Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XIV. Untersuchungen über Benzylwolframverbindungen-Darstellung und Charakterisierung des Wolframtetrabenzyls

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.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XXXII. Über Benzylverbindungen des Kupfers

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.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XXVIII. Zur Benzylierung der Acetylacetonate des dreiwertigen Titans,Vanadiums und Chroms

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).     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. IV Über Darstellung und Eigenschaften von Alkyl- und Aryltitantrihalogeniden

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.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. 63. Darstellung und Kristallstruktur von Tetramethyltitan-tetrahydrofuran

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.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XV. Bildung und Eigenschaften von Phenylvanadindichlorid

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.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XL. Über Lithium-alkenylmanganate(II)

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.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XLI. Darstellung und Thermolyseprodukte von Methyltitanhalogeniden

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XLI. Preparation and Thermolysis Products of Methyl Titanium Halides (CH₃)_nTiX_{4 ? 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.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. 62. Darstellung und NMR-spektroskopische Untersuchung von Komplexen des Tetramethyltitans

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.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XVIII. Darstellung und Eigenschaften von Vanadintetrabenzyl und von Benzyltantalchloriden

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.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XXXVI. Zur Existenz von 3(N,N-Dimethylamino)propyl-Verbindungen der 3d-Elemente und des Zirconiums

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.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. VI. Über Versuche zur Alkylierung und Arylierung des Titan(III)-chlorids

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.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XXXV. Zum Reaktionsverhalten von Tetrabenzyltitan gegenüber Lithiumalkylen

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.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XXVII. Darstellung von Titanacetaten aus Tetramethyl- und Tetrabenzyltitan

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.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XXXIX. Über 3(N,N-Dimethylamino)propyllanthanoid-Verbindungen

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.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XXXVIII. Reaktion von Dibenzylmangan mit Sauerstoff

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.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XXIV. Darstellung und Eigenschaften von Tetrabenzylmolybdän und -uran

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.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XLIV. Tetrakis(alkoxycarbonylmethyl)titan-Verbindungen

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.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XXXVII. Zur Existenz von 1-Norbornylverbindungen des Wolframs und Molybdäns

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.