Beiträge zur Chemie der Trifluormethylquecksilber-Verbindungen

Contribution to the Chemistry of Trifluoromethylmercury (II) Compounds CF₃HgI (I) has been obtained in appreciable amount by a newly modified method, The reaction of I with silver salts AgX or AgY₂ (X = CN, NCO, SCN, SeCN, N₃, SCF₃, IO₃; Y = O, C₂O₄, NCN) gives corresponding CF₃HgX derivatives (II–VIII, XI, XII, XVII) mostly in good yield. The synthesis of (CF₃Hg)₂S (IX) has been attained by the reaction of I with Tl₂CS₃, while it gives with Ag₂O (CF₃Hg)₂O (VIII) instead of the hydroxide. VIII reacts in ethereal solution with H₂Se giving (CF₃Hg)₂Se (X). Stable CF₃HgN and (CF₃Hg)₂N derivatives (XIII–XVII) could only be obtained when at least one more substituent on N atom, which reduces its basicity, is present. I.r., ¹⁹F-n.m.r. and mass spectroscopic data for the prepared compounds have been reported.     

Beiträge zur Chemie der Übergangsmetall-Diolefinkomplexe. II. Zur Charakterisierung phosphinstabilisierter Eisendiolefinkomplexe

Contributions to the Chemistry of Transition Metal Diolefin Complexes. II. Characterization of Phosphine-stabilized Iron Diolefin Complexes Bis(butadiene)triphenylphosphine iron and Bis(isoprene)triphenylphosphine iron are characterized by protolytic reactions, mass spectrometrical fragmentations and NMR-spectra. A structure for this compounds is proposed on the basis of the NMR spectra.     

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 Silicium-Stickstoff-Verbindungen. 163. Untersuchungen über einige Verbindungen mit BNSi-Struktureinheiten

Chemistry of Silicon-Nitrogen Compounds. 163. Investigation of Some Compounds with BNSi Structure Fragments Some formerly unknown compounds with BNSi structure fragments were prepared (or obtained on a not expected way), confirmed in their structure and described in their properties: (EtO)₂BN(SiMe₃)₂ ( V ), FB[N(SiCl₃)₂]₂ ( XIII ), the derivatives IV, XVI – XIX of the six-, five- and four-membered ring systems cyclotriazatriborane, cyclodisilaboradiazane, and cyclosilaboradiazane and XXIII of a [3, 4]-spiro system. Br₂BN(SiMe₃)₂ ( III ), already known, was prepared by a different method.     

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 Schwefelhalogenide. 7. Trifluormethyliodsulfan

Contributions to the Chemistry of Sulfur Halides. 7. Trifluoromethyliodosulfane The preparation of CF₃SI is reported. The molecule is characterized by vibrational, nuclear magnetic resonance, UV/VIS, and mass spectra. CF₃SI chemically behaves like the interhalogen compound ICl. At higher temperatures the compound completely decomposes in CF₃SSCF₃ and I₂.     

Beiträge zur Chemie der Silicium-Stickstoff-Verbindungen. XCI. Dekamethylcyclotetrasilazan

Decamethylcyclotetrasilazane (I) was prepared starting with 1,3-dichloropentamethyldisilazane (II), 1.3-dichlorotetramethyldisilazane (III) and 1,3-bis-(methylamino)tetramethyldisilazane (IV). respectively, according to scheme 1, equ. (1), (2) and (3) in the text. (I) does not form, as given in the literature (equ. 4)⁵, by thermal transformation of bis(methylaminodimethylsilyl)-tetramethylcyclodisilazane (V); in this case exclusively – in equ. (2) and (3) only in side steps – the reaction products are a mixture of N-methylcyclotrisilazanes (scheme 2, VI–IX).     

Beiträge zur Chemie der Silicium-Schwefel-Verbindungen. 44. Trialkoxysilylthioderivate der Permethylpolysilane

Contributions to the Chemistry of Silicon-Sulphur Compounds. 44. Trialkoxysilylthio Derivatives of Permethylpolysilanes By reaction of (RO)₃SiSH · NEt₃ (R = i-Pr, t-Bu) with α,ω-Cl₂(SiMe₂)_n (n = 1, 2, 3, 4, 6) or with 1-Cl(SiMe₂)_nMe (n = 2, 4) trialkoxysilylthio derivatives of polysilanes of the two series α,ω-(RO)₃SiS(SiMe₂)_nSSi(OR)₃ and 1-(RO)₃SiS(SiMe₂)_nMe have been prepared. Some properties of obtained new compounds were given. The resistance of the Si? S bond on protolytic splitting has been characterized by half-life times of the alcoholysis reaction.     

Beiträge zur Chemie der Silicium-Schwefel-Verbindungen. XXVIII. Trimethylsilylderivate der Trialkoxysilanthiole

Contributions to the Chemistry of Silicon-Sulphur Compounds. XXVIII. Trimethylsilylderivatives of Trialkoxysilanethiols The reactions of trialkoxysilanethiols and their salts with trimethylchlorosilane and hexamethyldisilazane were investigated. The preparation of trimethyltrialkoxydisilthianes has been described. Some properties of the obtained compounds were given and about their silylation ability has been considered.     

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. 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 Silicium-Schwefel-Verbindungen. XXIX. 29Si-NMR-Untersuchungen

Contributions to the Chemistry of Silicon-Sulphur Compounds. XXIX. ²⁹Si-N.M.R. Investigations Three series of silicon-sulphur compounds (RO)₃SiSR′ (I), (i-PrO)_4?nSi(SEt)_n (II) and cyclic Si? S compounds (III) were prepared, some of them at the first time and their ²⁹Si-N.M.R. spectra were measured. In the series of trialkoxysilylthio derivatives (I) were the steric and inductive effects of the RO and R'S groups evaluated. In the series II were the ²⁹Si-N.M.R. chemical shifts related to the relative paramagnetic screening constants σ^* and netto charge at the silicon atom q(Si) using the EN-quantum-chemical model discussed. In the series III were the shift contribution of the (SiS)₂ and 1-sila-2,5-dithiacyclopentan rings determined.     

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. 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 Si-N-Bindung,XVIII [1]. Über lineare,cyclodisilazan-modifizierte Oligosiloxane

Linear oligosiloxanes with cyclodisilazane rings built into the siloxane chain were prepared by the reaction of hydroxysilyl substituted cyclodisilazanes in the form of their lithiumsilanolates with dimethyldichlorosilane, α,ω-chlorosiloxanes or dimethylchlorosilyl substituted cyclodisilazanes.     

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 Übergangsmetall-Diolefinkomplexe. III. Elektrochemische Darstellung von Kobaltkomplexverbindungen acyclischer 1,3-Diolefine

Contributions to the Chemistry of Transition Metal Diolefin Complexes. III. Electro-chemical Preparation of Cobalt Complex Compounds of Noncyclic 1,3-Diolefins The synthesis is described of butadiene coordination compounds of the type (π-C₄H₆)Co(π-C₄H₆R) · L by electrolytic reduction of cobalt salts in presence of butadiene, where R represents an H or C₄H₇ radical and L P(n-C₄H₉)₃ or P(C₆H₅)₃.