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. 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. 64. Darstellung und Kristallstruktur von Bis[N,N′-bis(trimethylsilyl)benzamidinato]dimethyltitan

Contributions to the Chemistry of Transition Metal Alkyl Compounds. 64 [1] Preparation and Crystal Structure of Bis[N,N′ -bis(trimethylsilyl)-benzamidinato]dimethyltitanium Tetramethyltitanium reacts with excess N,N′-bis(trimethylsilyl)-benzamidine ( 1 ) to give bis[N,N′-bis(trimethylsilyl)benzamidinato]dimethyl-titanium ( 2 ) via protolysis. This compound was isolated and characterized by X-ray crystal structure analysis. In the crystal, 2 adopts an octahedral coordination with the methyl groups in cis-positions. The monomethyl complexes [PhC(NSiMe₃)₂]₂M(Me)Cl ( 3 : M = Ti, 4 : M = Zr) have been prepared by treatment of the dichloro precursors with one equivalent of methyllithium.     

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. 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. 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. 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. 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. XXXIV. Darstellung und Eigenschaften von 3-(N,N-Dialkylamino)-propylmangan-Verbindungen

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXXIV. Synthesis and Properties of 3-(N,N-dialkylamino)propyl Manganese Compounds MnCl₂ reacts with lithium organyls of the type R₂N(CH₂)₃Li with formation of definite organomanganese complexes. The pure [(CH₃)₂N(CH₂)₃]₂Mn, [(C₂H₅)₂N(CH₂)₃]₂Mn, [(CH₂)₅N(CH₂)₃]₂Mn and the complexes [(CH₃)₂N(CH₂)₃]₂Mn · LiCl and Li{Mn[(CH₂)₃N(CH₃)₂]₃} · 1,5 THF were isolated. [(CH₃)₂N(CH₂)₃]₂Mn · 2 Li(acac) was obtained as a result of reactions of Mn(acac)₂ and Mn(acac)₃ with the corresponding lithium organyl. The σ-organomanganese(II) derivatives were characterized in detail by elementary analysis, molecular weight determination, ESR- and IR-spectra, conductivity measurements and the magnetic moments.     

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. 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. XLIV. Zur Bildung von Tetraorganylzirconaten(II)

Contributions to the Chemistry of Transition Metall Alkyl Compounds. XLIV. Formation of Tetraorganylzirconates(II) Zirconiumtetraorganyls are reduced by n-butyl lithium with formation of dilithium tetraorganyl zirconates(II). Li₂[Zr(CH₂C₆H₅)₄] and Li₂[Zr(CH₃)₄] were isolated in a definite form as extremely air sensitive compounds, from which a polymer structure can be assumed. The compounds were characterized by elementary analysis, hydrolyses products, reactions with iodine, magnetic moments, and the ESR 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. 59. Cyclopentadienyl-2-(dimethylaminomethyl)ferrocenyl-Verbindungen elektronenarmer 3 d-Elemente

Contributions to the Chemistry of Transition Metal Alkyl Compounds. 59. Cyclopentadienyl-2-(dimethylaminomethyl)ferrocenyl Compounds of Early 3 d-Elements Compounds of the type (C₅H₅)₂M(FcN) (M = Sc ( 1 ), Ti ( 2 ), V ( 3 ), Cr ( 4 ); FcN = 2-dimethylaminomethyl)ferrocenyl group), and (C₅H₅)M(FcN)₂ (M = Ti ( 5 ), Cr ( 6 ) were synthesized and investigated. A detailled characterization with respect to the existence of chelate structures was realized by the uv-vis, ¹H-n.m.r. spectroscopic measurements and determination of magnetic moments.     

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. XLIX. Reaktionen von Cerium(IV)-acetylacetonat mit Lithium- und Magnesiumorganylen

Contributions to the Chemistry of Organo Transition Metal Compounds. XLIX. Reactions of Cerium(IV) Acetylacetonate with Organolithium and Organomagnesium Compounds Reacting Ce(acac)₄ with lithium organyls RLi (R = CH₃ 1-Nor¹), ((CH₃)₂NCH₂CH₂CH₂) in the molar ratio 1:1 the cerium compound is reduced with formation of Li[Ce(acac)₄]. Using a molar ratio of Ce:Li = 1:4 organocerium complexes of the composition R₃Ce · 3 Li(acac) or Li₃[R₃Ce(acac)₃] are formed. From reactions with excess CH₃Li (Ce: Li = 1:7) Li₃[Ce(CH₃)₆] · 3 Li(acac) could be isolated. All cerium complexes are characterized by elementary analysis, hydrolysis products, i.r. spectra, and molecular weight determination.     

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. 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. 47. Zur Reaktion von Hexachloroceraten(IV) mit Lithiumorganylen

Contributions to the Chemistry of Organo-Transition Metal Compounds. 47. Reactions of Hexachlorocerates(IV) with Organolithium Compounds Pyridinium hexachlorocerate(IV) reacts with lithium organyls RLi RLi (R = 1-Nor, (CH₃)₂NCH₂CH₂CH₂, n-C₄H₉) in the molar ratio 1:2 with formation of Li₂[CeCl₆] · 2 NC₅H₅. A further mol RLi effects a reduction to Li₃[CeCl₆] · 2 NC₅H₅. With an excess of RLi amidocerium(III) complexes of the typ Li₄ are formed. Li₂[CeCl₆] is formed also at reactions of quartery ammonium salts, e. g. [C₆H₅CH₂N(C₂H₅)₃]₂[CeCl₆], with RLi (R = 1-Nor, Me₂₂NCH₂CH₂CH₂) followed by an reduction to Li₃[CeCl₆]. An excess of the lithium organyl effects the formation Li₄[RCeCl₆] complexes. The yielded compounds were characterized by elementary analysis, the hydrolysis and deuterolysis products, magnetic moments, and IR-spectra.