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1.
Contributions to the Chemistry of Transition Metal Alkyl Compounds. XIV. Investigations on Benzyl Tungsten Compounds. – On the Formation and Characterization of Tetrabenzyl Tungsten Unstable benzyl tungsten pentachloride is formed from tribenzyl boron and tungsten hexachloride. Other benzylating agents yield only less defined reduction products. – Reacting WCl4 · 2 THF with dibenzyl magnesium W(CH2C6H5)4 can be obtained. The new compound is stable at room temperature and is thoroughly characterized. 相似文献
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Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXXII. On Benzyl Copper Compounds Benzyl copper is formed reacting copper dichloride or acetylacetonate with dibenzyl zinc complexed by chlorides or acetylacetonates of copper and zinc. The complexes decompose between ?15 and +25°C with separation of copper and benzyl radicals proved by spin trap experiments. The stability of the compound is not influenced remarkably by substituents in o-position but is caused by complex formation with triphenyl phosphine. Pure benzyl copper, obtained by decomposition of BzCu · 0.25 BzZn(acac) · 0.75 Zn(acac)2 by means of diethyl ether, decomposes spontaneously even at a temperature of ?50°C. 相似文献
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Contribution to the Chemistry of Transition Metal Alkyl Compounds. XXVIII. Benzylation of the Trivalent Titanium, Vanadium, and Chromium Acetylacetonates BzCr(acac)2, 2Bz(Vacac)2 · Mg(acac)2 and 3BzV(acac)2 · Al(acac)3 were obtained in definite form by reaction of Cr(acac)3 and V(acac)3 with Bz3Al, Bz2Mg, and BzMgCl. Ti(acac)3, reacts with Bz2Mg and BzLi forming deep green Bz3Ti, which could'nt be isolated free of impurities (Bz = C6H5CH2, acacH = acetylacetone). 相似文献
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Titanium(IV)chloride and bromide react with zinc dialkyls forming the corresponding titanium trihalides. In detail the preparation and charakterisation of methyltitanium trichloride, methyltitanium tribromide, phenyltitanium trichloride and of complexes of proypl-, pentyl- and phenyltitanium trichloride are described. Furthermore some considerations are made on the stabilities of organotitanium compounds. 相似文献
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Contributions to the Chemistry of Transition Metal Alkyl Compounds. 63. Preparation and Crystal Structure of Tetramethyltitanium Tetrahydrofuran Me4Ti · 2THF 1 dissoziates partially in n-pentane. The formed Me4Ti · THF 2 could be isolated. According to X-ray structure determination the molecules of 2 have a trigonalbipyramidal shape with the THF molecule in axial position. 相似文献
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Contributions to the Chemistry of Transition Metal Alkyl Compounds. XV Preparation and Properties of Phenyl Vanadium Dichloride Vanadium(IV) chloride reacts with diphenyl zinc forming extremely air sensitive, at room temperature stable phenyl vanadium dichloride. The diffuse reflectance spectrum indicates an octahedral structure of the vanadium compound which is to regard as a coordination polymer. – Diethyl ether causes a cleavage of the V – C bond with formation of a vanadium dichloride etherate. 相似文献
7.
Contributions to the Chemistry of Transition Metal Alkyl Compounds. XL. About Lithium Alkenylmanganates(II) MnCl2 reacts with vinyl, 2,2-dimethylvinyl, allyl, and methallyl lithium giving rise to alkenyl manganates(II). In a pure state the compounds Li2[Mn(CH?CH2)4] · 1.5 diox, Li2[Mn(CH?C(CH3)2)4] · 1.5 diox, Li2[Mn(CH2? CH?CH2)4] · 2.5 diox and Li3[Mn(CH2? C(CH3)?CH2)5] · 2 diox were isolated. The compounds were characterized by elementary analysis, EPR and IR spectra, magnetic moments, and reactions with iodine. 相似文献
8.
Contributions to the Chemistry of Transition Metal Alkyl Compounds. XLI. Preparation and Thermolysis Products of Methyl Titanium Halides (CH3)nTiX4 ? n derivatives (X = Cl, Br, I) can be prepared by comproportionation reactions of tetramethyl titanium with titanium tetrahalides at deep temperature. Furthermore, the methyl titanium iodides are formed from tetramethyl titanium and iodine. Thermolysis of CH3TiX3 derivatives yields titanium(III) halides. At decomposition of the (CH3)2TiX2 compounds in ether solution titanium(II) halides are obtained in a fine-distributed, very reactive form. 相似文献
9.
Contributions to the Chemistry of Transition Metal Alkyl Compounds. 62. Preparation and NMR-spectroscopic Characterization of Tetramethyltitanium Complexes Complexes of tetramethyltitanium with THF and oxygen, nitrogen and phosphorous containing chelating ligands were synthesized and characterized by low temperature n.m.r. spectroscopy. The obtained complexes show a dynamic behaviour in solutions. The results of semiempirical MO calculations favour octahedral and not a trigonal prismatic configuration of the complexes. 相似文献
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Contributions to the Chemistry of Transition Metal Alkyl Compounds. XVIII. On the Preparation and Properties of Tetrabenzyl Vanadium and Benzyl Tantalum Chlorides Pure tetrabenzyl vanadium was isolated and characterized by elementary analyses, EPR and 1H-NMR spectra, by hydrolysis and thermal decomposition. — Experiments for the preparation of tetra or pentabenzyl compounds of niobium and tantalum failed, but we could prepare C6H5CH2TaCl4, (C6H5CH2)2TaCl3, and (C6H5CH2)3TaCl2, the last two in form of bipyridyl complexes. 相似文献
11.
Ernst Langguth Nguyen Van Thu A. Shakoor Klaus Jacob Karl-Heinz Thiele 《无机化学与普通化学杂志》1983,505(10):127-133
Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXXVI. About the Existence of 3(N, N-Dimethylamino)propyl Compounds of 3d-Metals and Zirconium 3(N, N-dimethylamino)propyl lithium reacts with 3d-metal halides in a different manner. In crystalline state the compounds RTiCl3, R3Cr, R4Zr, and the complexes LiVR3Cl · 0.7 O(C2H5)2 and Li2CoR4 (R = (CH3)2NCH2CH2CH2) were isolated. The formation of the unstable R4Ti and R2Ni derivatives could be proved. Iron and nickel halides are reduced to the metals by dimethylaminopropyl lithium, even at a temperature of ?60°C. 相似文献
12.
Experiments on alkylation and arylation of titanium trichloride by means of organometallic compounds are reported. The formation of trimethyl titanium and derivates of triphenyl titanium was proved, and diphenyl titanium chloride was isolated in the crystalline state in form of a complex with diethyl ether. 相似文献
13.
Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXXV. Reactions in Tetrabenzyl Titanium/Alkyllithium Systems Organotitanium(IV) complexes of the type Li[(C6H5CH2)4TiR] (R = CH3, C2H5, n-C4H9) were isolated from tetrabenzyl titanium and lithium alkyls at deep temperature. The reddish brown, crystalline compounds decompose between ?30 and 0°C with formation of benzyltitanates(II) which composition differs between Li2[Ti(CH2C6H5)4] and Li[Ti(CH2C6H5)3]. From these complexes pure dibenzyl titanium can be isolated. The reaction mechanism is discussed. Experiments for isolation of a benzyl titanium(III) compound from (C6H5CH2)4Ti/RLi systems failed in all cases. Recent informations about stable tribenzyl titanium obtained from tetrabenzyl titanium and ethyl lithium could not be confirmed. 相似文献
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Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXVII. Preparation of Titanium Acetates from Tetramethyl and Tetrabenzyl Titanium (CH3)4Ti reacts with CH3COOH at deep temperature to the colourless Ti(OCOCH3)4. Using ClCH2COOH slight violet Ti(OCOCH2Cl)4 is formed containing small amounts of reduction products. A complete reduction occurs in the analogous reaction with CF3COOH yielding dark green Ti(OCOCF3)3. From (C6H5CH2) 4 Ti and CH3COOH a green titanium(III,IV) acetat of the formula 4 Ti(OCOCH3) · Ti(OCOCH3)4 was obtained. – The isolated titanium acetates were characterized by elementary analyses, magnetic moments and i.r. spectra. 相似文献
16.
Contributions to the Chemistry of Transition Metal alkyl Compounds. XXXIX. About 3(N,N-Dimethylamino) propyl Lanthanide Compounds LaCl3, PrCl3, and ErCl3 react with dimethylaminopropyl lithium (RLi) in tetrahydro-furan as a solvent with formation of complexes of the type Li3[LnR3Cl3]. In a similar way the Li3[CeR6] derivative is formed from CeCl3. The organolanthanide complexes were characterized by elementary analysis, hydrolysis and thermolysis products, the effective magnetic moments and the i.r. spectra. 相似文献
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Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXXVIII. Reactions of Dibenzyl Manganese with Oxygene (C6H5CH2)2Mn · C4H8O2 reacts with oxygen forming an unstable deep violet compound which changes in a stable unsoluble yellow peroxide of the formula C6H5CH2MnO? OMnCH2C6 H5. With excess oxygen a polynuclear complex of 3 valent manganese is formed with the composition Mn4O4(OH)4(OCHC6H5)2. The compounds isolated were characterized by the products of hydrolyses and thermolyses, anaerobic reaction with iodine, magnetic moments, i.r. and e.s.r. spectra. 相似文献
18.
Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXIV. Preparation and Properties of Tetrabenzyl Molybdenum and Tetrabenzyl Uranium Tetrabenzyl molybdenum, (C6H5CH2)4Mo, can be obtained by the reaction of MoCl4 · 2 THF with dibenzyl magnesium. The compound forms darkbrown crystals, which are stable at room temperature. The analogous reaction of UCl4 · 3 THF with dibenzyl magnesium yields a reddish brown complex of tetrabenzyl uranium of the formula (C6H5CH2)4U · MgCl2. The synthesized compounds are characterized more in detail. 相似文献
19.
Contributions to the Chemistry of Transition Metal Alkyl Compounds. XLIII. Tetrakis(alkoxycarbonylmethyl)titanium Compounds Organotitanium(IV) compounds of the type (ROCOCH2)4Ti (R ? C2H5, i-C3H7, t-C4H9, C6H5, C6H5CH2) were obtained by reactions of ROCOCH2Li derivatives with TiCl4 at low temperature. The compounds which decompose only above 90°C were characterized by the hydrolysis products, anaerobic reactions with iodine, and the i.r. spectra. The bond conditions are discussed. 相似文献
20.
Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXXVII. About the Existence of 1-Norbornyl Compounds of Tungsten and Molybdenum Reactions of WCl6, WCl4, WO2Cl2, WOCl4, MoCl5, and MoO2(acac)2 with 1-Norbornyl lithium (1-NorLi1)) are described. From WCl6 and WCl4 [(1-Nor)2W]n is formed, whereas in dependence of the solvent WO2Cl2 and WOCl4 are transformed into the complexes Li2[1-NorWOCl4] · THF, Li[WOCl4], Li[WO2Cl2], and Li2[WO2Cl2]. MoCl5 and MoO2(acac)2 are reduced with formation of Li[MoCl5], Li[MoO2(acac)2] and Li2[MoO2(acac)2]. — Stable (1-Nor)4M-derivatives of molybdenum and tungsten, comparable those of 3d-metals (M = Ti? Co) seem not to exist. 相似文献