Modellrechnungen zu den Schwingungsspektren von Tris(trimethylsilyl)phosphan und Tris(triphenylsilyl)phosphan

The vibrational spectra of Tris(trimethylsilyl)phosphane-d ₀ and -d ₂₇ as well as Tris(triphenylsilyl)phosphane are reported and assigned. A normal coordinate analysis has been performed. The resulting SiP valence force constants (190 and 200 N/m) are compared with the force constants of other silylphosphanes.

     

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 ).     

Dialkylamino-bis(trimethylsilyl)amino-chlorborane und ihre Reaktion mit Natrium-bis(trimethylsilyl)amid

Zusammenfassung Verbindungen des Typs R₂NBCIN(Sime ₃)₂ ^* (R=C₂H₅,ⁱC₃H₇, C₆H₁₁, C₆H₅) bleiben bis zu hohen Temperaturen beständig. Sie reagieren jedoch mit NaN(Sime ₃)₂ unter Übertragung einer Methylgruppe von einem Silicium-zu einem Boratom zu N,N-Bis(trimethylsilyl)-tetramethylcyclodisildiazan und R₂NBmeN(Sime ₃) (R=C₂H₅,ⁱC₃H₇).

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Compounds of the type R₂NBClN(Sime ₃)₂ ^* were prepared. (R=C₂H₅,ⁱC₃H₇, C₆H₁₁, C₆H₅. They do not show any tendency to condense thermally under elimination of trimethylchlorosilane. When these silylaminoboranes were allowed to react with NaN(Sime ₃)₂, complicated rearrangements were observed. The compounds in which R=C₂H₅ orⁱC₃H₇ rearranged under formation of N,N-bis(trimethylsilyl)-tetramethylcyclodisildiazane and R₂NBmeN(Sime)₂. In this reaction a migration of a methyl group from silicon to boron occurs.

     

Base-freie Tris(trimethylsilyl)methyl-Derivate des Lithiums,Aluminiums, Galliums und Indiums

Base-free Tris(trimethylsilyl)methyl Derivatives of Lithium, Aluminium, Gallium, and Indium Base-free LiR* (R*=-C(SiMe₃)₃) has been prepared from R*Cl and Li-metal in toluene at 85?90°C and used to synthesize the metallanes R*MMe₂ with M = Al, Ga and In, respectively. The NMR (¹H, ¹³C, ²⁹Si) and the vibrational spectra of these trisyl compounds have been discussed. AlCl₃ and LiR*(ratio 1 : 1) forms the metallate metallate Li[R*AlCl₃]. The triclinic unit cell (space group P1 ) consists of a centrosymmetric assoziate, formed by four Li[R*AlCl₃]- units with Al? Cl…?Li bridges, two pairs of Li-atoms differing in their chlorine-coordination and two disordered toluene molecules, inserted in the crystal lattice (R₁wR₂ =0,0444/0,1072). The reaction of GaCl₃ with LiR* (I :1) gives the unusual sesquichloride (R*Ga(Cl_1,33)Me_0,67)₃ in moderate yield. The X-ray structure determination shows a Ga₃Cl₃-skeleton with chairconformation and disordered, terminal gallium ligands (R₁/wR₂= 0,0646/0,2270).     

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.     

Mono- und Bis(trimethylsilyl)formamid

Zusammenfassung Die Umsetzung von Formamid mit Hexamethyldisilazan (Rk. 3) oder mit Trimethylsilylcyanid (Rk. 1) in Benzol ergibt Trimethylsilylformamid (I). Dieses läßt sich nach metallierung durch nachfolgende Umsetzung mit Trimethylchlorsilan bei –65° in mäßiger Ausb. (30%) in Bis(trimethylsilyl)formamid (II) überführen (Rk. 13). Den NMR- und IR-Spektren nach liegt II in der N,N-, nicht in der N,O-Bis(trimethylsilyl)-carbonsäureamid-Struktur vor. Die direkte Umsetzung von Formamid mit Hexamethyldisilazan ergibt in hoher Ausbeute Triazin (Rkk. 5, 6). Diese Methode ist allen anderen Triazin-Synthesen überlegen.

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Mono- and bis-(trimethylsilyl)-formamide (LXXXIInd contribution to the chemistry of silicon—Nitrogen compounds)

Reactions of formamide with hexamethyldisilazane (equ. 3) or with trimethylsilylcyanide (equ. 1) in benzene give trimethylsilylformamide (I). After metallation of I and succeeding reaction with trimethylchlorosilane at –65°, bis(trimethylsilyl)formamide (II) can be isolated with 30% yield (equ. 13). Infrared as well as nmr spectra point to a N,N-, not to a N,O-bis(trimethylsilyl)derivative in the compound II. The solvent free reaction of formamide with hexamethyldisilazane leads in high yield to triazine (equ. 5, 6); this method is superior to all other triazine syntheses.

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81. Mitt.:A. Blaschette, G. Schirawski undU. Wannagat, Inorg. Nucl. Chem. Letters (im Druck).

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Mit Auszügen aus der DissertationG. Schirawski, Techn. Univ. Braunschweig 1969.

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Sonderdrucke überU. W., D-33 Braunschweig (Germany), Pockelsstr. 4, Institut für Anorganische Chemie der Techn. Universität.     

Halogen- und aminofunktionelle Tris(trimethylsilyl)silyl-silane

Halogeno- and Aminofunctional Tris(trimethylsilyl)silyl-silanes Lithium-tris(trimethylsilyl)silane 1 reacts with halogenosilanes to give thermally stable compounds of the type ( 2 – 11 ). The substitution of the bulky (trimethylsilyl)amino group occurs in reactions of 1 with aminofluorosilanes — ( 12 – 14 ). In excess 1 reacts with 2–14 under formation of (Me₃Si)₄Si. The substitution compounds 15–17 are obtained in the reaction of 3 and 9 with lithium salts of primary amines. The 1,3-diaza-2,4-disilacyclobutan 18 is formed by HF-elimination of 15 .     

Synthese,Spektren und Strukturen einfacher Derivate des Tris(bis(trimethylsilyl)methyl)indiums,In(CH(Si(CH3)3)2)3

Syntheses, Spectra, and Structures of Simple Derivatives of Tris(bis(trimethylsilyl)methyl Indium, In(CH(Si(CH₃)₃)₂)₃ Like trimethyl- or triethylindium tris(disyl)indium, In(CH(SiMe₃)₂)₃ (≙ InR₃) also reacts with equimolar amounts of water, D₂O, MeOH, HCl and HCOOH, respectively, in ether solution at room temperature to form the corresponding alkane, here (Me₃Si)₂CH₂, and the simple monosubstitution products R₂InX. With the dibasic oxalic and sulfuric acid the multinuclear derivatives (R₂In)₂C₂O₄ and [RIn(R₂In)₂(SO₄)₂]₂ are formed, respectively. The halogenides R₂InCl, RInCl₂, and RInBr₂ have been prepared by metathesis from InHal₃ and InR₃ (molar ratios 1 : 2 and 2 : 1). The ¹H, ¹³C, and ²⁹Si NMR- as well as the vibrational spectra (IR, Raman) are discussed. According to the X-ray structure elucidations the monosubstitution products R₂InX (with X = OH, OMe, Cl) are dimeric in the solid state and consist of planar, centrosymmetric fourmembered In₂X₂ skeletons. The dibromide RInBr₂ forms a polymeric chain structure with five-fold co-ordinated metal centres and vertex linked, alternately appearing planar as well as slightly folded In₂Br₂-moities. The “sesquisulfate” [R₅In₃(SO₄)₂]₂ has an uncommon, cage-like structure with four as well as five-fold co-ordinated In atoms. The structural data could not be optimally refined due to the highly disordered disyl groups.     

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.     

Synthese und struktur von dicyclopentadienyl(trimethylsilyl)titanchlorid

Dicyclopentadienyl(trimethylsilyl)titanium chloride, a stable trimethylsilyltitanium compound, is synthesized by reaction of dicyclopentadienyltitanium dichloride and tris(trimethylsilyl)aluminium, coordinated with diethyl ether, or lithium tetarakis(trimethylsilyl)aluminate. The IR and NMR spectra are reported. The crystal structure of the title compound has been determined. It shows a distorted tetrahedral surrounding of the titanium atom; the Ti–Si distance is 267 pm.     

Bis(trimethylsilyl)amino-halogenoborane und ihre cyclischen Kondensationsprodukte

Zusammenfassung Bis-[bis(trimethylsilyl)amino]-fluorboran (I), Bis-(trimethylsilyl)-amino-dichlorboran (II) und Bis-[bis(trimethylsilyl)-amino]-chlor-boran (III) werden durch Umsetzung von BCl₃ und BF₃ mit NaN(Sime ₃)₂ in Äther dargestellt. Alle Verbindungen lassen sich thermisch unter Abspaltung von Trimethylhalogenosilanen kondensieren. Während II zu B-Trichloro-N-tris(trimethylsilyl)-borazol kondensiert, ergeben I und III überraschend ein viergliedriges B–N-Ringsystem.Phenyl-alkoxy-bis(trimethylsilyl)aminoborane gehen ähnliche Kondensationsreaktionen ein.

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Bis-[bis(trimethylsilyl)amino]-fluoroborane (I), bis(trimethylsilyl)amino-dichloroborane (II) and bis-[bis-(trimethylsilyl)amino-]chloroborane (III) were synthesized by reaction of BF₃ and BCl₃ with sodium-bis(trimethylsilyl)-amide. All compounds undergo thermal condensation under elimination of the corresponding trimethylhalosilane. So II forms B-trichloro-N-tris(trimethylsilyl)-borazene, while I and III unexpectedly yield a fourmembered B–N-ring system. Phenyl-alkoxy-bis-(trimethylsilyl)-aminoboranes condense in a similar way to B-phenyl-N-trimethylsilyl-borazene.

     

Synthese von Bis- und Tris(trimethylsilyl)methyl-aminofluorsilanen

Synthesis of Bis- and Tris(trimethylsilyl)-methyl-aminofluorosilanes Lithium-tris(trimethylsilyl)methane reacts with fluoro-silanes to give (Me₃Si)₃C—SiF₂R ( 1—3 , R = F, C₆H₅, CMe₃). 1 and 2 react with lithiated amines to aminofluorosilanes 4 a, 5 a, 6 a , and with a 1, 3-migration of a silyl group to the structure isomeric trimethylsilylaminofluorsilanes 4 b, 5 b, 6 b, 7, 8 . The disubstituted NH-compound 9 is obtained in the reaction of 1 with LiNH₂.     

Dimethylgallium-bis(trimethylsilyl)phosphan Schwingungsspektrum,Kraftkonstanten und Struktur

Dimethylgallium-bis(trimethylsilyl)phosphane, Vibrational Spectrum, Force Constants, and X-Ray Structure Dimeric dimethylgallium-bis(trimethylsilyl)phosphane, [Me₂Ga? P(SiMe₃)₂]₂, (Me = CH₃) is synthesized from Me₂GaCl and P(SiMe₃)₃ in hot toluene. The compound crystallizes in the triclinic space group P1 with the cell parameters a = 909.8(2), b = 960.5(2), c = 971.6(2) pm; α = 76.75(1)°, β = 80.35(1)°, γ = 63.94(1)° and Z = 1 (dimer). The Ga? P distances are 244.8 and 245.2 pm, the ring angles are 91.8° (Ga? P? Ga) and 88.2° (P? Ga? P), respectively. The vibrational spectrum (IR and Raman for the solid) has been measured and assigned; force constants calculations are carried out for the skeleton [C₂Ga? P(SiC₃)₂]₂ using Fleischhauers [26] PC-program.