Reaktionen von R4Sb2 (R = Me,Et) mit (Me3SiCH2)3M (M = Ga,In) und Kristallstrukturen von [(Me3SiCH2)2InSbMe2]3 und [(Me3SiCH2)2GaOSbEt2]2

Reactions of R₄Sb₂ (R = Me, Et) with (Me₃SiCH₂)₃M (M = Ga, In) and Crystal Structures of [(Me₃SiCH₂)₂InSbMe₂]₃ and [(Me₃SiCH₂)₂GaOSbEt₂]₂ The reaction of (Me₃SiCH₂)₃In with Me₂SbSbMe₂ gives [(Me₃SiCH₂)₂InSbMe₂]₃ ( 1 ) and Me₃SiCH₂SbMe₂. [(Me₃SiCH₂)₂GaOSbEt₂]₂ ( 2 ) is formed by the reaction of (Me₃SiCH₂)₃Ga with Et₂SbSbEt₂ and oxygen. The syntheses and the crystal structures of 1 and 2 are reported.     

Synthese und Eigenschaften teilsilylierter Tri- und Tetraphosphane. Reaktionen lithiierter Diphosphane mit Chlorphosphanen

Synthesis and Properties of Partially Silylated Tri- and Tetraphosphanes. Reaction of Lithiated Diphosphanes with Chlorophosphanes The reactions of Li(Me₃Si)P? P(SiMe₃)(CMe₃) 1 , Li(Me₃Si)P? P(CMe₃)₂ 2 , and Li(Me₃C)P? P(SiMe₃)(CMe₃) 3 with the chlorophosphanes P(SiMe₃)(CMe₃)Cl, P(CMe₃)₂Cl, or P(CMe₃)Cl₂ generate the triphosphanes [(Me₃C)(Me₃Si)P]₂P(SiMe₃) 4 , (Me₃C)(Me₃Si)P? P(SiMe₃)? P(CMe₃)₂ 6 , [(Me₃C)₂P]₂P(SiMe₃) 7 , and (Me₃C)(Me₃Si)P? P(SiMe₃)? P(CMe₃)Cl 8 . The triphosphane (Me₃C)₂P? P(SiMe₃)? P(SiMe₃)₂ 5 is not obtainable as easily. The access to 5 starts by reacting PCl₃ with P(SiMe₃)(CMe₃)₂, forming (Me₃C)₂ P? PCl₂, which then with LiP(SiMe₃)₂ gives (Me₃C)₂ P? P(Cl)? P(SiMe₃)₂ 11 . Treating 11 with LiCMe₃ generates (Me₃C)₂P? P(H)? P(SiMe₃)₂ 16 , which can be lithiated by LiBu to give (Me₃C)₂P? P(Li)? P(SiMe₃)₂ 13 and after reacting with Me₃SiCl, finally yields 5 . 8 is stable at ?70°C and undergoes cyclization to P₃(SiMe₃)(CMe₃)₂ in the course of warming to ambient temperature, while Me₃SiCl is split off. 7 , reacting with MeOH, forms [(Me₃C)₂P]₂PH. (Me₃C)₂P? P(Li)? P(SiMe₃)₂ 18 , which can be obtained by the reaction of 5 with LiBu, decomposes forming (Me₃C)₂P? P(Li)(SiMe₃), P(SiMe₃)₃, and LiP(SiMe₃)₂, in contrast to either (Me₃C)₂P? P(Li)? P(SiMe₃)(CMe₃) 19 or [(Me₃C)₂P]₂PLi, which are stable in ether solutions. The Li phosphides 1 , 2 , and 3 with BrH₂C? CH₂Br form the n-tetraphosphanes (Me₃C)(Me₃Si)P? [P(SiMe₃)]₂? P(SiMe₃)(CMe₃) 23 , (Me₃C)₂P? [P(SiMe₃)]₂? P(CMe₃)₂ 24 , and (Me₃C)(Me₃Si)P? [P(CMe₃)]₂? P(SiMe₃)(CMe₃) 25 , respectively. Li(Me₃Si)P? P(SiMe₃)₂, likewise, generates (Me₃Si)₂P? [P(SiMe₃)]₂? P(SiMe₃)₂ 26 . Just as the n-triphosphanes 4 , 5 , 6 , and 7 , the n-tetraphosphanes 23 , 24 , and 25 can be isolated as crystalline compounds. 23 , treated with LiBu, does nor form any stable n-tetraphosphides, whereas 24 yields (Me₃C)₂P? P(Li)? P(SiMe₃)? P(CMe₃)₂, that is stable in ethers. With MeOH, 24 , forms crystals of (Me₃C)₂P? P(H)? P(SiMe₃)? P(CMe₃)₂.     

Substitutionsreaktionen mit Schwefeldiimiden

Substitution Reactions with Sulphur Diimides Substituted sulphur diimides are obtained by the reactions of (CH₃)₃Si? N?S?N? Si(CH₃)₃ with CH₃SO₂Cl and CCl₃SCl or with P₂O₃F₄ and (CH₃)₃Si? N?S?N? SN(CH₃)₂. S₄N₄ reacts with (CH₃)₂Si[N(CH₃)₂]₂ to from (CH₃)₂Si(N(CH₃)₂)? N?S?N? SN(CH₃)₂ while S₃N₂Cl₂ yields (CH₃)₂Si(Cl)? N?S?N? SN(CH₃)₂. It is possible to substitute the chlorine atom by diethylamine in the last compound. The new compounds are intermediates for the syntheses of cyclic sulphur-nitrogen compounds. They were characterized by mass-, ir-, ¹H-nmr spectra and elemental analysis.     

Bildung siliciumorganischer Verbindungen. 73. Reaktionen C-chlorierter 1,3-Disilapropane mit CH3MgCl

Formation of Organosilicon Compounds. 73. Reactions of C-chlorinated 1,3-Disilapropanes with CH₃MgCl (Cl₃Si)₂CCl₂ reacts with an excess of meMgCl (me = CH₃) in Et₂O (diethylether) forming (me₃Si)₂₂C?CH₂ mainly besides Si-methylated 1,3-disilapropanes with CmeCl, CHCl, CH₂ groups [6]. For investigating the mechanism of formation of the methylidengroup reactions were carried out with differently Si-methylated and Si-chlorinated 2-methyl-1-2-chloro-1,3-disilapropanes and 2,2-dichloro-1,3-disilapropanes. Whereas (me₃Si)₂CmeCl reacts neither with meMgCl nor with Lime. it forms (me₃Si)₂C?CH₂ and (me₃Si)₂CmeH with Li or Mg resp. The reaction starts with the metallation to (me₃Si)₂CmeLi and (me₃Si)₂Cme(MgCl) resp., followed by elimination of LiH and HMgCl resp. with formation of (me₃Si)₂C?CH₂. LiH and HMgCl resp. reduces (me₃Si)₂CmeCl to (me₃Si)₂CmeH. This mechanism is supported by the reactions of (me₃Si)₂CCl(CD₃). The Si-chlorination increases the reactivity of the CmeCl group and the created C?CH₂ group favours Si-methylation. The CCl₂ group is more reactive than the CmeCl group; (me₃Si)₂CCl₂ already forms the methyliden group with meMgCl in Et₂O via the not isolated intermediate (me₃Si)₂CCl(MgCl). which prefers the methylation to (me₃Si)₂Cme(MgCl). The n.m.r. data of the investigated compounds are given.     

A comparison of local structures in crystalline P(EO)3LiCF3SO3 and glyme-LiCF3SO3 systems

The newly discovered crystal structures of CH₃(OCH₂CH₂)OCH₃(LiCF₃SO₃)₂, monoglyme:(LiTf)₂, and CH₃(OCH₂CH₂)₃OCH₃(LiCF₃SO₃)₂, triglyme:(LiTf)₂, are briefly described. The coordination of lithium cations and the CF₃SO₃⁻ anions in these structures is compared with the cation and anion coordination in the crystalline phase of high molecular weight P(EO)₃LiCF₃SO₃. Comparison is also made with the previously reported crystalline phase of CH₃(OCH₂CH₂)₂OCH₃LiCF₃SO₃, diglyme:LiTf. A tendency to form trans-gauche-trans conformations for the bond order -O-C-C-O- is noted in adjacent ethylene oxide sequences interacting with a five-coordinate lithium ion.     

Fluordiazadiphosphetidine. 21. Mitt. Die Photochemische Chlorierung von 2,2,2,4,4,4-Hexafluoro-1,3-diethyl (und dipropyl)-1,3,2λ5,4λ5-diazadiphosphetidin und die Herstellung von 2,2,2,4,4,4-Hexafluoro-1-(cyanometyl)-3-methyl-1,3,2λ5,4λ5-diazadiphosphetidin

Summary The result of the chlorination of (CH₃CH₂NPF₃)₂ and (CH₃CH₂CH₂NPF₃)₂ with chlorine under UV-radiation were the new compounds CH₃CH₂(NPF₃)₂CH₂CH₂Cl and CH₃CH₂CH₂(NPF₃)₂CH₂CH₂CH₂Cl. The reaction of CH₃(NPF₃)₂CH₂Cl with KCN and crown-ether gave the new compound CH₃(NPF₃)₂CH₂CN.

     

Reaktionen von Silylphosphanen mit Schwefel

Reactions of Silylphosphines with Sulphur We report about reactions of Me₂P? SiMe₃ 2 , MeP(SiMe₃)₂ 3 , (Me₃Si)₃P 4 , P₂(SiMe₃)₄ 5 , and (Me₃Si)₃P₇ 1 with elemental sulphur. Without using a solvent 2 reacts very vigorously. The reactions with 3 and 4 show less reactivity which is even more reduced with 5 and 1 . With equivalent amounts of sulphur the reactions with 2 , 3 , 4 lead to compounds with highest content of sulphur. These compounds are Me₃SiS? P(S)Me₂ 9 from 2 , (Me₃SiS)₂P(S)Me 13 from 3 and (Me₃SiS)₃P(S) 16 from 4 . Besides, the by-products (Me₃Si)₂S 8 , P₂Me₄ 7 , and Me₂P(S)? P(S)Me₂ 11 can be obtained. The reactions of silylphosphines in a pentane solution run much slower so that the formation of intermediates can be observed. Reaction with 2 yields Me₃SiS? PMe₂ 6 and Me₂P(S)PMe₂ 10 , which lead to the final products in a further reaction with sulphur. From 3 (Me₃SiS)(Me₃Si)PMe 14 and (Me₃SiS)₂PMe 12 can be obtained which react with sulphur to (Me₃SiS)₂P(S)Me 13. 4 leads to the intermediates (Me₃SiS)(Me₃Si)₂P 18 , (Me₃SiS)₂(Me₃Si)P 17 , (Me₃SiS)₃P 15 yielding (Me₃SiS)₃P(S) 16 with excess sulphur. Depending on the molar ratio (P₂SiMe₃)₄ 5 reacts to (Me₃Si)₂P? P(SSiMe₃)(Sime₃), (Me₃SiS)(Me₃Si)P? P(SSiMe₃). (Diastereoisomer ratio 10:1), (Me₃SiS)₂P? P(SiMe₃)₂ and (Me₃SiS)₂P? P(SSiMe₃)(Sime₃). With the molar ratio 1:4 the reaction yields (Me₃SiS)₂P? P(SSiMe₃)₂ (main product), (Me₃SiS)₃P(S) and (Me₃SiS)₃P. All silylated silylphosphines tend to decompose under formation of (Me₃Si)₂S. (Me₃Si)₃P₇ reacts with sulphur at 20°C (15 h) under decomposition of the P₇-cage and formation of (Me₃SiS)₃P(S). The products of the reaction of 5 with sulphur in hexane solution (molar ratio more than 1:3) undergo readily further reactions at 60°C under cleavage of P? P bonds and splitting off (Me₃Si)₂S, leading to (Me₃SiS)₃P(S) and cage molecules like P₄S₃, P₄S₇, and P₄S₁₀ and P? S-polymers. (Me₃SiS)₃P(S) isi thermally unstable and decomposes to P₄S₁₀ and (Me₃Si)₂S. Sulphur-containing silylphosphines like (Me₃SiS)P(S)Me₂ react with HBr at ?78°C under formation of Me₃SiBr (quantitative cleavage of the Si? S bond) and Me₂P(S)SH, which reacts with HBr to produce H₂S and Me₂P(S)Br.     

Zur Bildung von Disilylphosphino-Element-Verbindungen des C,Si, P

The Formation of Disilylphosphino-Element Compounds of C, Si, P The reactions of (me₃Si)₂PLi · OR₂ a (OR₂ = 1 monoglyme or 2 THF; me = CH₃) with CH₃Cl, CH₂Cl₂, ClCH₂CH₂Cl and ClCH₂? C₆H₅ give the compounds (me₃Si)₂Pme, (me₃Si)₂P? CH₂? P(Sime₃)₂, (me₃Si)₂P? CH₂CH₂Cl, (me₃Si)₂P? CH₂CH₂? P(Sime₃)₂ and (me₃Si)₂P? CH₂C₆H₅ respectively. In the same manner a reacts with me₂SiCl₂ in a molar ratio 1:1 to (me₃Si)₂P? Sime₂Cl and in a molar ratio 2:1 to (me₃Si)₂P? Sime₂? P(Sime₃)₂ b . The compound b decomposes to [me₃SiP? Sime₂]₂ and (me₃Si)₃P at 220°C. In the reactions of a with ClP(C₆H₅)₂ and ClPme₂ the compounds (me₃Si)₂P? P(C₆H₅)₂ and (me₃Si)₂P? Pme₂, respectively, are obtained. a reacts with HgCl₂ to (me₃Si)₂P? P(Sime₃)₂. (me₃Si)₃P can be cleaved with ClP(C₆H₅)₂ and ClPme₂ yielding (me₃Si)₂P? P(C₆H₅)₂ and (me₃Si)₂P? Pme₂, respectively. The ¹H- and ³¹P-n.m.r. and mass spectroscopic data are reported.     

Perfluoralkyljod-verbindungen: das trifluormethyljoddinitrat CF3J(NO3)2

CF₃I(NO₃)₂ is formed from the reactions of CF₃IF₂ or CF₃IO with N₂O₅ as well as CF₃I with ClNO₃. During the reactions of CF₃IF₂ with N₂O₅ or CF₃I with ClNO₃ the intermediate products CF₃IF(NO₃) or CF₃ICl(NO₃) can be identified. The preparations, properties, ¹⁹F-nmr spectra and the thermal decomposition of CF₃I(NO₃)₂ are described.     

Thermodynamics of Bromo-Adamantane and Carbon Tetrabromide Under Pressure

Excess molar volumes at 298.15 K of the ternary system {CH₃(CH₂)₂CO₂(CH₂)₃CH₃+ CH₃(CH₂)₇OH+CH₃(CH₂)₆CH₃} and the binary mixtures {CH₃(CH₂)₂CO₂(CH₂)₃CH₃+ CH₃(CH₂)₇OH}, {CH₃(CH₂)₂CO₂(CH₂)₃CH₃+CH₃ (CH₂)₆CH₃} and {CH₃(CH₂)₇OH+ CH₃(CH₂)₆CH₃} were determined using an Anton Paar DMA 60/602 densimeter. All experimental values were compared with the results obtained with empirical expressions for estimation of the ternary properties from the binary data. Variable-degree polynomials were fitted to the results. This revised version was published online in July 2006 with corrections to the Cover Date.     

Bildung siliciumorganischer Verbindungen. 70 [1]. Reaktionen Si-fluorierter 1,3,5-Trisilapentane mit CH3MgCl und LiCH3

Formation of Organosilicon Compounds. 70. Reactions of Si-fluorinated 1,3,5-Trisilapentanes with CH₃MgCl and LiCH₃ F₃Si? CCl₂? SiF₂? CH₂? SiF₃ 3 reacts with meMgCl. (me = Ch₃ starting with a Si-methylation and not with a C-metallation as in the corresponding Si- and C-chlorinated compounds, e. g. (Cl₃Si? CCl₂)₂SiCl₂ [2]. A CCl-hydrogenation is observed too, which in the case of F₃Si? CCl₂? SiF₂? CHCl? SiF₃ 4 gives meS₃Si? CCl₂? Sime₂? CH₂? Sime₃. (F₃Si? CCl₂)_{2 5} reacts with meMgCl to form preferentially 1,2-Disilapropanes by cleaving a Si? Cbond. The isolation of F₃Si? CCl₂H and meF₂Si? CCl₂? SiF₂me allows to locate the bond where 5 is cleaved at the beginning of the reaction. With meLi 5 reacts to form mainly me₃Si? C?C? Sime₃, showing that in the reaction of meLi, being a stronger reagent than meMgCl, and 5 a C-metallation occurs, following the same mechanism as in the reaction with (Cl₃Si? CCl₂)₂)SiCl₂ [2]. The reaction conditions for the synthesis of Si-fluroinated and C-chlorinated 1,3,5-Trisilapentanes in a 0.1 mol scale are reported. N.m.r. data of all investigated compounds are tabulated.     

Metal to ligand group transfer reactions : II. Reactions of some π-allylrhodium(I) complexes with trifluoroacetic acid and alkyl,acyl and trimethyltin halides

Rh(π-C₃H₅)(PF₃)₃ (I), reacts with trifluoroacetic acid to form propene and [Rh(CF₃COO)(PF₃)₂]₂ (II). I reacts with t-butyl bromide to give [RhBr(PF₃)₂]₂ and a mixture of propene and 2-methyl-1-propene and with n-propyl bromide to give propene and [RhBr(PF₃)₂]₂. Rh(π-C₃H₅)(PPh₃)₂ (III), and t-butyl bromide yield propene and 2-methyl-1-propene. In these reactions a mechanism involving β-hydrogen abstraction and hydrogen migration via the metal to carbon is proposed. When III reacts with Me₃SnCl the Me₃Sn—moiety migrates intact to the π-allyl group. I reacts with acetyl chloride to give propene, [RhCl(PF₃)₂]₂ and the carbonyl rhodium complex Rh₂Cl₂(PF₃)₃(CO). II does not apparently undergo phosphine ligand exchange unlike the analogous halogeno-bridged dimers.     

Reaktionen von Nitrosylkomplexen: VIII. Ein alternativer Weg zu Cp3Co3(μ3-NO)2 sowie Synthese des isoelektronischen Clusters Cp3Co2Fe(μ3-NH)(μ3-NO)

Treatment of CpCo(C₂H₄)₂ with NO in hexane yields Cp₃Co₃(μ₃-NO)₂ together with the dinitrosoethane complex CpCo(NO)₂C₂H₄; the mixture of these known compounds can easily be separated. The reaction of [CpFeNO]₂ with excess CpCo(C₂H₄)₂ in THF gives Cp₃Co₂Fe(μ₃-NH)(μ₃-NO) as the main product, which is an isoelectronic congener of Cp₃Co₃(μ₃-NO)₂. Another isoelectronic species of possible composition Cp₃CoFe₂(μ₃-NH)₂ is found as a by-product.     

Rapid intramolecular interactions between organic isocyanates and hexafluorobut-2-yne on a dirhodium centre; X-ray crystal structure of (η-C5H5)2Rh2 {μ2(η3-C(CF3)C(CF3)C(O)N(Ph)}

Complexes of formula (η-C₅H₅₂Rh₂{CF₃C₂CF₃ · RNCO} have been prepared by three methods, from reactions between organic isocyanates and (η-C₅H₅)₂Rh₂(CO)(CF₃C₂CF₃) or (η-C₅H₅)₂Rh₂(CO)₂(CF₃C₂CF₃); by treatment of (η-C₅H₅)₂Rh₂(CO)(CF₃C₂CF₃) with organic azides; and by oxidation with Me₃NO of the organic isocyanide in (η-C₅H₅)₂Rh₂(CO)(CNR)(CF₃C₂CF₃). The crystal and molecular structure of the complex (η-C₅H₅)₂Rh₂{CF₃C₂CF₃ · RNCO} with R = Ph has been determined from single crystal X-ray diffraction data. This reveals that the isocyanate has condensed with the hexafluorobut-2-yne to form an amide ligand of the form C(CF₃)C(CF₃)C(=O)N(R); this bridges the two rhodium atoms in a μ₂η³-manner.     

The fluorination of uranium and vanadium oxides with some metal fluorides

UO₃ reacts with CrF₃ or CuF₂ forming UO₂F₂ and Cr₂O₃ or CuO respectively. Further fluorination occurs above 800°C to form UF₆ though the presence of excess CrF₃ gives mainly UF₄. The fluorination of U₃O₈ with CrF₃ gave UO₂F₂, UF₄ and Cr₂O₃ but with CuF₂ gave UO₂F₂, CuO and Cu₂O. VO₂ reacts with excess CrF₃ forming VF₃, VF₅ and Cr₂O₃. If there is a deficiency of CrF₃ the products are VOF₃, V₃O₅ and Cr₂O₃. CuF₂ and VO₂ form VOF₃, CuO and Cu₂O.     

Coordination,oligomerisation and transfer hydrogenation of acetylenes by some ruthenium and osmium carboxylates: Crystal and molecular structures of bis(trifluoroacetato)carbonyl-(methanol) bis(triphenylphosphine)ruthenium(II) and (1,4-diphenylbut-1-en-3-yn-2-yl)trifluoroacetato-(carbonyl) bis(triphenylphosphine)ruthenium(II)

The hydrides [MH(O₂CCF₃)(CO)(PPh₃)₂] (M = Ru or Os) react with disubstituted acetylenes PhCCPh and PhCCMe to afford vinylic products [M{C(Ph)CHPh}(O₂CCF₃)(CO)(PPh₃)₂] and [M{C(Ph)CHMe}(O₂CCF₃)(CO) (PPh₃)₂]/[M{C(Me)CHPh}(O₂CCF₃)(CO)(PPh₃)₂] respectively. Acidolysis of these products with trifluoroacetic acid in cold ethanol liberates cis-stilbene and cis-PhHCCHMe respectively thus establishing the cis-stereochemistry of the vinylic ligands. The complexes [M(O₂CCF₃)₂(CO)(PPh₃)₂] formed during the acidolysis step undergo facile alcoholysis followed by β-elimination of aldehyde to regenerate the parent hydrides [MH(O₂CCF₃)(CO)(PPh₃)₂] and thereby complete a catalytic cycle for the transfer hydrogenation of acetylenes. The molecular structure of the methanol-adduct intermediate, [Ru(O₂CCF₃)₂(MeOH)(CO)(PPh₃)₂] has been determined by X-ray methods and shows that the coordinated methanol is involved in H-bonding with the monodentate trifluoroacetate ligand [MEO-H---OC(O)CF₃; O...O = 2.54 Å]. The hydrides [MH(O₂CCF₃)(CO) (PPh₃)₂]react with 1,4-diphenylbutadiyne to afford the complexes [M{C(CCPh)CHPh} (O₂CCF₃)(CO)(PPh₃)₂]. The ruthenium product, which has also been obtained by treatment of [RuH(O₂CCF₃)(CO)(PPh₃)₂] with phenylacetylene, has been shown by X-ray diffraction methods to contain a 1,4-diphenylbut-1-en-3-yn-2-yl ligand. The osmium complexes [Os(O₂CCF₃)₂(CO)(PPh₃)₂], [OsH(O₂CCF₃)(CO)(PPh₃)₂] and [Os{C(CCPh)CHPh}(O₂CCF₃)(CO)(PPh₃)₂] all serve as catalysts for the oligomerisation of phenylacetylene. Acetylene reacts with [Ru(O₂CCF₃)₂(CO)(PPh₃)₂] in ethanol to afford the vinyl complex [Ru(CHCH₂)(O₂CCF₃)(CO)(PPh₃)₂].     

Cyclothiazeno-Komplexe des Wolframs mit Phosphaniminatound tertiär-Butoxyliganden

Cyclothiazeno Complexes of Tungsten with Phosphoraneiminato and t-Butoxy Ligands The cyclothiazeno complex [WCl₃(N₃S₂)]₂ reacts with the silylated phosphaneimine Me₃SiNPPh₃ in THF solution forming the cyclothiazenophosphoraneiminato complex [Cl₂W(N₃S₂)(NPPh₃)]_n which forms green crystals of [Cl₂W(N₃S₂)(NPPh₃)(Py)] ( 1 ) when pyridine is added. The corresponding reaction with Me₃SiNPMe₃ leads to the methyl derivative which is analogous to 1 and which is obtained as dark green crystals along with the tetrakis(phosphoraneiminato) complex of the crystal composition [W(NPMe₃)₄]Cl₂ · 2 [Cl₂W(N₃S₂)(NPMe₃)(Py)] · 2 CH₂Cl₂ ( 2 ). According to the crystal structure analyses the phosphoraneiminato ligands NPR₃^– cause as a result of the short WN bonds of approximately 180 pm a strong trans influence on one of the WN bonds of the planar WN₃S₂ rings and alternatingly long SN bonds. With LiOCMe₃ [WCl₃(N₃S₂)]₂ reacts forming the centrosymmetrically dimeric cyclothiazeno alkoxy complex [(Me₃CO)₄W(N₃S₂)Li₂Cl]₂ ( 3 ) the ion ensemble of which is linked via the lithium and the chlorine atoms.     

Fast orthometalation reactions at a binuclear dirhodium(II) complex. Synthesis,crystal structure and reactivity of Rh2(O2CCH3)3[(C6H4)PPh2]·(HO2CCH3)2

From the reaction of Rh₂(O₂CCH₃)₄(MeOH)₂, in hot acetic acid with PPh₃ the monometalated intermediate Rh₂(O₂CCH₃)₃[(C₆H₄)PPh₂](HO₂CCH₃)₂ has been isolated and characterized by an X-ray study. This compound rapidly reacts with an excess of PPh₃ in dichloromethane at room temperature to give Rh₂(O₂CCH₃)₂-[(C₆H₄)PPh₂]₂(PPh₃)₂ with a head-to-tail structure. The same procedure at higher temperatures gives a mixture of this compound and another doubly metalated compound with a head-to-head structure.     

Umsetzungen der Silylphosphine mit LiP(C2H5)2 und LiCH3

Whereas (CH₃)₃Si? P(C₂H₅)₂ does not react with LiP(C₂H₅)₂ (I), there are reactions of SiH-containing silylphosphines with one P(C₂H₅)₂ group as well as of SiH- and Simethylated silylphosphines with (I), yielding phosphorylated products and LiH according to equ. (1) (2). SiH-containing Silylphosphines, being Si? CH₃-free and having more than one P(C₂H₅)₂-group, such as HSi[P(C₂H₅)₂]₃, react with LiP(C₂H₅)₂ by exchange of Li for H, acc. to equ.(3). With (CH₃)₃SiCl, LiSi[P(C₂H₅)₂]₃ yields (CH₃)₃Si? Si[P(C₂H₅)₂]₃ and with SiH₃Br H₃Si? Si[P(C₂H₅)₂]₃. There is a cleavage of the Si? P bond with Li-CH₃ or n? LiC₄H₉. The reaction starts as shown in equ. (4), yielding (CH₃)₃SiH and (CH₃)₃Si? P(C₂H₅)₂ as intermediate products and finally (CH₃)₄Si (equ. 5).     

Diamino-di-tert-butylsilane als Bausteine cyclischer (SiN)2−, (SiNBN)2−, (SiN2Sn)- und spirocyclischer (SiN2)2Si-, (SiN2Sn)2S-Verbindungen

Diamino-di-tert-butylsilanes - Building Blocks for Cyclic (SiN)₂, (SiNBN)₂, (SiN₂Sn), and Spirocyclic (SiN₂)₂Si, (SiN₂Sn)₂S Compounds The aminochlorosilanes (Me₃C)₂SiClNHR ( 1 : R?H, 2 : R?Me) are obtained by the ammonolysis ( 1 ) respectively aminolysis ( 2 ) of di-tert-butyldichlorosilane in the n-hexane. The dilithium derivative of diamino-di-tert-butylsilane reacts with FSiMe₂R′ ( 3 : R′?Me, 4 : R′?F) in a molar ratio 1 : 2 to give the 1,3,5-trisilazanes 3 and 4 , (Me₃C)₂SiNHSiMe₂R′, in a molar ratio 1 : 1 with F₃SiN(SiMe₃)₂ to give the 1,3-diaza-2,4-disilacyclobutane 5 , (Me₃C)₂Si(NH)₂SiFN(SiMe₃)₂, and with F₂BN(SiMe₃)₂ to give the 1,3,5,7-tetraaza-2,6-dibora-4,8-disilacyclooctane 6 , [(Me₃C)₂SiNH-BN(SiMe₃)₂-NH]₂. The dilithium derivative of di-tert-butyl-bis(methylamino)silane reacts with SiF₄ with formation of the 1,3,5-trisilazane 7 , (Me₃C)₂Si(NMeSiF₃)₂, and the spirocycic compound 8 , [(Me₃C)₂Si(NMe)₂]₂Si, with SnCl₂ the cyclosilazane 9 , (Me₃C)₂SiNMe₂ is obtained. The dilithium derivative of 3 reacts with SnCl₂ to give the cyclo-1,3-diaza-2-sila-4-stannylen 10 , (Me₃C)₂Si(NSiMe₃)₂Sn. The oxidation of 10 with elemental sulfur leads to the formation of the spirocyclus 11 , [(Me₃C)₂Si(NSiMe₃)₂SnS]₂.