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. XLIII. Über die Reduktion von Organozirconium(IV)-Verbindungen mit Lithiumorganylen

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XLIII. Reduction of Organozirconium(IV) Compounds with Lithium Organyls. (C₅H₅)₂ZrR₂ derivatives react with lithium organyls by forming of organozirconium(III) or organozirconium(II) compounds. (C₅H₅)Zr(CH₂C₆H₅)₂ · O(C₂H₅)₂ and (C₅H₅)ZrC₆H₅ · 3 O(C₂H₅)₂ were isolated in a definite form. Informations on the formation of (C₅H₅)Zr(C₆H₅)₂ · 2 O(C₂H₅)₂ could be confirmed. The compounds obtained were characterized by elementary analysis, hydrolysis products, reactions with iodine, magnetic moments, and the IR and EPR spectra.     

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. 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. 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. 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. XIII. Über die Reaktion von Vanadinsäure-triisopropylester mit Zinkdimethyl—Zur Kenntnis des Methylvanadinoxiddiisopropoxids

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XIII. the Reaction of Vanadium Isopropyl Ester with Dimethyl Zinc. — On the Formation of CH₃VO(i-OC₃H₇)₂ Dimethyl zinc reacts with ortho vanadium acid triisopropyl ester forming methyl zinc isopropoxide (CH₃Zn-i-OC₃H₇)_n and methyl vanadium oxide diisopropoxide CH₃VO(i-OC₃H₇)₂. The new σ-organovanadium compound was isolated and thoroughly characterized.     

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. 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. 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. 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. 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. 50. Eine ungewöhnliche Organolanthanverbindung

Contributions to the Chemistry of Transition Metal Alkyl Compounds. 50. A non-common Organolanthanum Compound Lanthanum reacts with dibenzyl mercury in tetrahydrofuran as a solvent with splitting of solvent molecules and with formation of ethylene and a benzyl hydrido vinyloxide lanthanum complex of the composition C₆H₅CH₂La(H)OCH?CH₂ · 2 THF. This complex, primary well soluble in tetrahydrofuran, is extremely sensitive against air and moisture and undergoes a fast coordination polymerisation with a strong decrease of the solubility. The compound was characterized by elementary analysis, the hydrolysis and deuterolysis reaction, and by the 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. XXI [1] Versuche zur Alkylierung von Vanadin(IV)-chlorid und Vanadinoxidtrichlorid

Inhaltsübersicht. Es wird über Reaktionen von Vanadin(IV)-chlorid mit Zinkdialkylen und Bortrialkylen berichtet. Dabei entstehen aus Vanadin(IV)-chlorid und Zinkdialkylen Komplexe des Vanadin(III)-chlorids, Vanadin(II)-chlorids und von Alkylvanadindichloriden mit Zinkchlorid, Alkylzinkchloriden oder Zinkdialkylen. Bortrialkyle bewirken die Bildung von reaktivem Vanadin(III)-chlorid, das in Komplexe mit Diäthyläther der Formel VCl₃ · n O(C₂H₅)₂ (n = 1–3) übergeführt werden konnte. Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXI. Experiments for the Alkylation of Vanadium Tetrachloride and Vanadium Oxidetrichloride Abstract. It is reported on experiments for alkylating vanadium tetrachloride by means of zinc dialkyls and boron trialkyls. Zinc dialkyls causes the formation of complexes of vanadium tetrachloride, vanadium trichloride and alkyl vanadium dichlorides with zinc chloride, alkyl zinc chlorides and zinc dialkyls. In the reactions with boron trialkyls high reactive vanadium trichloride is formed, which reacts with diethyl ether to complexes with the formula VCl₃ · n O(C₂H₅)₂ (n = 1–3).     

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. 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. 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. 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).