed at 85 C. In the range up to 100 C., it can be seen that residual traces of Hhmds are still present in the product. Starting from a temperature of 103 C., an initial melting process of the lanthanum complex occurs, wherein the maximum mass reduction is achieved at a temperature of 250 C. No significant mass degradation can be observed any more from a temperature of about 400 C.

Example 11: Synthesis of [Co(dbt).SUB.2.]

[0186] ##STR00025##

[0187] Li(dbt) (654 mg, 4.00 mmol, 2.00 eq) was provided with CoCl.sub.2 (260 mg, 2.00 mmol, 1.00 eq) and blended with 15 mL toluene. The reaction mixture was heated at 80 C. for 8 h, during which time a color change from blue to dark red was observed. The solvent of the cooled reaction mixture was removed in FV and the desired product was directly sublimated from the residue in FV at 100 C. [Co(dbt).sub.2] was obtained as a dark red, almost black solid with a yield of 53% (394 mg, 1.06 mmol).

Thermogravimetric Analysis and Residue Determination of [Co(dbt).SUB.2.]

[0188] In the TGA curve to 900 C. at 10 K/min (FIG. 5), a one-stage mass loss can be observed, in which the maximum mass degradation per time can be observed at a temperature of 248 C. At a temperature of 156 C., the sample degraded to 3%. Starting at a temperature of 91 C., an endothermic, very broad peak can be observed, which can be assigned to an irregular melting process. The total mass loss is 97%, the residue obtained being examined in more detail by means of XRPD. It was found that the residue is elemental cobalt.

Example 12: Synthesis of [Co.SUB.2.(mbt).SUB.4.]

[0189] ##STR00026##

[0190] Li(mbt) (193 mg, 1.59 mmol, 4.00 eq) and CoCl.sub.2 (103 mg, 0.79 mmol, 2.00 eq) were provided together and blended with 10 mL toluene at 0 C. Upon thawing of the reaction mixture, a color change from blue to dark brown could be observed. The reaction mixture was heated at 80 C. for 10 h and the solvent was removed in FV at RT. The desired product was sublimated from the dark brown residue in a dynamic vacuum at 85 C. The dinuclear cobalt complex was obtained as a red-brown solid with a yield of 51% (116 mg, 0.20 mmol). Single crystals for crystal structure analysis could be obtained by light vacuum sublimation at 100 C. Due to spin-pairing of the two cobalt cores in [Co.sub.2(mbt).sub.4], this, in contrast to [Co(dbt).sub.2], shows diamagnetic behavior.

Thermogravimetric Analysis and Residue Determination of [Co.sub.2(Mbt).sub.4]

[0191] The TGA curve to 900 C. at 10 K/min (FIG. 6) of the cobalt complex shows a one-stage course, wherein the maximum mass degradation per time can be observed at a temperature of 189 C. The 3% degradation was determined at a temperature of 147 C. Starting at a temperature of 184 C., an initial exothermic process can be detected, which leads to maximum mass degradation per time and can be assigned to a decomposition process. The total mass degradation was 82%, the residue obtained from this measurement being analyzed by means of XRPD. This could be identified as elemental cobalt.

Example 13: Synthesis of [Ru(dbt)(Cl)(p-Cymene)]

[0192] ##STR00027##

[0193] Li(dbt) (248 mg, 1.52 mmol, 1.00 eq) was provided in 5 mL toluene. The ruthenium precursor (465 mg, 0.76 mmol, 0.50 eq) was added portionwise and rinsed with 4 mL of toluene. After a short time, a color change from dark red to black was observed. The reaction mixture was stirred overnight at RT and filtered via syringe filter. The solvent of the yellow-black filtrate was removed in FV. The desired product was obtained in the form of a dark green solid with a yield of 51% (331 mg, 0.77 mmol, melting point: 66.5 C.).

Thermogravimetric Analysis of [Ru(dbt)(Cl)(p-Cymene)]

[0194] The TGA curve to 600 C. at 5 K/min (FIG. 7) shows a one-stage course with a maximum mass loss per time at 235 C. While the 3% degradation is at a temperature of 153 C., the total mass degradation is 67%. At a temperature of 67 C., a melting process starts, which proceeds almost continuously into a sublimation process. From a temperature of 200 C., a further exothermic peak can be observed on the basis of the SDTA curve, which can be assigned to the decomposition process (not shown). From a temperature of about 400 C., the mass degradation no longer changes significantly. The residue obtained in the measurement was examined in more detail by means of XRPD and elemental ruthenium could be confirmed.

Example 14: Synthesis of [Ru(dbt)(H)(p-Cymene)]

[0195] ##STR00028##

[0196] [Ru(dbt)(CI)(p-cymene)] (227 mg, 0.51 mmol, 1.00 eq) was provided in 5 mL toluene. At 0 C., a solution of Li[HBEt.sub.3] in THF (0.56 mL, 1 m, 0.56 mmol, 1.10 eq) was provided. The reaction mixture was slowly warmed to RT and stirred for 16 h. Precipitation of a colorless solid could be observed. The precipitated solid was separated by filtration and the solvent of the filtrate was removed in FV. The desired product could be obtained after repeated freeze drying in the form of a green-black viscous liquid. For purification, the ruthenium hydrido complex was recondensed in FV at 95 C.

[0197] Alternatively, the synthesis can also be carried out with LiAlH.sub.4 (0.25 equivalents). By contrast, the methyl-substituted complex, which can be represented by the conversion of [Ru(dbt)(CI)(p-cymene)] and methyllithium, is present as a solid.

Thermogravimetric Analysis of [Ru(dbt)(H)(p-Cymene)]

[0198] The crude product was examined through thermogravimetric analysis to 600 C. at 10 K/min (FIG. 8). The analysis shows a one-step process with an overall mass degradation of about 67.8%. A weight decrease of 3% of the starting material was observed at 150.5 C.

Example 15: Synthesis of [Ru(mbt)(Cl)(p-Cymene)]

[0199] ##STR00029##

[0200] Li(mbt) (221 mg, 1.82 mmol, 1.00 eq) was provided in 10 mL toluene and portionwise blended with [RuCl.sub.2(p-cymene)]2 (559 mg, 0.91 mmol, 0.50 eq) at 0 C. Upon slow thawing of the mixture to RT, a color change from brown to dark green could be observed. The reaction mixture was stirred for 16 h at RT and was filtered via a syringe filter. The solvent of the reddish filtrate was removed in FV and the remaining solid was freeze-dried several times. The desired product was obtained in the form of a dark red solid with a yield of 59% (414 mg, 1.07 mmol, melting point: 51.9 C.).

Thermogravimetric Analysis of [Ru(mbt)(Cl)(p-Cymene)]

[0201] The measured TGA/SDTA curve to 700 C. at 5 K/min (FIG. 9) shows a one-step mass degradation with a maximum degradation at a temperature of 169 C. Above this temperature, the mass loss per time decreases again, which can be observed in itself on the basis of a positive slope from the minimum. The 3% degradation of the ruthenium complex is at 118 C. Starting at a temperature of 52 C., an initial melting process can be observed, which proceeds continuously into a sublimation process. The total mass loss is at 64%. The residue obtained from this measurement was assayed by XRPD analysis and could be identified as elemental ruthenium.

Example 16: Synthesis of [Ru(mbt)(H)(p-Cymene)]

[0202] ##STR00030##

[0203] [Ru(mbt)(CI)(p-cymene)] (196 mg, 0.49 mmol, 1.00 eq) was dissolved in 5 mL toluene and blended with a solution of Li[HBEt.sub.3] in THF (0.54 mL, 1 m, 0.54 mmol, 1.10 eq) at 0 C. The reaction mixture was warmed slowly to RT and stirred for 16 h, wherein a colorless solid precipitated. This was separated and the solvent of the filtrate was removed in FV. The desired product could be obtained after repeated freeze drying in the form of a black viscous liquid.

[0204] .sup.1H-NMR (C.sub.6D.sub.6, 300 MHz, 300 K): /ppm=2.93 (s, 1H, RuH), 1.21 (d, .sup.3J.sub.HH=6.6 Hz, 6H, CHMe.sub.2), 1.31 (s, 9H, CMe.sub.3), 2.00 (s, 3H, C.sub.arom.Me), 2.49 (sept, .sup.3J.sub.HH=6.6 Hz, 1H, CHMe.sub.2), 3.40 (s, 3H, NMe), 4.72 (d, 3J.sub.HH=4.6 Hz, 2H, CH.sub.arom), 4.91 (d, .sup.3J.sub.HH=4.6 Hz, 2H, CH.sub.arom.).

[0205] IR: {tilde over (v)}/cm.sup.1=2958 (m), 2920 (m), 2864 (m), 1884 (w), 1457 (w), 1382 (w), 1356 (m), 1290 (w), 1260 (st), 1216 (w), 1193 (w), 1086 (st), 1021 (st), 913 (w), 799 (vst), 661 (w), 631 (w), 552 (w).

[0206] TGA: (T.sub.S=25 C., T.sub.E=600 C., 10 C./min), stages: 2

[0207] 3% degradation: 108.2 C., max. degradation (1st stage): 181.3 C., max. degradation (2nd stage): 436.1 C.,

[0208] Mass degradation (1st stage): 58.0%, Total mass degradation: 64.8%.

[0209] SDTA: T.sub.D1(Onset): 97.3 C., TD1(max.): 127.8 C., T.sub.D2(onset): 162.1 C., T.sub.D2(max): 169.8 C., T.sub.D3 (Onset): 183.8 C., T.sub.D3(max): 192.1 C.

[0210] FIG. 14 shows a graphical representation of the TGA and SDTA measurements.

Example 17: Synthesis of [Ru(mbt)(Cp*)(CO)]

[0211] ##STR00031##

[0212] [RuCp*Cl].sub.4 (90 mg, 0.45 mmol, 1.00 eq) and Li(mbt) (216 mg, 1.79 mmol, 4.00 eq) were provided together and taken up in 25 mL toluene. The dark brown solution was heated to 50 C. for 1 h, then cooled to RT. For 1 h, CO was passed through the reaction mixture at RT. The dark red black reaction solution was filtered over Celite. The solvent was removed in FV, leaving a dark red, almost black, honey-like solid which could be identified as the desired product.

Thermogravimetric Analysis of the Crude Product [Ru(mbt)(Cp*)(CO)]

[0213] The crude product was analyzed to 800 C. at 10 K/min by thermogravimetric analysis (FIG. 10). In this case, a stepwise degradation can be observed, with a total mass degradation of 67%. The decomposition begins at a temperature of about 75 C. with an endothermic peak. A weight decrease of 3% of the starting material was observed at 116.0 C. The residue obtained from this measurement was analyzed by XRPD and could be identified as elemental ruthenium.

Example 18: Synthesis of [Ru(mbt)(Cp*)]

[0214] ##STR00032##

[0215] [RuCp*Cl].sub.4 (100 mg, 0.50 mmol, 1.00 eq) and Li(mbt) (244 mg, 1.98 mmol, 4.00 eq) were provided together and taken up in 10 mL toluene. The dark brown suspension was heated to 50 C. for 2 h and was cooled to RT. The dark red-black reaction mixture was filtered over Celite and the solvent of the filtrate was removed in FV to isolate a dark green, almost black, honey-like solid.

[0216] Thermogravimetric Analysis of the Crude Product [Ru(mbt)(Cp*)]

[0217] The crude product was examined through thermogravimetric analysis to 800 C. at 10 K/min (FIG. 11), wherein a stepwise degradation can be observed. The total mass loss is at 57%. The decomposition begins at a temperature of about 79 C. with an endothermic peak. A weight decrease of 3% of the starting material was observed at 87.6 C. The residue obtained from this measurement was analyzed by XRPD and could be identified as elemental ruthenium.

Example 19: Synthesis of [Cu.SUB.2.(dbt).SUB.2.]

[0218] ##STR00033##

[0219] Li(dbt) (280 mg, 1.72 mmol, 1.00 eq) was provided together with CuCl (170 mg, 1.72 mmol, 1.00 eq) and blended with 10 mL pre-cooled toluene. The reaction mixture was stirred for 16 h at RT, whereupon a color change from yellow to brown was observed. The suspension was filtered over Celite and the solvent of the filtrate removed in FV. The crude product was purified by sublimation in a dynamic vacuum at 70 C. and could be obtained in a yield of 71% (268 mg, 0.61 mmol) as a yellow solid. Single crystals for crystal structure analysis were obtained from a saturated solution of n-hexane at 21 C.

[0220] Thermogravimetric Analysis

[0221] The crude product was examined through thermogravimetric analysis to 1000 C. at 10 K/min (FIG. 12). [Cu.sub.2(dbt).sub.2] shows a one-stage mass loss, wherein the 3% degradation is at 156 C. The total mass loss is 96%, which is attributable to the good sublimatability of the copper compound. From a temperature of about 260 C. onwards, no significant mass degradation is observed any longer. Elemental copper in the crucible was observed as residue.

Example 20: Synthesis of [Cu.SUB.4.(mbt).SUB.4.]

[0222] ##STR00034##

[0223] Li(mbt) (208 mg, 1.72 mmol, 1.00 eq) and CuCl (170 mg, 1.72 mmol, 1.00 eq) were provided and blended with 10 mL pre-cooled toluene. The colorless reaction mixture was stirred for 48 h at RT, whereby a color change to bright yellow could be observed. The suspension was filtered over Celite and the solvent of the filtrate was removed in FV. The bright yellow crude product was purified by sublimation under dynamic vacuum at 65 C. to 75 C. and could be obtained in a yield of 82% (248 mg, 0.35 mmol). Single crystals for crystal structure analysis could be obtained from a saturated solution of n-hexane at RT.

Thermogravimetric Analysis

[0224] The crude product was examined through thermogravimetric analysis to 900 C. at 10 K/min (FIG. 13). [Cu.sub.4(mbt).sub.4] shows a one-stage degradation with a total mass loss of 79%. The 3% degradation is at 198 C., while the maximum mass degradation was determined to be at approximately 250 C. No significant mass loss can be observed any more from a temperature of about 255 C. The SDTA curve shows various melting or phase conversion processes until the decomposition begins, starting at a temperature of 236 C. (not shown). The residue from the thermal gravimetric analysis was examined by XRPD and could be identified as elemental copper.

Example 21: Synthesis of [Ca(dbt).SUB.2.]

[0225] ##STR00035##

[0226] Ca(hmds).sub.2 (122 mg, 0.338 mmol, 1.00 eq) was provided in 10 mL toluene and cooled to 0 C. Dropwise, Hdbt (106 mg, 0.684 mmol, 2.00 eq) was added. The colorless reaction mixture was stirred for 72 h at RT, then filtered off, and the filtrate was evaporated to dryness. The product was obtained as a light-yellow solid with a yield of 63% (116 mg, 0.22 mmol).

[0227] .sup.1H-NMR (C.sub.6D.sub.6, 300 MHz, 300 K): /ppm=1.38 (s, CMe.sub.3).

[0228] .sup.13C-NMR (C.sub.6D.sub.6, 75 MHz, 300 K): /ppm=31.1 (CMe.sub.3), 56.2 (CMe.sub.3).

[0229] IR: {tilde over (v)}/cm.sup.1=2958 (m), 2860 (w), 1601 (w), 1473 (w), 1459 (w), 1384 (w), 1356 (m), 1295 (st), 1243 (m), 1194 (st), 1026 (w), 989 (w), 806 (w), 748 (w), 614 (st), 472 (st).

[0230] TGA: (T.sub.S=25 C., T.sub.E=800 C., 10 C./min), stages: 1 [0231] 3% degradation: 115.3 C., max. degradation: 309.0 C., total mass degradation: 79.3%.

[0232] SDTA: T.sub.D(Onset): 194.4 C., T.sub.D(max.): 263.7 C.

[0233] RPD: Residue from TGA analysis: 2.sub.Lit..sup.[62](2.sub.obs.) for Ca.sub.3N.sub.2: 32.779 (32.785), 35.598 (35.545), 36.191 (36.175), 37.279 (37.375), 38.611 (38.455), 44.599 (44.755), 50.979 (50.665), 60.458 (60.415), 66.228 (66.265).

Example 22: Synthesis of [Si(dbt).SUB.4.]

[0234] ##STR00036##

[0235] .sup.1H-NMR (C.sub.6D.sub.6, 300 MHz, 300 K): /ppm=1.30 (s, CMe.sub.3).

[0236] .sup.13C-NMR (C.sub.6D.sub.6, 75 MHz, 300 K): /ppm=30.7 (CMe.sub.3), 56.7 (CMe.sub.3).

[0237] IR: {tilde over (v)}/cm.sup.1=2957 (m), 2862 (w), 2000 (w), 1669 (w), 1473 (w), 1381 (w), 1355 (m), 1334 (m), 1282 (m), 1244 (m), 1170 (st), 1027 (w), 957 (m), 826 (w), 787 (w), 752 (w), 620 (m), 564 (m), 473 (m), 424 (m).

[0238] Elemental analysis: for C.sub.32H.sub.72N.sub.12Si

[0239] calculated: C: 58.85%, H: 11.11%, N: 25.74%.

[0240] found: C: 58.66%, H: 10.95%, N: 24.04%.

[0241] TGA: (T.sub.S=25 C., T.sub.E=900 C., 10 C./min), stages: 1 [0242] 3% degradation: 184.3% C, max. degradation: 261.3 C., total mass degradation: 96.0%.

[0243] SDTA: T.sub.D1(Onset): 237.2 C., T.sub.D1(max): 263.6 C.

[0244] FIG. 15 shows a graphical representation of the TGA and SDTA measurements.

[0245] pRFA: 97.6 wt-% Si.

Example 23: Synthesis of [Sb(dbt).SUB.3.]

[0246] ##STR00037##

[0247] SbCl.sub.3 (92 mg, 0.403 mmol, 1.00 eq) was provided in 5 mL n hexane and cooled to 78 C. A pre-cooled solution of [Li(dbt)] (197 mg, 1.21 mmol, 3.03 eq) in 5 mL nhexane was slowly added dropwise, wherein the suspension changed color to dark gray. The reaction mixture was stirred for 1 h at 78 C. and then stirred for 3 h at RT. The dark gray suspension was filtered and the filtrate was evaporated to dryness in FV. The crude product was purified sublimatively in FV at 90 C. The product was isolated as a dark yellow solid with a yield of 43% (100 mg, 0.17 mmol).

[0248] HR-EI-MS: calculated for Cl.sub.6H.sub.36N.sub.6: 433.2040 m/z, found: 433.2037 m/z.

[0249] Melting point: 132 C. (visual, 5 C./min).

[0250] 1H-NMR (C.sub.6D.sub.6, 300 MHz, 300 K): /ppm=1.39 (s, CMe.sub.3).

[0251] 13C-NMR (C.sub.6D.sub.6, 75 MHz, 300 K): /ppm=30.6 (CMe.sub.3), 60.9 (CMe.sub.3).

[0252] IR: /cm-1=2965 (st), 2927 (m), 2866 (w), 1471 (w), 1456 (w), 1413 (m), 1385 (w), 1357 (st), 1257 (m), 1221 (m), 1201 (st), 1144 (vst), 1017 (m), 930 (w), 884 (w), 802 (w), 757 (w), 618 (st), 562 (w), 499 (m), 473 (w), 431 (w).

[0253] Elemental Analysis: for C.sub.24H.sub.54SbN.sub.9

[0254] calculated: C: 48.82%, H: 9.22%, N: 21.35%; found: C: 47.95%, H: 9.11%, N: 19.23%.

[0255] TGA: (T.sub.S=25 C., T.sub.E=700 C., 10 C./min), stages: 1

[0256] 3% degradation: 150.6 C., max. degradation: 211.1 C., total mass degradation: 92.8%.

[0257] SDTA: T.sub.D(Onset): 192.7 C., T.sub.D(max): 209.4 C.

Example 24: Synthesis of [Sb(mbt).SUB.3.]

[0258] ##STR00038##

[0259] SbCl.sub.3 (250 mg, 1.10 mmol, 1.00 eq) and [Li(mbt)] (400 mg, 3.30 mmol, 3.00 eq) were provided together and cooled to 0 C. With stirring, 10 mL of toluene pre-cooled to 0 C. were added. The yellow reaction mixture was stirred for 20 h at RT and the solvent removed in FV. After addition of 10 mL of n pentane, the suspension was filtered through Celite and the solvent of the slightly yellow filtrate was removed in FV. The crude product was obtained with a yield of 63% (320 mg, 0.69 mmol) and quantitatively sublimated in FV at 60 C. The product is in the form of a colorless solid.

[0260] .sup.1H-NMR (C.sub.6D.sub.6, 300 MHz, 300 K): /ppm=1.21 (s, 27H, CMe.sub.3), 3.27 (s, 9H, NMe).

[0261] .sup.13C-NMR (C.sub.6D.sub.6, 75 MHz, 300 K): /ppm=29.3 (CMe.sub.3), 37.5 (NMe), 59.1 (CMe.sub.3).

[0262] IR: {tilde over (v)}/cm.sup.1=2966 (m), 2926 (w), 2867 (w), 1430 (st), 1400 (m), 1358 (m), 1272 (m), 1249 (m), 1203 (st), 1054 (m), 1015 (st), 919 (w), 785 (w), 656 (w), 606 (st), 569 (st), 483 (w), 450 (st).

[0263] Elemental analysis: for C.sub.15H.sub.36SbN.sub.3

[0264] calculated: C: 38.81%, H: 7.82%, N: 27.15%.

[0265] found: C: 37.25%, H: 7.55%, N: 26.62%.

[0266] EI-MS: calculated for C.sub.10H.sub.24SbN.sub.6: 349.1101 m/z, found: 349.1005 m/z.

[0267] Melting point: 112 C. (optically 5 C./min).

[0268] TGA: (T.sub.S=25 C., T.sub.E=900 C., 10 C./min), stages: 1 [0269] 3% degradation: 134.4 C., max. degradation: 199.6 C., total mass degradation: 96.1%.

[0270] SDTA: T.sub.M(Onset): 110.8 C., T.sub.M(max): 116.3 C., T.sub.D(Onset): 187.2 C., T.sub.D(max.): 202.6 C. FIG. 16 shows a graphical representation of the TGA and SDTA measurements.

Example 25: Synthesis of [Bi(dbt).SUB.3.]

[0271] ##STR00039##

[0272] BiCl.sub.3 (103 mg, 0.33 mmol, 1.00 eq) was provided in 10 mL toluene and cooled to 16 C. A solution of [Li(dbt)] (162 mg, 0.99 mmol, 3.00 eq) in 5 mL toluene was added dropwise. The brown reaction mixture was first warmed to RT and then stirred at 50 C. for 3 hours. The solid was filtered off and the red filtrate solvent removed in FV. leaving a red solid. The product was purified by sublimation in FV at 60 C. and obtained with a 61% yield (136 mg, 0.20 mmol) as a red solid.

[0273] .sup.1H-NMR (C.sub.6D.sub.6, 300 MHz, 300 K): /ppm=1.32 (s, CMe.sub.3).

[0274] .sup.13C-NMR (C.sub.6D.sub.6, 75 MHz, 300 K): /ppm=30.7 (CMe.sub.3), 56.7 (CMe.sub.3).

[0275] TGA: (T.sub.S=25 C., T.sub.E=900 C., 10 C./min), stages: 1

[0276] 3% degradation: 126.6 C., max. degradation: 223.6 C., total mass degradation: 57.3%.

[0277] SDTA: T.sub.D(Onset): 102.6 C., T.sub.D(max.): 153.4 C. FIG. 17 shows a graphical representation of the TGA and SDTA measurements.

Example 26: Synthesis of [Bi(mbt).SUB.3.]

[0278] ##STR00040##

[0279] BiCl.sub.3 (175 mg, 0.56 mmol, 0.98 eq) was provided in 5 mL toluene and cooled to 70 C. and blended with [Li(mbt)] (207 mg, 1.71 mmol, 3.00 eq), dissolved in 10 mL toluene. The reaction mixture was slowly warmed to RT, stirred for 16 h and then heated to 50 C. for 4 h. The solvent of the green suspension was removed in FV, the product was sublimated from the residue at 65 C. and obtained in a yield of 90% (277 mg, 50.2 mmol) as a yellow solid.

[0280] .sup.1H-NMR (C.sub.6D.sub.6, 300 MHz, 300 K): /ppm=1.20 (s, 27H, CMe.sub.3), 3.69 (s, 9H, NMe).

[0281] .sup.13C-NMR (C.sub.6D.sub.6, 75 MHz, 300 K): /ppm=29.7 (CMe.sub.3), 42.6 (NMe), 59.3 (CMe.sub.3).

[0282] IR: {tilde over (v)}/cm.sup.1=2965 (m), 2924 (w), 2900 (w), 2863 (w), 1455 (w), 1417 (st), 1387 (st), 1357 (st), 1283 (st), 1248 (m), 1201 (st), 1055 (w), 1015 (m), 921 (w), 785 (w), 601 (st), 566 (st), 481 (w), 435 (st).

[0283] EI-MS: calculated for C.sub.10H.sub.24BiN.sub.6: 437.1866 m/z, found: 437.1902 m/z.

[0284] Melting point: 105 C. (visually 5 C./min).

[0285] TGA: (T.sub.S=25 C., T.sub.E=900 C., 10 C./min), stages: 1 [0286] 3% degradation: 152.4 C., max. degradation: 231.5 C., total mass degradation: 81.9%.

[0287] SDTA: T.sub.M(Onset): 106.9 C., T.sub.M(max.): 109.5 C., T.sub.D(Onset): 233.4 C., T.sub.D(max.): 243.4 C. FIG. 18 shows a graphical representation of the TGA and SDTA measurements

[0288] RPD: Residue from TGA analysis: 2.sub.Lit..sup.[63](2.sub.obs.) for Bi: 22.468 (22.570), 23.794 (23.620), 27.164 (27.205), 37.955 (37.975), 39.619 (39.655), 44.554 (44.575), 45.863 (45.970), 46.020 (46.030), 46.470 (46.600), 48.700 (48.700), 56.027 (56.050), 59.325 (59.290), 61.126 (61.270), 62.181 (62.185), 62.895 (62.815), 64.513 (64.525), 67.439 (67.510), 70.786 (70.795), 71.528 (71.515), 71.885 (71.920), 73.711 (73.750), 75.333 (75.340), 76.408 (76.330), 81.143 (81.100), 85.000 (84.970), 85.341 (85.390), 87.089 (87.085), 89.582 (89.590).

Example 27: Synthesis of [Hg(mbt).SUB.2.]

[0289] ##STR00041##

[0290] [Li(mbt)] (200 mg, 1.65 mmol, 2.00 eq) was provided in 2 mL THF and cooled to 0 C. HgCl.sub.2 (224 mg, 0.83 mmol, 1.00 eq), dissolved in 8 mL THF, was added dropwise. The reaction mixture was stirred for 16 h at RT. The slightly gray suspension was concentrated to dryness, taken up in n pentane and filtered over Celite. After removal of the solvent of the filtrate, the product was obtained as a slightly yellow viscous liquid with a yield of 12% (40 mg, 0.09 mmol).

[0291] .sup.1H-NMR (C.sub.6D.sub.6, 300 MHz, 300 K): /ppm=1.28 (m, 18H, CMe.sub.3), 3.31 (m, 6H, NMe).

[0292] .sup.13C-NMR (C.sub.6D.sub.6, 75 MHz, 300 K): /ppm=31.0 (CMe.sub.3), 44.1 (NMe), 57.8 (CMe.sub.3).

[0293] IR: {tilde over (v)}/cm.sup.1=2964 (st), 2926 (m), 2903 (m), 2864 (w), 1437 (st), 1379 (m), 1360 (st), 1260 (st), 1227 (st), 1203 (st), 1095 (st), 1072 (st), 1015 (st), 922 (w), 865 (w), 799 (st), 665 (m), 608 (m), 569 (m), 475 (w).

[0294] TGA: (T.sub.S=25 C., T.sub.E=600 C., 10 C./min), stages: 2 [0295] 3% degradation: 127.1 C., max. degradation (1st stage): 162.4 C., max. degradation (2nd stage): 358.4 C., Mass degradation (1st stage): 68.1%, Total mass degradation: 100%.

[0296] SDTA: T.sub.D(Onset): 143.0 C., T.sub.D(max.): 161.4 C.

Example 28: Synthesis of [Ce(dbt).SUB.3.]

[0297] ##STR00042##

[0298] HR-EI-MS: calculated for C.sub.24H.sub.54 CeN.sub.9: 608.3557 m/z, found: 608.3566 m/z.

Examples 29 and 30: Synthesis of [Zr(dbt).SUB.2.(NMe.SUB.2.).SUB.2.] and [Hf(dbt).SUB.2.(NMe.SUB.2.).SUB.2.]

[0299] ##STR00043##

[0300] M(NMe.sub.2).sub.4 (with M=Zr or Hf) was dissolved in 10 mL and/or 22 mL Et.sub.2O, cooled to 78 C. and dropwise blended with Hdbt. The reaction mixture was warmed to RT and stirred for 16 h. The solvent was then removed in FV. The yellow residue was taken up in 10 mL of n hexane and the slightly turbid solution was filtered. The solvent of the filtrate was removed in a fine vacuum and the product was dried.

Example 29: [Zr(dbt).SUB.2.(NMe.SUB.2.).SUB.2.]

[0301] Yield: 91%.

[0302] .sup.1H-NMR (C.sub.6D.sub.6, 300 MHz, 300 K): /ppm=1.33 (s, 36H, CMe.sub.3), 3.05 (s, 12H, NMe.sub.2).

[0303] .sup.13C-NMR (C.sub.6D.sub.6, 75 MHz, 300 K): /ppm=30.2 (CMe.sub.3), 43.9 (NMe.sub.2), 57.5 (CMe.sub.3).

[0304] Elemental analysis: for C.sub.20H.sub.48ZrN.sub.8

[0305] calculated: C: 48.84%, H: 9.84%, N: 22.78%.

[0306] found: C: 48.41%, H: 9.77%, N: 23.23%.

Example 30: [Hf(dbt).SUB.2.(NMe.SUB.2.).SUB.2.]

[0307] Yield: 96%.

[0308] .sup.1H-NMR (C.sub.6D.sub.6, 300 MHz, 300 K): /ppm=1.32 (s, 36H, CMe.sub.3), 3.15 (s, 12H, NMe.sub.2).

[0309] .sup.13C-NMR (C.sub.6D.sub.6, 75 MHz, 300 K): /ppm=30.2 (CMe.sub.3), 43.9 (NMe.sub.2), 58.6 (CMe.sub.3).

[0310] Elemental analysis: for C.sub.20H.sub.48HfN.sub.8

[0311] calculated: C: 41.48%, H: 8.35%, N: 19.35%.

[0312] found: C: 40.29%, H: 8.14%, N: 19.24%.

Example 31: Synthesis of Cs(dbt)

[0313] ##STR00044##

[0314] Cshmds was taken up in 10 mL Et.sub.2O and blended dropwise with Hdbt at 0 C. The slightly turbid solution was warmed to RT, stirred for 16 h and filtered over Celite. The solvent of the filtrate was removed in FV. Yield: 76%.

[0315] .sup.1H-NMR (C.sub.6D.sub.6/THF-d.sub.8 (5/1), 300 MHz, 300 K): /ppm=1.35 (s, CMe.sub.3).

[0316] .sup.13C-NMR (C.sub.6D.sub.6/THF-d.sub.8 (5/1), 75 MHz, 300 K): /ppm=31.3 (CMe.sub.3), 55.8 (CMe.sub.3).

[0317] Elemental analysis: for C.sub.8H.sub.18CsN.sub.3

[0318] calculated: C: 33.23%, H: 6.27%, N: 14.53%.

[0319] found: C: 32.60%, H: 6.07%, N: 14.64%.

Example 32: Synthesis of [Au.SUB.2.(dbt).SUB.2.]

[0320] ##STR00045##

[0321] AuCl (253 mg, 1.09 mmol, 1.00 eq) was suspended in 5 mL THF, cooled to 75 C. and blended with a solution of [Li(dbt)] (179 mg, 1.09 mmol, 1.00 eq) in 10 mL THF. The reaction mixture was kept at 75 C. for 5 h, heated to RT and stirred for a further 16 h. The solvent of the brown reaction mixture was removed in a fine vacuum (FV), the residue taken up in n hexane and the resulting suspension filtered. The solvent of the filtrate was removed in FV and the residue was purified sublimatively in FV at 80 C. The product was obtained in the form of a yellow solid with a yield of 13% (50 mg, 0.14 mmol).

[0322] .sup.1H-NMR (C.sub.6D.sub.6, 300 MHz, 300 K): /ppm=1.12 (s, 9H, CMe.sub.3), 1.27 (s, 18H, CMe.sub.3), 1.45 (s, 9H, CMe.sub.3). .sup.13C-NMR (C.sub.6D.sub.6, 75 MHz, 300 K): /ppm=30.2 (CMe.sub.3), 30.4 (CMe.sub.3), 31.0 (CMe.sub.3), 56.5 (CMe.sub.3), 60.2 (CMe.sub.3), 62.4 (CMe.sub.3).

[0323] IR: {tilde over (v)}/cm-1=2956 (m), 2858 (w), 1469 (w), 1404 (st), 1381 (st), 1356 (st), 1317 (w), 1222 (m), 1184 (st), 1020 (w), 803 (w), 650 (m), 578 (m), 510 (w), 483 (w).

[0324] Elemental Analysis: for C.sub.16H.sub.36Au.sub.2N.sub.6

[0325] calculated: C: 27.20%, H: 5.14%, N: 11.90%; found: C: 29.77%, H: 5.75%, N: 13.46%.

[0326] HR-EI-MS: calculated for C.sub.16H.sub.36Au.sub.2N.sub.6: 706.2333 m/z, found: 706.2324 m/z.

[0327] TGA: (T.sub.S=25 C., T.sub.E=900 C., 10 C./min), stages: 1

[0328] 3% degradation: 121.8 C., max. degradation: 221.4 C., total mass degradation: 62.0%.

[0329] SDTA: T.sub.D(Onset): 212.6 C., T.sub.D(max.): 217.4 C. FIG. 19 shows a graphical representation of the TGA and SDTA measurements.

Example 33: Synthesis of [Ag.SUB.4.(dbt).SUB.4.]

[0330] ##STR00046##

[0331] AgCl (250 mg, 1.70 mmol, 1.00 eq) was provided in 5 mL THF, cooled to 70 C., and a solution of [Li(dbt)] (277 mg, 1.70 mmol, 1.00 eq) was added in 10 mL THF. The deep-brown reaction mixture was warmed to RT, stirred for 16 h and then freed of all volatile constituents in FV. The residue was taken up in 10 ml of n hexane and the weakly reddish suspension was filtered. The solvent of the filtrate was removed in FV, the residue was purified by sublimation at 90 C. in FV and the product was obtained as a colorless solid with a yield of 47% (178 mg, 0.20 mmol).

Reaction Mixture and Product should be Handled in the Absence of Light.

[0332] .sup.1H-NMR (C.sub.6D.sub.6, 300 MHz, 300 K): /ppm=1.27 (s, 36H, CMe.sub.3), 1.43 (s, 36H, CMe.sub.3).

[0333] .sup.13C-NMR (C.sub.6D.sub.6, 75 MHz, 300 K): /ppm=31.0 (CMe.sub.3), 31.9 (CMe.sub.3).

[0334] IR: {tilde over (v)}/cm.sup.1=2957 (m), 2859 (w), 1471 (w), 1403 (st), 1354 (st), 1316 (m), 1222 (st), 1179 (st), 1101 (w), 1055 (w), 1016 (w), 921 (w), 888 (w), 802 (w), 766 (w), 642 (st), 574 (st), 503 (w), 478 (m), 411 (w).

[0335] Elemental Analysis: for C.sub.16H.sub.48Ag.sub.4N.sub.12

[0336] calculated: C: 36.38%, H: 6.87%, N: 15.91%; found: C: 36.79%, H: 6.93%, N: 16.60%.

[0337] TGA: (T.sub.S=25 C., T.sub.E=700 C., 10 C./min), stages: 1

[0338] 3% degradation: 205.4 C., max. degradation: 256.6 C., total mass degradation: 78.7%.

[0339] SDTA: T.sub.D(Onset): 212.5 C., T.sub.D(max.): 215.2 C.

[0340] FIG. 20 shows a graphical representation of the TGA and SDTA measurements.

Example 34: Synthesis of [Ga(mbt)Me.SUB.2.]

[0341] ##STR00047##

[0342] GaMe.sub.3 (146 mg, 1.27 mmol, 2.00 eq) was provided in 5 mL n pentane and added at 0 C. to a solution of GaCl.sub.3 (112 mg, 0.64 mmol, 1.00 eq) in 10 mL n pentane. The colorless solution was warmed to RT, stirred for 16 h, re-cooled to 0 C. and added to a solution of [Li(mbt)] (231 mg, 1.91 mmol, 3.00 eq) in 10 mL of n pentane. The reaction mixture was warmed to RT and stirred for 16 h. The solvent of the suspension was removed in FV and the desired product isolated from the residue by condensation in FV. The product was obtained in the form of a colorless liquid with a yield of 57% (233 mg, 1.09 mmol).

[0343] .sup.1H-NMR (C.sub.6D.sub.6, 300 MHz, 300 K): /ppm=0.05 (s, 6H, GaMe.sub.2), 1.17 (s, 18H, CMe.sub.3), 3.03 (s, 3H, NMe).

[0344] .sup.13C-NMR (C.sub.6D.sub.6, 75 MHz, 300 K): /ppm=5.6 (GaMe.sub.2), 29.7 (CMe.sub.3), 39.4 (NMe).

[0345] IR: {tilde over (v)}/cm.sup.1=2969 (m), 2902 (w), 1524 (w), 1459 (w), 1435 (m), 1361 (st), 1309 (m), 1271 (w), 1199 (st), 1068 (m), 1026 (w), 955 (w), 930 (w), 866 (st), 787 (w), 737 (st), 688 (m), 646 (st), 572 (st), 534 (st), 481 (w), 460 (m), 438 (w).

[0346] TGA: (T.sub.S=25 C., T.sub.E=450 C., 10 C./min), stages: 1

[0347] 3% degradation: 63.2 C., max. degradation: 100.9 C., total mass degradation: 87.4%.

[0348] SDTA: T.sub.D(Onset): 81.6 C., T.sub.D(max.): 100.3 C.

[0349] FIG. 21 shows a graphical representation of the TGA and SDTA measurements.

Example 35: Synthesis of [Ga(dbt)Me.SUB.2.]

[0350] ##STR00048##

[0351] GaMe.sub.3 (181 mg, 1.58 mmol, 2.00 eq) was provided in 10 mL n pentane and added at 0 C. to a solution of GaCl.sub.3 (139 mg, 0.79 mmol, 1.00 eq) in 10 mL n pentane. The reaction mixture was warmed to RT and stirred for 16 h. At 0 C., a solution of [Li(dbt)] (387 mg, 2.37 mmol, 3.00 eq) was added dropwise, and the precipitation of a colorless solid was observed instantly. The suspension was slowly warmed to RT and stirred for 16 h. The solvent was removed in the fine vacuum (FV) and the product was condensed in the form of a colorless liquid from the residue in FV. The product was obtained with a yield of 43% (261 mg, 1.02 mmol).

[0352] .sup.1H-NMR (C.sub.6D.sub.6, 300 MHz, 300 K): /ppm=0.10 (s, 6H, GaMe.sub.2), 1.17 (s, 18H, CMe.sub.3).

[0353] .sup.13C-NMR (C.sub.6D.sub.6, 75 MHz, 300 K): /ppm=5.2 (GaMe.sub.2), 29.7 (CMe.sub.3), 55.8 (NMe).

[0354] IR: {tilde over (v)}/cm.sup.1=2967 (st), 2870 (w), 1459 (w), 1387 (w), 1361 (m), 1295 (st), 1217 (st), 1029 (w), 924 (w), 767 (m), 699 (m), 630 (m), 583 (st), 545 (st), 484 (m).

[0355] TGA: (T.sub.S=25 C., T.sub.E=450 C., 10 C./min), stages: 1

[0356] 3% degradation: 64.2 C., max. degradation: 116.0 C., total mass degradation: 89.9%.

[0357] SDTA: T.sub.D(onset): 79.5 C., T.sub.D(max.): 115.7 C.

[0358] FIG. 22 shows a graphical representation of the TGA and SDTA measurements.

Example 36: Synthesis of [Al(mbt).SUB.3.]

[0359] ##STR00049##

[0360] A solution of AlCl.sub.3 (131 mg, 0.98 mmol, 1.00 eq) in 10 mL Et.sub.2O was added dropwise at 0 C. to a solution of [Li(mbt)] (357 mg, 2.95 mmol, 3.00 eq) in 10 mL Et.sub.2O. The colorless reaction mixture was slowly warmed to RT, stirred for 16 h, and then filtered. The residue was extracted with 10 mL Et.sub.2O, and the filtrate evaporated to dryness in FV. The pale-yellow solid was sublimated in fine vacuum at 45 C. and the product was obtained with a yield of 21% (76 mg, 0.21 mmol).

[0361] .sup.1H-NMR (C.sub.6D.sub.6, 300 MHz, 300 K): /ppm=1.31 (s, 27H, CMe.sub.3), 3.16 (s, 9H, NMe).

[0362] .sup.13C-NMR (C.sub.6D.sub.6, 75 MHz, 300 K): /ppm=30.3 (CMe.sub.3), 37.5 (NMe), 55.8 (CMe.sub.3).

[0363] .sup.27Al-NMR (C.sub.6D.sub.6, 130 MHz, 300 K): /ppm=28.1.

[0364] IR: {tilde over (v)}/cm.sup.1=2968 (m), 2926 (m), 2896 (m), 2802 (w), 1473 (w), 1457 (w), 1415 (w), 1387 (w), 1358 (m), 1300 (st), 1263 (st), 1229 (st), 1199 (st), 1106 (w), 1025 (w), 954 (w), 796 (w), 625 (m), 572 (w), 524 (st), 435 (w).

[0365] Elemental Analysis: for C.sub.15H.sub.36AlN.sub.9

[0366] calculated: C: 48.76%, H: 9.82%, N: 34.12%; found: C: 47.95%, H: 9.63%, N: 33.55%.

[0367] TGA: (T.sub.S=25 C., T.sub.E=700 C., 10 C./min), stages: 1

[0368] 3% degradation: 124.6 C., max. degradation: 216.1 C., total mass degradation: 96.4%.

[0369] SDTA: T.sub.M(Onset): 45.6 C., T.sub.M(max.): 49.7 C., T.sub.D(onset): 205.1 C., T.sub.D(max.): 218.8 C.

[0370] FIG. 23 shows a graphical representation of the TGA and SDTA measurements.

Example 37: Synthesis of [Al(dbt).SUB.3.]

[0371] ##STR00050##

[0372] [Al(NMe.sub.2).sub.3].sub.2 (154 mg, 0.97 mmol, 0.50 eq) was provided in 10 mL toluene, cooled to 0 C. and blended dropwise with H(dbt) (458 mg, 2.91 mmol, 3.00 eq). The reaction solution was stirred for 1 h at 0 C. and was allowed to warm to RT. A gas evolution was observed. After the yellow solution was stirred for 16 h at RT, a pale-yellow solid was obtained by removing the solvent in FV. The crude product was purified sublimatively at 55 C. in FV and isolated as a colorless solid with a yield of 51% (244 mg, 0.49 mmol).

[0373] .sup.1H-NMR (C.sub.6D.sub.6, 300 MHz, 300 K): /ppm=1.38 (s, CMe.sub.3).

[0374] .sup.13C-NMR (C.sub.6D.sub.6, 75 MHz, 300 K): /ppm=31.2 (CMe.sub.3), 57.2 (CMe.sub.3).

[0375] .sup.27Al-NMR (C.sub.6D.sub.6, 130 MHz, 300 K): /ppm=24.6.

[0376] IR: {tilde over (v)}/cm.sup.1=2972 (m), 2929 (s), 2870 (s), 2812 (s), 2767 (s), 1474 (s), 1387 (s), 1360 (m), 1302 (st), 1257 (st), 1201 (st), 1160 (st), 1069 (s), 1034 (s), 977 (m), 899 (s), 845 (s), 767 (s), 627 (m), 570 (m), 543 (st), 438 (s).

[0377] Elemental Analysis: calculated for C.sub.24H.sub.54AlN.sub.9: C: 58.15%, H: 10.98%, N: 25.43%; found: C: 58.25%, H: 10.13%, N: 24.32%.

[0378] TGA: (T.sub.S=25 C., T.sub.E=700 C., 10 C./min), stages: 1

[0379] 3% degradation: 126.8 C., max. degradation: 172.6, 302.0 C., total mass degradation: 95.3%.

[0380] SDTA: T.sub.D(Onset): 270.0 C., T.sub.D(max): 302.7 C. FIG. 24 shows a graphical representation of the TGA and SDTA measurements.

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