Synthesis and characterization of organotin complexes with dithiocarbamates and crystal structures of (4‐NCC6H4CH2)2Sn(S2CNEt2)2 and (2‐ClC6H4CH2)2 Sn(Cl)S2CNBz2

Ten organotin derivatives with dithiocarbamates of the formulae (4‐NCC₆H₄CH₂)₂Sn(S₂CNEt₂)₂ (1), (4‐NCC₆H₄CH₂)₂Sn(S₂CNBz₂)₂ (2), (4‐NCC₆H₄CH₂)₂Sn[S₂CN(CH₂CH₂)₂NCH₃]₂ (3), (2‐ClC₆H₄CH₂)₂ Sn(S₂CNEt₂)₂ (4), (2‐ClC₆H₄CH₂)₂Sn(S₂CNBz₂)₂ (5), (4‐NCC₆H₄CH₂)₂Sn(Cl)S₂CNEt₂ (6), (4‐NCC₆H₄CH₂)₂Sn(Cl)S₂CNBz₂ (7), (4‐NCC₆H₄CH₂)₂Sn(Cl)S₂CN(CH₂CH₂)₂NCH₃ (8), (2‐ClC₆H₄CH₂)₂ Sn(Cl)S₂CNEt₂ (9) and (2‐ClC₆H₄CH₂)₂Sn(Cl)S₂CNBz₂ (10) have been prepared. All complexes were characterized by elemental analyses, IR and NMR. The crystal structures of complexes 1 and 10 were determined by X‐ray single crystal diffraction. For complex 1, the central tin atom exists in a skew‐trapezoidal planar geometry defined by two asymmetrically coordinated dithiocarbamate ligands and two 4‐cyanobenzyl groups. In addition, because of the presence of close intermolecular non‐bonded contacts, complex 1 is a weakly‐bridged dimer. In complex 10, the central tin atom is rendered pentacoordinated in a distorted trigonal bipyramidal configuration by coordinating with S atoms derived from the dithiocarbamate ligand. In vitro assays for cytotoxicity against five human tumor cell lines (MCF‐7, EVSA‐T, WiDr, IGROV and M226) furnished the significant toxicities of the title complexes. Copyright © 2006 John Wiley & Sons, Ltd.     

Metallation of aliphatic carbon atoms: II,syntheses and characterization of the cyclopalladated complexes of N,N-dimethylneopentylamine

N,N-Dimethylneopentylamine reacts with Pd(MeCO₂)₂ to give a novel trinuclear cyclopalladated complex [Me₂NCH₂CMe₂CH₂Pd(μ-MeCO₂)₂Pd(μ-MeCO₂)₂PdCH₂CMe₂CH₂NMe₂]?-0.5C₆H₆ (I). The reaction of I with PPh₃ affords both trans-[Pd(MeCO₂)₂(PPh₃)₂] (II) and [Pd(CH₂CMe₂CH₂NMe₂)(MeCO₂)(PPh₃)] (III). The reaction of III with LiCl yields a mononuclear cyclopalladated complex, [Pd(CH₂CMe₂CH₂NMe₂)Cl(PPh₃)] (IV).     

Dimethylphosphinato and dimethylarsinato complexes of Sb(III) and Bi(III) and their chemistry

Abstract  

The reaction of Me₂PO₂H and Me₂AsO₂H with SbCl₃, BiCl₃, and Bi(NO₃)₃·5H₂O gave the complexes Sb(Me₂PO₂)₃, Sb(Me₂AsO₂)₃, (Me₂PO₂)₂Bi-Cl, Bi(Me₂AsO₂)₃, (Me₂PO₂)₂Bi(NO₃), and (Me₂AsO₂)₂Bi(NO₃)·H₂O, respectively. The arsinato complexes did not react with the Lewis bases pyridine, Ph₃P, and Ph₃As in acetone. The compounds Sb(Me₂AsO₂)₃ and (Me₂AsO₂)₂Bi(NO₃)·H₂O reacted to a small extent with nicotinic acid in methanol but Bi(Me₂AsO₂)₃ gave (Me₂AsO₂-BiO) _x in good yields. (Me₂AsO₂)₂Bi(NO₃)·H₂O in methanol quantitatively rearranged to new complexes with the same composition, [(Me₂AsO₂)₂Bi(NO₃)·H₂O]′ and [(Me₂AsO₂)₂Bi(NO₃)·H₂O]″ in the presence of pyridine. With thiophenol in air, Sb(Me₂AsO₂)₃ gave PhSSPh and Me₂As-SPh (1:1 mol ratio), (Me₂AsO₂-SbO) _x and some Sb(Me₂AsO₂)₃ was reformed, Bi(Me₂AsO₂)₃ gave (Me₂AsO₂-BiO) _x , PhSSPh, and Me₂As-SPh (1:0.6 mol ratio), whereas (Me₂AsO₂)₂Bi(NO₃)·H₂O quantitatively gave PhSSPh, thus acting as a catalyst for the air oxidation of thiophenol.     

Organotin and tin(IV) derivatives of dimethyldithioarsinic acid

Organotin derivatives of dimethyldithioarsinic (dithocacodylic) acid have been obtained from the appropriate organotin chloride and the sodium salt of the latter. Tin(IV) chloride and NaS₂AsMe₂ · 2 H₂O yielded only two products, namely Cl₂Sn(S₂AsMe₂)₂ and Sn (S₂AsMe₂)₄, regardless of the reagent ratio. Spectroscopic characterization of the compounds (infrared and¹H NMR) provides structural information suggesting that the dimethyldithioarsinato group behaves as monodentate (or anisobidentate) ligand in Me₂Sn(S₂AsMe₂)₂, Bu₂Sn-(S₂AsMe₂)₂ and Cy₃Sn(S₂AsMe₂), as bidentate in Ph₂Sn(S₂AsMe₂)₂, Ph₃Sn(S₂AsMe₂) and Cl₂As(S₂AsMe₂)₂, whereas Sn(S₂AsMe₂)₄ contains both mono- and bidentate ligands, presumably in a six-coordinate structure.     

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.     

Wolframkomplexe von Diphosphanylacetylenen

Tungsten Complexes of Diphosphanylacetylenes Diphosphanylacetylenes, R₂P? C?C? PR₂ [R?N(C₂H₅)₂ ( 1 ), N[(CH₂)₂]₂O ( 2 ), OCH₃ ( 3 )] and W(CO)₅ · tetrahydrofurane form the mononuclear complexes R₂P? C?C? PR₂ · W(CO)₅ [R?N(C₂H₅)₂ ( 1a ), N[(CH₂)₂]₂O ( 2a )], the dinuclear complexes (CO)₅W? PR₂? C?C? PR₂? W(CO)₅ [R?N(C₂H₅)₂ ( 1b ), N[(CH₂)₂]₂O ( 2b ), OCH₃ ( 3b )], and the trinuclear complex (CO)₅W? PR₂? C?C? PR₂? W(CO)₄? PR₂? C?C? PR₂? W(CO)₅ [R?N(C₂H₅)₂ ( 4 )]. The new compounds are characterized by their NMR, mass, and IR spectra. The results of an X-ray structural analysis of 4 are reported.     

Pseudohalogenometallverbindungen: LVIII. Reaktionen von diphenylphosphorylazid und perfluor-n-hexylsulfonylazid mit triphenylphosphan-komplexen von platin(0), rhodium(I), iridium(I), ruthenium(0), kobalt(II) und kupfer(I)

Diphenylphosphorylazide N₃P(O)(OPh)₂ reacts with Pt(PPh₃)₃, Pt(PPh₃)₂(C₂H₄), trans-RhCl(CO)(PPh₃)₂, Ru(CO)₃(PPh₃)₂, CoCl₂(PPh₃)₂ and CuCl(PPh₃)₂ to give the azido complexes Pt(PPh₃)₂(N₃)R, Pt(PPh₃)₂(N₃)₂R₂, the urylene complex RhCl(PPh₃)₂(RNCONR) and the phosphine imine complexes Ru(CO)₃(RPPh₃)₂, CoCl₂(RNPPh₃)₂, CuCl(RNPPh₃)₂, respectively, (RP(O)(OPh)₂). The oxidative addition of n-C₆F₁₃SO₂N₃ to Pt(PPh₃)₄ and Pt(PPh₃)₂(C₂H₄) affords the complexes Pt(PPh₃)₂(N₃)R and Pt(PPh₃)₂(N₃)₂R₂, respectively, (RSO₂C₆F₁₃. The compounds are characterized by elemental analysis and by their IR spectra.     

Alternativ-Liganden. III. Koordinatives verhalten von chelatliganden des typs me2XSi(Me2)CH2XMe2 (X  N und/oder P: Me  CH3)

Co-ordinative Properties of Chelating Ligands of the Type Me₂XSi(Me₂)CH₂XMe₂ (X ? N and/or P; Me ? CH₃) The reactions of the ligands L ? Me₂XSi(Me₂)CH₂XMe₂ (X ? N and/or P; Me ? CH₃) with M(CO)₆ and M(CO)₄norbor (norbor ? norbornadiene) (M ? Cr, Mo), respectively, yield derivatives of the types M(CO)₅L, M(CO)₄L, and M(CO)₄L₂, respectively. M(CO)₅L compounds are formed from the hexacarbonyls with Me₂NSiMe₂CH₂PMe₂, whereas the ligand Me₂NSiMe₂CH₂NMe₂ does not afford analogous derivatives under the same conditions. Even on substitution of the diene-ligand in M(CO)₄norbor by Me₂NSiMe₂CH₂PMe₂ the chelate complexes M(CO)₄NMe₂SiMe₂CH₂PMe₂ are not obtained, but the cis-disubstituted products M(CO)₄[PMe₂CH₂SiMe₂NMe₂]₂ with phosphorus acting as donor atom are produced. The ligands Me₂PSiMe₂CH₂XMe₂(X ? N, P) give the chelate complexes M(CO)₄PMe₂SiMe₂CH₂XMe₂ in high yields. The new compounds were identified by analytical and spectroscopic (PMR, IR, mass spectra) methods.     

Alternativ-Liganden. XXIII. Rhodium(I)-Komplexe mit Donor/Akzeptor-Liganden des Typs (Me2PCH2CH2SiX2 und (2-Me2PC6H4)SiXMe2 (X = F,Cl)

Alternative Ligands. XXIII Rhodium(I) Complexes with Donor/Acceptor Ligands of the Type (Me₂PCH₂CH₂)₂SiX₂ and (2-Me₂PC₆H₄)SiXMe₂ (X = F, Cl) Donor/acceptor ligands of the type (Me₂PCH₂CH₂)₂SiX₂ and (2-Me₂PC₆H₄)SiXMe₂ (X = F, Cl) react with [Rh(CO)₂Cl]₂ (₁) to give the mononuclear complexes RhCl(CO)(Me₂PCH₂CH₂)₂SiX₂ [X = F( 4 ), Cl ( 5 )] and RhCl(CO)[2-Me₂PC₆H₄)SixMe₂]₂ [X = F ( 8 ), Cl ( 9 )], respectively. In case of the ligands (Me₂PCH₂CH₂)₂SiCl₂ ( 3 ) and (2-Me₂PC₆H₆)SiClMe₂ ( 7 ) the Rh(I) complexes formed in the first step partly undergo oxidative addition reactions of SiCl bonds yielding rhodium(III) compounds of low solubility. Only for 8 the coordination shifts Δδ = δ(complex)?δ(ligand) and coupling constants give some indication to possible Rh→Si interactions. However, the molecular structure of 8 determined by X-ray diffraction does not show RhSi or RhF bonding contacts. The new compounds were characterized by analytical (C, H) and spectroscopic investigations (MS, IR,-NMR).     

Reactions of 1-(3"-Amino)- and 1-(3"-Acetamido)propylsilatranes with Cobalt(II) Chloride and Dicobalt Octacarbonyl

1-(3"-Amino)propylsilatrane (I) and 1-(3"-acetamido)propylsilatrane (II) react with anhydrous cobalt(II) chloride to give dichlorobis[1-(3"-amino)propylsilatrane]cobalt(II) {Co[NH₂CH₂CH₂CH₂Si(OCH₂CH₂)₃N]₂Cl₂} (III) and dichlorobis[1-(3"-acetamido)propylsilatrane]cobalt(II) {Co[CH₃C(O)NHCH₂CH₂CH₂Si(OCH₂CH₂)₃N]₂Cl₂} (IV). Being unstable, compound IV transforms into an imidic acid derivative. Reactions of silatranes I and II with dicobalt octacarbonyl afford hexakis[1-(3"-aminoamido)propylsilatrane]cobalt(II) bis(tetracarbonylcobaltate) {Co[NH₂CH₂CH₂CH₂Si(OCH₂CH₂)₃N]_4.8[HC(O)NHCH₂CH₂CH₂Si(OCH₂CH₂)₃N]_1.2}[Co(CO)₄]₂ (V) and hexakis[1-(3"-acetamido)propylsilatrane]cobalt(II) bis(tetracarbonylcobaltate) {Co[CH₃C(O)NHCH₂CH₂CH₂Si(OCH₂CH₂)₃N]₆}[Co(CO)₄]₂ (VI), respectively. In acetonitrile, tetracarbonylcobaltate anions of compound VI are oxidized with atmospheric oxygen and moisture to cobalt hydroxocarbonate, giving a carbonate gel (VII).     

Synthese und Charakterisierung neuer intramolekular stickstoffstabilisierter Organoaluminium‐ und Organogalliumalkoxide

Synthesis and Characterization of New Intramolecularly Nitrogen‐stabilized Organoaluminium‐ and Organogallium Alkoxides The intramolecularly nitrogen stabilized organoaluminium alkoxides [Me₂Al{μ‐O(CH₂)₃NMe₂}]₂ ( 1a ), Me₂AlOC₆H₂(CH₂NMe₂)₃‐2,4,6 ( 2a ), [(S)‐Me₂Al{μ‐OCH₂CH(i‐Pr)NH‐i‐Pr}]₂ ( 3a ) and [(S)‐Me₂Al{μ‐OCH₂CH(i‐Pr)NHCH₂Ph}]₂ ( 4 ) are formed by reacting equimolar amounts of AlMe₃ and Me₂N(CH₂)₃OH, C₆H₂[(CH₂NMe₂)₃‐2,4,6]OH, (S)‐i‐PrNHCH(i‐Pr)CH₂OH, or (S)‐PhCH₂NHCH(i‐Pr)CH₂OH, respectively. An excess of AlMe₃ reacts with Me₂N(CH₂)₂OH, Me₂N(CH₂)₃OH, C₆H₂[(CH₂NMe₂)₃‐2,4,6]OH, and (S)‐i‐PrNHCH(i‐Pr)CH₂OH producing the “pick‐a‐back” complexes [Me₂AlO(CH₂)₂NMe₂](AlMe₃) ( 5 ), [Me₂AlO(CH₂)₃NMe₂](AlMe₃) ( 1b ), [Me₂AlOC₆H₂(CH₂NMe₂)₃‐2,4,6](AlMe₃)₂ ( 2b ), and [(S)‐Me₂AlOCH₂CH(i‐Pr)NH‐i‐Pr](AlMe₃) ( 3b ), respectively. The mixed alkyl‐ or alkenylchloroaluminium alkoxides [Me(Cl)Al{μ‐O(CH₂)₂NMe₂}]₂ ( 6 ) and [{CH₂=C(CH₃)}(Cl)Al{μ‐O(CH₂)₂NMe₂}]₂ ( 8 ) are to obtain from Me₂AlCl and Me₂N(CH₂)₂OH and from [Cl₂Al{μ‐O(CH₂)₂NMe₂}]₂ ( 7 ) and CH₂=C(CH₃)MgBr, respectively. The analogous dimethylgallium alkoxides [Me₂Ga{μ‐O(CH₂)₃NMe₂}]₂ ( 9 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)NH‐i‐Pr}]_n ( 10 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)NHCH₂Ph}]_n ( 11 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)N(Me)CH₂Ph}]_n ( 12 ) and [(S)‐Me₂Ga{μ‐OCH₂(C₄H₇NHCH₂Ph)}]_n ( 13 ) result from the equimolar reactions of GaMe₃ with the corresponding alcohols. The new compounds were characterized by elemental analyses, ¹H‐, ¹³C‐ and ²⁷Al‐NMR spectroscopy, and mass spectrometry. Additionally, the structures of 1a , 1b , 2a , 2b , 3a , 5 , 6 and 8 were determined by single crystal X‐ray diffraction.     

Untersuchungen zur Lithiierung und Substitution des HP[Si(t-Bu)2]2PH

Investigations on Lithiation and Substitution of HP[Si(t-Bu)₂]₂PH HP[Si(t-Bu)₂]₂PH 1 is monolithiated by reaction with LiPH₂ · DME or LiBu in toluene. The crystalline compound HP[Si(t-Bu)₂]₂PLi · 2 DME 2 can be isolated in DME. Reaction of 2 with Me₂SiCl₂ leads to HP[Si(t-Bu)₂]₂P? SiMe₂Cl 4 , ClMe₂Si? P[Si(t-Bu)₂]₂P? SiMe₂Cl 5 , HP[Si(t-Bu)₂]₂P? SiMe₂? P[Si(t-Bu)₂] ₂PH 6 . Isomerization by Li/H migration between 4 and 2 leads to the formation of 5 . Reaction of Li(t-Bu) with 1 or 2 yields LiP[Si(t-Bu)₂]₂PLi 3 by further lithiation. 3 could not be obtained purely, only in a mixture with 2 . These compounds favourably generate with t-BuPCl₂ in hexane Cl(t-Bu)P? P[Si(t-Bu)₂]₂P? P(t-Bu)Cl 9 , in THF HP[Si(t-Bu)₂]₂P? P(t-Bu)? P[Si(t-Bu)₂]₂ PH 12 (main product), 9 , H(t-Bu)P? P[Si(t-Bu)₂]₂P? P(t-Bu)Cl 10 , H(t-Bu)P? P[Si(t-Bu)₂]₂P? P(t-Bu)H 11 as well as HP[Si(t-Bu)₂]₂P? P(t-Bu)H 13 and HP[Si(t-Bu)₂]₂P? P(t-Bu)₂ 14 .     

Synthese,Röntgenstrukturanalyse und Multikern‐NMR‐spektroskopische Untersuchung einiger intramolekular stickstoffstabilisierter Bor‐, Aluminium‐ und Galliumorganyle

Synthesis, X‐Ray Structure, and Multinuclear NMR Investigation of some intramolecularly Nitrogen stabilized Organoboron, ‐aluminum, and ‐gallium Compounds The intramolecularly nitrogen stabilized organoaluminum‐ and organoboron compounds Me₂Al(CH₂)₃NMe₂ ( 1 ), Me₂AlC₁₀H₆‐8‐NMe₂ ( 2 ), ⁱPr₂Al(CH₂)₃NEt₂ ( 3 ), (CH₂)₅Al(CH₂)₃NMe₂ ( 4 ), and (CH₂)₅B(CH₂)₃NMe₂ ( 5 ) are synthesized from Me₂AlCl and the corresponding organolithium compounds and from AlCl₃ or BCl₃, the lithium alkyl and ⁱPrMgCl or BrMg(CH₂)₅MgBr, respectively. AlCl₃ and GaCl₃ react with Li(CH₂)₃NMe₂ or LiCH₂CHMeCH₂NMe₂ forming Cl₂AlCH₂CHMeCH₂NMe₂ ( 6 ), Cl₂Al(CH₂)₃NMe₂ ( 8 ), and Cl₂Ga(CH₂)₃NMe₂ ( 9 ). The reaction of 6 and of 8 or 9 with BrMg(CH₂)₅MgBr and BrMg(CH₂)₆MgBr, respectively, yields (CH₂)₅AlCH₂CHMeCH₂NMe₂ ( 7 ), (CH₂)₆Al(CH₂)₃NMe₂ ( 10 ), and (CH₂)₆Ga(CH₂)₃NMe₂ ( 11 ). MeAlCl₂, made by the redistribution reaction of AlCl₃ with Me₂AlCl, reacts with 2 equivalents of Li(CH₂)₃NMe₂ yielding MeAl[(CH₂)₃NMe₂]₂ ( 12 ) and with MeN[(CH₂)₃MgCl]₂ under formation of MeAl[(CH₂)₃]₂NMe ( 13 ). MeAlCl₂, MeGaCl₂, or GaCl₃ accordingly react with one equivalent of organolithium reagent to give the intramolecularly nitrogen stabilized organoaluminum and organogallium chlorides MeClAl(CH₂)₃NMe₂ ( 14 ), MeClGa(CH₂)₃NMe₂ ( 15 ), MeClGaC₆H₄‐2‐CH₂NMe₂ ( 16 ) as well as Cl₂GaC₆H₄‐2‐CHMeNMe₂ ( 17 ). The compounds were characterized by elemental analyses, mass spectroscopy, ¹H, ¹¹B, ¹³C and ²⁷Al NMR investigations. Single crystal X‐ray structure analyses of 1 , 2 , 4 , 5 and 17 reveal the monomeric molecular structures with intramolecular nitrogen coordination.     

Syntheses and Characterizations of Novel One-dimensional Coordination Polymers Self-assembled from Co(NCS)_2 and Flexible Diester-bridged Pyridine-based Ligands

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Silicon‐ and Tin‐Containing Open‐Chain and Eight‐Membered‐Ring Compounds as Bicentric Lewis Acids toward Anions

Herein, we report the syntheses of silicon‐ and tin‐containing open‐chain and eight‐membered‐ring compounds Me₂Si(CH₂SnMe₂X)₂ ( 2 , X=Me; 3 , X=Cl; 4 , X=F), CH₂(SnMe₂CH₂I)₂ ( 7 ), CH₂(SnMe₂CH₂Cl)₂ ( 8 ), cyclo‐Me₂Sn(CH₂SnMe₂CH₂)₂SiMe₂ ( 6 ), cyclo‐(Me₂SnCH₂)₄ ( 9 ), cyclo‐Me_(2?n)X_nSn(CH₂SiMe₂CH₂)₂SnX_nMe_(2?n) ( 5 , n=0; 10 , n = 1, X= Cl; 11 , n=1, X= F; 12 , n=2, X= Cl), and the chloride and fluoride complexes NEt₄[cyclo‐ Me(Cl)Sn(CH₂SiMe₂CH₂)₂Sn(Cl)Me?F] ( 13 ), PPh₄[cyclo‐Me(Cl)Sn(CH₂SiMe₂CH₂)₂Sn(Cl)Me?Cl] ( 14 ), NEt₄[cyclo‐Me(F)Sn(CH₂SiMe₂CH₂)₂Sn(F)Me?F] ( 15 ), [NEt₄]₂[cyclo‐Cl₂Sn(CH₂SiMe₂CH₂)₂SnCl₂?2 Cl] ( 16 ), M[Me₂Si(CH₂Sn(Cl)Me₂)₂?Cl] ( 17 a , M=PPh₄; 17 b , M=NEt₄), NEt₄[Me₂Si(CH₂Sn(Cl)Me₂)₂?F] ( 18 ), NEt₄[Me₂Si(CH₂Sn(F)Me₂)₂?F] ( 19 ), and PPh₄[Me₂Si(CH₂Sn(Cl)Me₂)₂?Br] ( 20 ). The compounds were characterised by electrospray mass‐spectrometric, IR and ¹H, ¹³C, ¹⁹F, ²⁹Si, and ¹¹⁹Sn NMR spectroscopic analysis, and, except for 15 and 18 , single‐crystal X‐ray diffraction studies.     

Gold(I) and Silver(I) Complexes of Diphosphacyclobutadiene Cobaltate Sandwich Anions

The synthesis and structural characterization of the first coordination compounds of bis(diphosphacyclobutadiene) cobaltate anions [M(P₂C₂R₂)₂]^? is described. Reactions of the new potassium salts [K(thf)₃{Co(η⁴‐P₂C₂tPent₂)₂}] ( 1 ) and [K(thf)₄{Co(η⁴‐P₂C₂Ad₂)₂}] ( 2 ) with [AuCl(tht)] (tht=tetrahydrothiophene), [AuCl(PPh₃)] and Ag[SbF₆] afforded the complexes [Au{Co(P₂C₂tPent₂)₂}(PMe₃)₂] ( 3 ), [Au{Co(P₂C₂Ad₂)₂}]_x ( 4 ), [Ag{Co(P₂C₂Ad₂)₂}]_x ( 5 ), [Au(PMe₃)₄][Au{Co(P₂C₂Ad₂)₂}₂] ( 6 ), [K([18]crown‐6)(thf)₂][Au{Co(P₂C₂Ad₂)₂}₂] ( 7 ), and [K([18]crown‐6)(thf)₂][M{Co(P₂C₂Ad₂)₂}₂] ( 8 : M=Au 9 : M=Ag) in moderate yields. The molecular structures of 2 and 3 , and 6 – 9 were elucidated by X‐ray crystallography. Complexes 4 – 9 were thoroughly characterized by ³¹P and ¹³C solid state NMR spectroscopy. The complexes [Au{Co(P₂C₂Ad₂)₂}]_x ( 4 ) and [Ag{Co(P₂C₂Ad₂)₂}]_x ( 5 ) exist as coordination polymers in the solid state. The linking mode between the monomeric units in the polymers is deduced. The soluble complexes 1 – 3 , 6 , and 7 were studied by multinuclear ¹H‐, ³¹P{¹H}‐, and ¹³C{¹H} NMR spectroscopy in solution. Variable temperature NMR measurements of 3 and 6 in deuterated THF reveal the formation of equilibria between the ionic species [Au(PMe₃)₄]⁺, [Au(PMe₃)₂]⁺, [Co(P₂C₂R₂)₂]^?, and [Au{Co(P₂C₂R₂)₂}₂]^? (R=tPent and Ad).     

CO2 fixation by [WIVO(S2C2(CN)2)2]2?: functional model for the tungsten-formate dehydrogenase of Clostridium thermoaceticum

(NEt₄)₂[W^IVO(S₂C₂(CN)₂)₂] (1), isolated by reaction of Na₂ WO₄, Na₂S₂C₂(CN)₂ (Na₂mnt) in acidified (pH5.5) aqueous medium in the presence of excess of sodium dithionite and NEt₄Br, reduces CO₂/HCO ₃ ⁻ (pH 7.5) to yield HCOO⁻ and (NEt₄)₂[W^VIO₂(S₂C₂(CN)₂)₂] (2) mimicking tungsten-formate dehydrogenase (W-FDH) activity. (1) reacts with Na₂MoO₄ in acidic medium to produce [Mo^IvO(S₂C₂(CN)₂)₂]²⁻ implicating the displacement of tungsten by molybdenum from the cofactor complex in W-FDH.     

Synthesen und Eigenschaften von Pentafluorethylkupfer(I)‐ und ‐(III)‐Verbindungen: Cu(C2F5) · D, [Cu(C2F5)2]– und (C2F5)2CuSC(S)N(C2H5)2

Syntheses and Properties of Pentafluoroethylcopper(I) and ‐copper(III) Compounds: CuC₂F₅ · D, [Cu(C₂F₅)₂]^–, and (C₂F₅)₂CuSC(S)N(C₂H₅)₂ The reactions of Cd(C₂F₅)₂ · D and Zn(C₂F₅)₂ · D (D = 2 CH₃CN, 2 DMF), respectively, with copper(I) halides in the presence of halides quantitatively yield the CuC₂F₅ compounds CuC₂F₅ · D and [Cu(C₂F₅)₂]^–. The CuC₂F₅ complexes are identified by NMR spectroscopy, while [Cu(C₂F₅)₂]^– is isolated as PNP salt (PNP = (C₆H₅)₃PNP(C₆H₅)₃⁺). Both compounds are excellent C₂F₅ group transfer reagents, even at low temperature. Oxidation of [Cu(C₂F₅)₂]^– with [(C₂H₅)₂NC(S)S]₂ yields the crystalline Cu(III) compound (C₂F₅)₂CuSC(S)N(C₂H₅)₂ (monoclinic, C2/c).     

Metallation studies of organofunctional trisiloxanes

Summary The organofunctional trisiloxanes Me₃SiOSiMe(R)OSiMe₃ [R=(CH₂)₂PPh₂, (CH₂)₃C₅H₄N, (CH₂)₃CN, (CH₂)₂Ph, (CH₂)₂SPh, CH=CH₂ and CH₂CH=CH₂] have been reacted with metal halide and-carbonyl moieties in order to determine the coordination preferences of materials being used as models for metallated longchain linear functionalised polysiloxanes. The products [Me₃SiOSiMe(R)OSiMe₃]₃ML_n [R=(CH₂)₂PPh₂, ML_n=RhCl],cis-[Me₃SiOSiMe(R)OSiMe₃]₂ML_n [R=(CH₂)₂PPh₂ or (CH₂)₃C₅H₄N, ML_n=Mo(CO)₄],trans-[Me₃SiOSiMe(R)OSiMe₃]₂ML_n[R=(CH₂)₂PPh₂, ML_n=NiCl₂, PdCl₂, PtCl₂ and [Rh(CO)Cl] and [Me₃SiOSiMe(R)OSiMe₃]ML_n [R=(CH₂)₂PPh₂, ML_n=Mo(CO)₃(2,2-bipyridine); R=(CH₂)₂Ph, ML_n=Mo(CO)₃; R=(CH₂)₃C₅H₄N, (CH₂)₃CN, or (CH₂)₂SPh, ML_n=Rh(CO)₂Cl; R=CH=CH₂ or CH₂CH=CH₂, ML_n=Fe(CO)₄] have been isolated and characterised spectroscopically in the course of these studies.     

Structurally different divalent metallasiloxanes [Mg{O(Ph2SiO)2}2]-μ-(LiPy)-μ-{(LiPy)3(OH)(Cl)}], [Cr{O(Ph2SiO)2}-μ-(LiPy2)2], and [{O(Ph2SiO)2}Co{O(Ph2SiO)3)}-μ-(LiPy2)2] from Ph2Si(OH)2/2BuLi and the metal dichlorides

Three structurally different metallasiloxanes were formed from reactions between in situ generated suspensions of Ph₂Si(OH)₂/BuLi (1∶2) in tetrahydrofuran (THF) with, metal dichlorides MgCl₂·2THF, CrCl₂, or CoCl₂ followed by toluene/Py (Py=pyridine) work-up. The X-ray structures are reported for: [Mg{O(Ph₂SiO)₂}₂]-μ-(LiPy)-μ-{(LiPy)₃(OH)(Cl)] (1) incorporating two six-membered magnesiasiloxane rings and an MgLi₃O₃Cl cubane fragment, [{O(Ph₂SiO)₂}Co{O(Ph₂SiO)₃}-μ-(LiPy₂)₂] (2) with both six-and eight-membered cobaltasiloxane rings and [Cr{O(Ph₂SiO)₂}₂-μ-(LiPy₂)₂] (3) with two six-membered chromiasiloxane rings. Structure assembly in these cases is apparently dictated by the metal dichloride. The compound [{O(Ph₂SiO)₂}Mg{O(Ph₂SiO)₃}-μ-(CoClPy)₂]·Py (4) is formed from [{O(Ph₂SiO)₂}Mg{O(Ph₂SiO)₃}-μ-(LiPy₂)₂] and CoCl₂ (1∶2).