Zinn(II)-halogenid-Komplexe mit Tri-tert-butylphosphin und Tris(dimethylamino)phosphin

Tin(II) Halide Complexes with Tri-tert-butylphosphine and Tris(dimethylamino)-phosphine TIn(II) chloride and tin(II) bromide react with tri-tert-butylphosphine and with tris(dimethylamino)phosphine to give stable 1:1 adducts. Infrared and raman data as well as¹H-n.m.r., ³¹P-n.m.r., and ^119mSn-Mössbauer spectra of the novel phosphine dihalogennostannylenes are discussed in terms of an ylidic type of bonding.     

Alkoholyse von Tris(dimethylamino)-arsin

Alcoholysis of Tris (dimethylamino)arsine The reaction of tris(dimethylamino)arsine with alcoholes and thioles leads to the formation of esters of the general formula As(XR)₃ (X = O and S). The reaction is a suitable preparative method for the synthesis of the esters As(XR)₃ (X = O and S). By alcoholysis in steps results an equilibrium system containing the molecules AsX₃, AsX₂Y, AsXY₂, and AsY₃ (X = OR, Y = N(CH₃)₂).     

Darstellung und Kristallstruktur von Tris[1,3-bis(phenyltriazenido)benzol]-di-thallium(III)

Synthesis and Crystal Structure of Tris[1,3-bis(phenyltriazenido)benzene]-di-Thallium(III) Tris[1,3-bis(phenyltriazenido)benzene]-di-thallium(III) is formed by the reaction of di-sodium-1,3-bis(phenyltriazenido)benzene with thallium(I)-sulfate in a THF/H₂O mixture in the presence of oxygen. The compound crystallizes in the triclinic space group P1 1 with the lattice parameters a = 1368.8(2), b = 1539.3(2), c = 1676.0(3) pm, α = 106.04(3)°, β = 90.50(3)°, γ = 109.94(3)° and two formula units in the unit cell. The complex consists of two Tl atoms and three ligands, of which each N₃-unit acts as bidentate chelating group. The coordination sphere of Tl is trigonal prismatic with a coordination number of 6. The distances Tl? N range from 228 to 244 pm.     

Über die Umsetzung von Tris(dimethylamino)phosphin,Triisopropylphosphin und tButyldifluorphosphin mit tertiären Alkylaziden: Phosphazidbildung versus Phosphinimidbildung. Röntgenstrukturen von Triphenylmethylazid und Tris(dimethylamino)-N-triphenylmethylphosphazid

Reaction of Tris(dimethylamino)phosphine, Triisopropylphosphine and ^tButyldifluorophosphine with Tertiary Alkyl Azides: Phosphazide Formation versus Phosphinimide Formation. X-Ray Crystal Structures of triphenylmethylazide and Tris(dimethylamino)-N-triphenylmethyl Phosphazide Tris(dimethylamino)-phosphine and triisopropylphosphine react with tertiary alkyl azides RN₃ (R = ^tBu, 1-Ad, Trt) to give the corresponding phosphazides 1a–1c and 2a–2c , which involve a linear PN₃R-unit. The coordination geometries of the N₃ chains in triphenylmethylazide and 1c are completely different, associated with a change of hybridisation. Hence, the N₃-group of the triphenylmethylazide is nearly linear, whereas that of 1c shows approximately tetrahedral angles. The coordination geometry at the central nitrogen atom also depends on the substituents, possibly because of their varying ability to delocalize the π-electron system. In contrast, the reaction of ^tbutyldifluorophosphine with the same azides RN₃ led to the ^tbutyldifluorophosphinimides 3a–3c of the type ^tBuP(:NR)F₂. The hydrolysis of these compounds afforded the ^tbutylphosphonamidic fluorides ^tBuP(:O)(NHR)F (R = 1-Ad: 4b , Trt: 4c ), instead of the expected substitution products ^tBuP(:NR)(OH)F.     

Acyl- und Alkylidenphosphane. XVII. Triacetylphosphan aus Tris(trimethylsilyl)phosphan

Acyl- and Alkylidenephosphines. XVII. Triacetylphosphine from Tris(trimethylsilyl)-phosphine Tris(trimethylsilyl)phosphine reacts at 0°C with excess acetyl chloride in cyclopentane to form chlorotrimethylsilane and triacetylphosphine 3a . In contrast to the corresponding 2,2-dimethylpropionyl derivate (Z)- 5b the intermediate compounds (E)- and (Z)-acetyl-[1-(trimethylsiloxy)ethylidene]phosphine 5a are thermally instable. They could not be isolated in a pure state, but were characterized by NMR spectroscopic methods only. The isomers differ scarcely in their chemical shift values, but very much in their coupling constants. If the solution is cooled unsufficiently diacetyl-[1-(trimethylsiloxy)vinyl]phosphine 7 and the keto-enol-tautomers of diacetylphosphine K-/E- 2a are formed to a greater extend. ¹H-{³¹P}-INDOR experiments allowed the correlation between ¹H- and ³¹P-NMR resonances and hence the correct identification of the phosphines formed. Within days the compounds 2a and 7 also react at +20°C with an excess of acyl halide to give triacetylphosphine 3a .     

Über Tris(siloxymethyl)-, Tris(silylmercaptomethyl)- und Tris(silylmethyl)amine

By the reaction of alkali salts of triorgano-silanols, -silanethiols and trimethylsilylmethanol as well as of triorganosilyllithium compounds with tris(chloromethyl)amine, silyl derivatives of tris(hydroxymethyl)-, tris(mercaptomethyl)- and tris(methyl)amine were prepared.     

Darstellung von kristallwasserfreien Boraten aus Tris(methoxy)boran und Diskussion des Reaktionsweges

Preparation of Anhydrous Borates from Tris(methoxy)borane and Discussion of the Reaction Path Borates and polyborates of lithium, potassium, rubidium, calcium, and strontium free from water of crystallization are prepared. The infrared, Raman, ¹H- and ¹¹B nuclear magnetic resonance spectra suggest that the slowest step in the hydrolysis of tris(methoxy) borane in the presence of metal alkoxides in organic solvents may be expressed by the equation [ROB(OH)₃]^? + ROB(OH)₂ ? [RO(HO)₂BOB(OR)(OH)]^? + H₂O (R = CH₃ or H). From this alkylated diborate triborates, tetraborates, and pentaborates are then formed by a similar condensation sequence.     

Mono-, Bis- und Tris(trimethylsilyl)hydroxylamin

Ohne ZusammenfassungMit 1 Abbildung77. Mitt.:U. Wannagat undM. Schulze, Z. Chem.8, 255 (1968).Vorläufige Mitt.:U. Wannagat, Angew. Chem.78, 648 (1966).Auszugsweise vorgetragen auf dem 155th National Meeting der American Chemical Society, San Francisco, April 1968.Sonderdrucke überU. W., D-33 Braunschweig, Pockelsstr. 4, Inst. für Anorg. Chem. der Techn. Universität.Mit Auszügen aus der DissertationO. Smrekar, Techn. Hochschule Graz 1969.     

Reaktionen von Zink- und Cadmiumhalogeniden mit Tris(trimethylsilyl)phosphan und Tris(trimethylsilyl)arsan

Reactions of Zinc and Cadmium Halides with Tris(trimethylsilyl)phosphane and Tris(trimethylsilyl)arsane ZnCl₂ reacts with E(SiMe₃)₃ (E = P, As) in toluene in the presence of PⁿPr₃ to give the binuclear complexes [Zn₂Cl₂{E(SiMe₃)₂}₂(PⁿPr₃)₂] · C₇H₈ (E = P 1 , As 2 ). Therefore by the use of PⁱPr₃ clusters consisting of ten metal atoms are obtained, [Zn₁₀Cl₁₂(ESiMe₃)₄(PⁱPr₃)₄] (E = P 3 , As 4 ). As a result of the reaction of CdBr₂ with P(SiMe₃)₃ the compound [CdBr₂{P(SiMe₃)₃}]₂ ( 5 ) can be isolated at –40 °C. In the presence of PⁿPr₃ CdBr₂ reacts with P(SiMe₃)₃ forming the binuclear complex [Cd₂Br₂{P(SiMe₃)₂}₂(PⁿPr₃)₂] · thf ( 6 ). The same reaction with PⁱPr₃ yields to the cluster [Cd₁₀Br₁₂(PSiMe₃)₄{P(SiMe₃)₃}₄] · 2 C₇H₈ ( 7 ). ZnI₂ and CdI₂ react with As(SiMe₃)₃ to yield the complexes [MI₂{As(SiMe₃)₃}]₂ (M = Zn 8 , Cd 9 ). In the case of CdI₂ additionally the cluster [Cd₁₀I₁₂(AsSiMe₃)₄ · {As(SiMe₃)₃}₄] · 4,5 C₇H₈ ( 10 ) is formed which is analogous to the compounds 3 , 4 and 7 . In the presence of [PⁿBu₄]I 8  reacts in THF to give the ionic compound [PⁿBu₄]₂[Zn₆I₆(AsSiMe₃)₄(thf)₂] · C₆H₆ ( 11 ).     

Triacetoxysilan und Tris(trifluoracetoxy)silan

Zusammenfassung Die Darstellung der bisher unbekannten Verbindungen (CH₃COO)₃SiH und (CF₃COO)₃SiH wird beschrieben, ihre Schwingungs- und Kernresonanzspektren werden mitgeteilt. Die extrem liegenden Werte der Fluorverbindung werden im Zusammenhang mit den bisher bekannten Werten diskutiert.

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Triacetoxy silane and tris(trifluoroacetoxy) silane

The preparation of the formerly unknown compounds (CH₃COO)₃SiH and (CF₃COO)₃SiH is described, their vibrational and NMR-spectra are reported. Some extreme values of the latter compound are discussed.

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Mit 1 Abbildung

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Herrn Prof. Dr.A. Wacek zum 75. Geburtstag gewidmet.     

Tris(trimethylsilyl)methanselenenylhalogenide und -chalkogenide

Tris(trimethylsilyl)methaneselenenyl Halides and Chalcogenides . Ditrisyldiselenide ( 1 ) (trisyl = TSi = (Me₃Si)₃C) reacts with SOCl₂, Br₂ and I₂ to provide trisylselenenyl halides TSiSeX ( 2 : X = Cl; 3 : X = Br, 4 : X = I). Insertion of S and Se into the Se? Se bond of 1 to yield (TSiSe)₂S_n ( 5 : n = 1; 6 : n = 2) and (TSiSe)₂Se_n ( 7 : n = 1; 8 : n = 2) was catalysed by iodine. 5 was isolated in pure state and examined by X-ray diffraction. Triselenide 7 can be cleaved by I₂ in CS₂ to give 4 and Se₂I₂ ( 9 ). From 2 with Me₃SiCN and Me₃SiNCS, the new selenenyl pseudohalides TSiSeCN ( 10 ) and TSiSeSCN ( 11 ) were prepared. The compounds were characterised by ¹H, ¹³C- and ⁷⁷Se n.m.r. spectra.