Synthese und Strukturen von [ReNBr2(Me2PhP)3] und (Me2PhPH)[fac‐Re(NBBr3)Br3(Me2PhP)2]

Syntheses and Structures of [ReNBr₂(Me₂PhP)₃] and (Me₂PhPH)[ fac ‐Re(NBBr₃)Br₃(Me₂PhP)₂] [ReNBr₂(Me₂PhP)₃] ( 1 ) has been prepared by the reaction of [ReNCl₂(Me₂PhP)₃] with Me₃SiBr in dichloromethane. The bromo complex reacts with BBr₃ under formation of [Re(NBBr₃)Br₂(Me₂PhP)₃] ( 2 ) or (Me₂PhPH)[fac‐Re(NBBr₃)Br₃(Me₂PhP)₂] ( 3 ) depending on the experimental conditions. The formation of the nitrido bridge leads to a significant decrease of the structural trans influence of the nitrido ligand which is evident by the shortening of the Re‐(trans)Br bond from 2.795(1) Å in [ReNBr₂(Me₂PhP)₃] to 2.620(1) Å in [fac‐Re(NBBr₃)Br₃(Me₂PhP)₂]^– and 2.598(1) Å in [Re(NBBr₃)Br₂(Me₂PhP)₃], respectively.     

Preparation of Dimethyl and Chloro/Methyl Complexes of Platinum(II) Supported by α‐Diimine Ligands: Trends in the Ease of Oxidation to Platinum(IV)

α‐Diimine ligands react with the platinum(II) alkyl complexes [(Me₂S)PtMe₂]₂ and (Me₂S)₂PtClMe to form (RDAB^R′)PtMe₂ and (RDAB^R′)PtClMe (RDAB^R′=RN=CR′−CR′=NR; R=2,6‐Me₂Ph, 2,6‐(CHMe₂)₂Ph, 3,5‐Me₂Ph, 3,5‐(CF₃)₂Ph, C₆H₁₁; R′=Me, H). The oxidation of these complexes with Cl₂, I₂, N‐chlorosuccinimide, [PtCl₆]²⁻ and (TMEDA)PtMe₂I₂ has been investigated. Attempts to determine the oxidation potentials of the Pt^II complexes electrochemically yielded only irreversible one‐electron oxidations. However, a qualitative ordering of increasing difficulty of oxidation has been determined for the series (RDAB^R′)PtMe₂<(RDAB^R′)PtClMe<(RDAB^R′)PtCl₂≪(RDAB^R′)PtMe(solvent)]⁺. The oxidation proceeds via a two‐electron inner‐sphere electron transfer from a bridged binuclear intermediate. The oxidation of (RDAB^R′)PtMe₂ by (TMEDA)PtMe₂I₂ exhibits characteristic third‐order kinetics, first‐order each in [Pt^II], [Pt^IV] and [I⁻]. Oxidation by a one‐electron process in MeCN solution results in a rapid subsequent disproportionation to Pt^IIMe and Pt^IVMe₃ cations with MeCN occupying the fourth or sixth coordination sites. Single‐crystal X‐ray structure determinations for [(2,6‐Me₂PhDAB^Me)PtMe₃(MeCN)]⁺[PtCl₆]_0.5(MeCN) and [(CyDAB^H)PtMe₃(MeCN)]⁺[PtCl₆]_0.5(MeCN) are reported.     

N,N,N′,N′-Tetramethylethylendiamin-di(tert-butyl)aluminium-Kationen — Molekülstruktur des [(Me3C)2Al · TMEDA]⊕[(Me3C)2AlBr2]⊖

(N,N,N′,N′ -tetramethylethylendiamine) di(tert-butyl)aluminium Cations — Molecular Structure of [(Me₃C)₂Al(TMEDA)]^⊕[(Me₃C)₂AlBr₂]^? Dimeric di(tert-butyl)aluminium halides (Me₃C)₂AlX (X = Cl, Br) react with N,N,N′,N′ -tetramethylethylendiamine (TMEDA) to give three compounds: the salt-like [(Me₃C)₂Al(TMEDA)]^⊕[(Me₃C)₂AlX₂]^? 1 , characterized by crystal structure determination, and [(Me₃C)₂Al(TMEDA)]^⊕X^? 3 both with chelating amine, and the more covalent, pentane soluble (Me₃C)₂AlX(TMEDA) 2 with TMEDA bound by only one nitrogen atom. The reaction resembles the symmetrical and unsymmetrical cleavage of diborane(6). 3 (X = Cl) is also formed by treatment of 1 with boiling n-hexane in the presence of TMEDA over a period of 24 hours, while for X = Br the more covalent 2 is the main product under similar conditions. In solution 2 decomposes slowly yielding different products in dependency of the solvent: in benzene 3 and in n-pentane 1 are formed.     

Destruktive Komplexierung des dimeren Diorganylzinn(IV)‐hydroxids [Me2Sn(A)(μ‐OH)]2 (HA = Benzol‐1,2‐disulfonsäureimid): Bildung und Strukturen der Einkernkomplexe [Me2Sn(A)2(OPPh3)2] und [Me2Sn(phen)2]2⊕ · 2 A⊖ · MeCN

Polysulfonylamines. CXVI. Destructive Complexation of the Dimeric Diorganyltin(IV) Hydroxide [Me₂Sn(A)(μ‐OH)]₂ (HA = Benzene‐1,2‐disulfonimide): Formation and Structures of the Mononuclear Complexes [Me₂Sn(A)₂(OPPh₃)₂] and [Me₂Sn(phen)₂]^2⊕ · 2 A^⊖ · MeCN Destructive complexation of the dimeric hydroxide [Me₂Sn(A)(μ‐OH)]₂, where A^⊖ is deprotonated benzene‐1,2‐disulfonimide, with two equivalents of triphenylphosphine oxide or 1,10‐phenanthroline in hot MeCN produced, along with Me₂SnO and water, the novel coordination compounds [Me₂Sn(A)₂(OPPh₃)₂] ( 3 , triclinic, space group P 1) and [Me₂Sn(phen)₂]^2⊕ · 2 A^⊖ · MeCN ( 4 , monoclinic, P2₁/c). In the uncharged all‐trans octahedral complex 3 , the heteroligands are unidentally O‐bonded to the tin atom, which resides on a crystallographic centre of inversion [Sn–O(S) 227.4(2), Sn–O(P) 219.6(2) pm, cis‐angles in the range 87–93°; anionic ligand partially disordered over two equally populated sites for N, two S and non‐coordinating O atoms]. The cation occurring in the crystal of 4 has a severely distorted cis‐octahedral C₂N₄ coordination geometry around tin and represents the first authenticated example of a dicationic tin(IV) dichelate [R₂Sn(L–L′)₂]^2⊕ to adopt a cis‐structure [C–Sn–C 108.44(11)°]. The five‐membered chelate rings are nearly planar, with similar bite angles of the bidentate ligands, but unsymmetric Sn–N bond lengths, each of the longer bonds being trans to a methyl group [ring 1: N–Sn–N 71.24(7)°, Sn–N 226.81(19) and 237.5(2) pm; ring 2: 71.63(7)°, 228.0(2) and 232.20(19) pm]. In both structures, the bicyclic and effectively C_S symmetric A^⊖ ions have their five‐membered rings distorted into an envelope conformation, with N atoms displaced by 28–43 pm from the corresponding C₆S₂ mean plane.     

A Novel Divalent Ytterbium Complex Supported by a Bridged Diamide Ligand: Synthesis and Structure of [{Me2Si(NPh)2Yb(THF)2}(μ3‐Cl)(μ4‐Cl){Li(THF)}2]2·2THF

The reaction of anhydrous YbCl₃ with 1 equiv. of Li₂Me₂Si(NPh)₂ in THF, after workup, yielded a ytterbium(III) chloride [{Me₂Si(NPh)₂Yb}(μ₂‐Cl)(TMEDA)]₂·3PhMe ( 1 ) (TMEDA=tetramethylethanediamine). The same reaction followed by treatment with Na‐K alloy afforded a new ytterbium(II) complex supported by a bridged diamide with four coordinated LiCl molecules, [{Me₂Si(NPh)₂Yb(THF)₂}(μ₃‐Cl)(μ₄‐Cl){Li(THF)}₂]₂·2THF ( 2 ) in high yield. Both complexes were structurally characterized by X‐ray analysis to be dimers. Complex 1 was a chlorine‐bridged dimer with ytterbium in a distorted octahedral geometry. In complex 2 two [Me₂Si(NPh)₂Yb(THF)₂]‐(μ₃‐Cl)[Li(THF)]₂ moieties were connected with each other by two μ₄‐Cl bridges to form a "chair‐form" framework.     

Halogenid‐Ionen als Katalysator: Metallzentrierte C–C‐Bindungsknüpfung ausgehend von Acetontril

Halide Ions as Catalyst: Metalcentered C–C Bond Formation Proceeded from Acetonitril AlMe₃ reacts at 20 ?C in acetonitrile to the complex [Me₃Al(NCMe)] ( 1 ). By addition of cesium halides (X^– = F^–, Cl^–, Br^–) a trimerisation to the heterocycle [Me₂Al{HNC(Me)}₂C(CN)] ( 2 ) has been observed. The reaction might be carried out under catalytic conditions (1–2 mol% CsX). The gallium complex [Me₂Ga{HNC(Me)}₂ · C(CN)] ( 3 ), generated under similar reaction conditions, can be converted to the silylated compound [Me₂Ga{Me₃SiNC(Me)}₂C(CN)] ( 4 ) by successive treatment with two equivalents n‐butyllithium and Me₃SiCl. 3 reacts under hydrolysis conditions (1 M hydrochloric acid) to the iminium salt [{H₂NC(Me)}₂C(CN)]Cl ( 5 ). A mixture of H₂O, Ph₂PCl and 3 in THF/toluene leads in a unusual conversion to the diphospane derivative [Ph₂P–P(O)(Me₂GaCl)] ( 6 ). 1 , 2 , 4 , 5 and 6 have been characterized by NMR, IR and MS techniques. X‐ray structure analyses were performed with 1 , 2 , 4 and 6 · 0.5 toluene. According this 1 possesses an almost linear axis AlNCC [Al1–N1–C3: 179,5(2)?; N1–C3–C4: 179,7(4)?]. 2 is an AlN₂C₃ six‐membered heterocycle with two iminium fuctions. One N–H group is responsible for a intermolecular chain‐formation through hydrogen bridges to an adjacent nitrile group along the direction [010]. The basic structural motif of the heterocycle 3 has been maintained after silylation to 4 . In 6 · 0.5 toluene an unit Me₂GaCl, originated from 3 , is coordinated to the oxygen atom of the diphosphane oxide Ph₂P–P(O)Ph₂.     

Gemischtligandkomplexe des Rheniums. V. Die Bildung von Nitrenkomplexen durch Kondensation von Aceton an koordinierten Nitridoliganden. Darstellung und Strukturen von fac-[Re{NC(CH3)2CH2C(O)CH3}X3(Me2PhP)2]-Komplexen (X = Cl,Br)

Mixed-ligand Complexes of Rhenium. V. The Formation of Nitrene Complexes by Condensation of Acetone at Coordinated Nitrido Ligands. Syntheses and Structures of fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}X₃(Me₂PhP)₂] Complexes (X = Cl, Br) The reaction of rhenium(V)-mixed-ligand complexes of the general formula [ReN(Cl)(Me₂PhP)₂(R₂tcb)] (HR₂tcb = N? (N,N-dialkylthiocarbamoyl)benzamidine) with HCl or HBr in acetone initializes a condensation of the solvent and results in nitrene-like compounds as a consequence of a nucleophilic attack of the coordinated nitrido ligand on the condensed acetone. The chelate ligands are removed during this reaction and complexes of the type fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}X₃(Me₂PhP)₂] (X = Cl, Br) are formed. fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Cl₃(Me₂PhP)₂] crystallizes triclinic in the space group P1, a = 8.575(4); b = 9.088(3); c = 18.389(9) Å; α = 75.67(3)°, β = 85.30(3)°, γ = 70.58(4)°; Z = 2. A final R value of 0.031 was obtained on the basis of 6011 independent reflections with I ≥ 2σ(I). Rhenium is coordinated in a distorted octahedral environment with the three chloro ligands in facial positions. The rhenium-nitrogen bond (1,68(1) Å) is only slightly longer than typical Re? N bonding distances in nitrido complexes. fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Br₃(Me₂PhP)₂] is isomorphous with the chloro complex. Triclinic cell with a = 8.625(4); b = 9.198(3); c = 18.581(5) Å; α = 75.62(3)°, β = 85.40(3)°, γ = 70.91(3)°; Z = 2. The R value converged at 0.049 on the basis of 3644 independent reflections with I ≥ 2σ(I). fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Cl₃(Me₂PhP)₂] as well as fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Br₃(Me₂PhP)₂] crystallizes in the noncentrosymmetric space group P1.     

Reaktionen eines Dibismutans und von Cyclobismutanen mit Metallcarbonylen ‐ Synthesen von Komplexen mit R2Bi‐, RBi‐, Bi2‐ und Bin‐Liganden (R = Me3CCH2, Me3SiCH2)

Reactions of a Dibismuthane and of Cyclobismuthanes with Metal Carbonyls ‐ Syntheses of Complexes with R₂Bi‐, RBi‐, Bi₂‐ and Bi_n‐ligands (R = Me₃CCH₂, Me₃SiCH₂) Reactions of [Fe₂(CO)₉] with [(Me₃CCH₂)₄Bi]₂ or cyclo‐(Me₃SiCH₂Bi)_n (n = 3 ‐ 5) lead to the complexes [(R₂Bi)₂Fe(CO)₄], [RBiFe(CO)₄]₂[R = Me₃CCH₂, Me₃SiCH₂] and [Bi₂Fe₃(CO)₉]. [Bi₂{Mn(CO)₂C₅H₄CH₃}₃] forms in a photochemical reaction of [Mn(CO)₃C₅H₄CH₃] with cyclo‐(Me₃SiCH₂Bi)_n.     

Studien zur Reaktion von [Me2AlP(SiMe3)2]2 mit basenstabilisierten Organogalliumchloriden und ‐hydriden

Investigations on the Reactivity of [Me₂AlP(SiMe₃)₂]₂ with Base‐stabilized Organogalliumhalides and ‐hydrides [Me₂AlP(SiMe₃)₂]₂ ( 1 ) reacts with dmap?Ga(Cl)Me₂, dmap?Ga(Me)Cl₂, dmap?GaCl₃ and dmap?Ga(H)Me₂ with Al‐P bond cleavage and subsequent formation of heterocyclic [Me₂GaP(SiMe₃)₂]₂ ( 2 ) as well as dmap?AlMe_xCl_3?x (x = 3 8 ; 2 3 ; 1 4 ; 0 5 ). The reaction between equimolar amounts of dmap?Al(Me₂)P(SiMe₃)₂ and dmap?Ga(t‐Bu₂)Cl yield dmap?Ga(t‐Bu₂)P(SiMe₃)₂ ( 6 ) and dmap?AlMe₂Cl ( 3 ). 2 – 8 were characterized by NMR spectroscopy, 2 and 6 also by single crystal X‐ray diffraction.     

Electroanalytical study of the kinetics of thefac-mer isomerization of [ReCl(CO)3(PMe2Ph)2]+ in acetonitrile

Summary The isomerization offac-[ReCl(CO)₃(PMe₂Ph)₂]⁺ to the corresponding meridional-trans isomer has been studied by electroanalytical techniques in MeCN solvent. Chronoamperometric and cyclic voltammetric data relative to the oxidation offac- andmer-[ReCl(CO)₃(PMe₂Ph)₂] allow the accurate determination of the very high kinetic rate constant for the isomerization and permit discussion of thermodynamic aspects of redox homogeneous chemical reactions involving species of the different redox couples arising from the anodic processes.     

[μ‐(Me3SiCH2Sb)5–Sb1,Sb3–{W(CO)5}2] und [{(Me3Si)2CHSb}3Fe(CO)4] – zwei cyclische Komplexe mit Antimon‐Liganden

Syntheses and Crystal Structures of [μ‐(Me₃SiCH₂Sb)₅–Sb¹,Sb³–{W(CO)₅}₂] and [{(Me₃Si)₂CHSb}₃Fe(CO)₄] – Two Cyclic Complexes with Antimony Ligands cyclo‐(Me₃SiCH₂Sb)₅ reacts with [(THF)W(CO)₅] (THF = tetrahydrofuran) to form cyclo‐[μ‐(Me₃SiCH₂Sb)₅–Sb¹,Sb³–{W(CO)₅}₂] ( 1 ). The heterocycle cyclo‐ [{(Me₃Si)₂CHSb}₃Fe(CO)₄] ( 2 ) is formed by an insertion reaction of cyclo‐[(Me₃Si)₂CHSb]₃ and [Fe₂(CO)₉]. The crystal structures of 1 and 2 are reported.     

Reaktion von (R,R)‐(N,N′)‐Diisopropylcyclohexyl‐1,2‐diamin mit Me2MCl (M = Ga,In)

Reaction of (R,R)‐(N,N′)‐Diisopropylcyclohexyl‐1,2‐diamine with Me₂MCl (M = Ga, In) (R,R)‐(N,N′)‐Diisopropylcyclohexyl‐1,2‐diamine (H₂L) was reacted with Me₂GaCl and Me₂InCl in boiling toluene, respectively. In both cases the salt [Me₂M(H₂L)][Me₂MCl₂] [M = Ga ( 1 ), In ( 2 )] was formed. 1 and 2 were characterized by NMR and vibrational spectroscopy. In addition, an X‐ray structure determination was applied on 2 . According to the spectroscopical and structural findings 1 and 2 consist of cations [Me₂M(H₂L)]⁺ and anions [Me₂MCl₂]^?.     

Chelating and Tellurolate Ligand‐Transfer Studies of the Complex fac‐[Fe(CO)3(TePh)3]−: Crystal Structures of Heterodinuclear (CO)3Mn(μ‐TePh)3Fe(CO)3 and CpNi(TePh)(PPh3)

Complex fac‐[Fe(CO)₃(TePh)₃]^? was employed as a “metallo chelating” ligand to synthesize the neutral (CO)₃Mn(μ‐TePh)₃Fe(CO)₃ obtained in a one‐step synthesis by treating fac‐[Fe(CO)₃(TePh)₃]^? with fac‐[Mn‐(CO)₃(CH₃CN)₃]⁺. It seems reasonable to conclude that the d⁶ Fe(II) [(CO)₃Fe(TePh)₃]^? fragment is isolobal with the d⁶ Mn(I) [(CO)₃Mn(TePh)₃]^2? fragment in complex (CO)₃Mn(μ‐TePh)₃Fe(CO)₃. Addition of fac‐[Fe(CO)₃(TePh)₃]^? to the CpNi(I)(PPh₃) in THF resulted in formation of the neutral CpNi(TePh)(PPh₃) also obtained from reaction of CpNi(I)(PPh₃) and [Na][TePh] in MeOH. This investigation shows that fac‐[Fe(CO)₃(TePh)₃]^? serves as a tridentate metallo ligand and tellurolate ligand‐transfer reagent. The study also indicated that the fac‐[Fe(CO)₃(SePh)₃]^? may serve as a better tridentate metallo ligand and chalcogenolate ligand‐transfer reagent than fac‐[Fe(CO)₃(TePh)₃]^? in the syntheses of heterometallic chalcogenolate complexes.     

Reactions of Distibanes with [Fe2(CO)9]: Synthesis,Structure and DFT Calculations of [(Et2Sb)4Fe4(CO)14], [(nPr2Sb)4Fe3(CO)10], [{(Me3SiCH2)2Sb}4Fe2(CO)6], and [2‐(Me2NCH2)C6H4SbFe2(CO)8]

The iron complexes [(Et₂Sb)₄Fe₄(CO)₁₄] ( 1 ), [(nPr₂Sb)₄Fe₃(CO)₁₀] ( 2 ), [{(Me₃SiCH₂)₂Sb}₄Fe₂(CO)₆] ( 3 ), and [2‐(Me₂NCH₂)C₆H₄SbFe₂(CO)₈] ( 4 ) were prepared by reactions of distibanes with Fe₂(CO)₉. Compounds 1 – 4 were characterized by X‐ray diffraction, ¹H NMR and IR spectroscopy as well as mass spectrometry; complex 1 was additionally characterized by density functional calculations.     

Synthesis of cationic carbonyl complexes of manganese(I) with bidentate ligands

Summary Bidentate ligands can readily replace acetone in thefac-[Mn(CO)₃(chel)(OCMe₂)]⁺ complexes or the perchlorate group fromfac-[Mn(CO)₃(chel)(OClO₃)] yieldingfac-[Mn(CO)₃(chel)(L-L)]⁺ or [{fac-Mn(CO)₃(chel)}₂(L-L)]²⁺ [chel = 1,10-phenanthroline (phen), 2,2-bipyridine (bipy), 1,2-bis(diphenylphosphine)ethane (dpe); L-L = bis(diphenylphosphine)methane (dpm), dpe, 1,4-bis(diphenylphosphine)butane (dpb), succinonitrile (suc), and glutaronitrile (glu)]. Some of these mononuclear complexes are precursors for binuclear complexes which are linked by bridging phosphines or nitriles.     

Gemischtligand-Komplexe des Rheniums. IV. Die Reaktion von [ReNCl2(Me2PhP)3] mit Dithiocarbamaten. Kristallstrukturen von trans-Chloro-dimethyldithiocarbamato-bis(dimethylphenylphosphan) nitridorhenium(V), [ReN(Cl)(Me2PhP)2(Me2dtc)], und Bis(diethyldithiocarbamato)(dimethylphenylphosphan)nitridorhenium(V), [ReN(Me2PhP)(Et2dtc)2]

Mixed-Ligand Complexes of Rhenium IV. The Reaction of [ReNCl₂(Me₂PhP)₃] with Dithiocarbamates. X-Ray Crystal Structures of trans-Chloro-dimethyldithiocarbamato-bis(dimethylphenylphosphine) nitridorhenium(V), [ReN(Cl)(Me₂PhP)₂(Me₂dtc)], and Bis(diethyldithiocarbamato)(dimethylphenylphosphine)nitridorhenium(V), [ReN(Cl)(Me₂PhP)(Et₂dtc)₂] [ReNCl₂(Me₂PhP)₃] reacts with dialkyldithiocarbamates, R₂dtc^?, under a stepwise ligand exchange. Final products of these reactions are the well-known [ReN(R₂dtc)₂] bischelates. Intermediatelly, however, complexes of the general formulae [ReN(Cl)(Me₂PhP)₂(R₂dtc)] and [ReN(Me₂PhP)(R₂dtc)₂] can be isolated. Representatives have been structurally characterized. [ReN(Cl)(Me₂PhP)₂(Me₂dtc)] crystallizes monoclinic in the space group P2₁/c, Z = 4. The dimensions of the unit cell are a = 13.071(3); b = 11.622(1); c = 15.667(3) Å; β = 97.09(1)°. The rhenium atom has a distorted octahedral environment; the Re≡N bond length is 1.71(1) Å. The Re? Cl bond distance is markedly lengthened (2.665(2) Å) as a consequence of the strong trans labilizing influence of the coordinated nitrido ligand. [ReN(Me₂PhP)(Et₂dtc)₂] crystallizes monoclinic in the space group P2₁/c, Z = 4, a = 17.262(3); b = 14.915(2); c = 9.888(2); β = 76.35(8)°. The equatorial coordination sphere is occupied by one phosphorus atom and three sulphur atoms. One of the dithiocarbamate ligands is coordinated bidentately; the second one with two distinct Re? S bond lengths. The Re? S(4) distance is 2.7983(2) Å which can be discussed as a weak interaction with the metal.     

Komplexe mit Antimon‐Liganden: [tBu2(Cl)SbW(CO)5], [tBu2(OH)SbW(CO)5], O[SbPh2W(CO)5]2, E[SbMe2W(CO)5]2 (E = Se,Te), cis‐[(Me2SbSeSbMe2)2Cr(CO)4]

Complexes Containing Antimony Ligands: [^tBu₂(Cl)SbW(CO)₅], [^tBu₂(OH)SbW(CO)₅], O[SbPh₂W(CO)₅]₂, E[SbMe₂W(CO)₅]₂ (E = Se, Te), cis‐[(Me₂SbSeSbMe₂)₂Cr(CO)₄] Syntheses of [^tBu₂(Cl)SbW(CO)₅] ( 1 ), [^tBu₂(OH)SbW(CO)₅] ( 2 ), O[SbPh₂W(CO)₅]₂ ( 3 ), Se[SbMe₂W(CO)₅]₂ ( 4 ), cis‐[(Me₂SbSeSbMe₂)₂Cr(CO)₄] ( 5 ) Te[SbMe₂W(CO)₅]₂ ( 6 ) and crystal structures of 1 – 5 are reported.     

Molecular Nitrides with Titanium and Group 13–15 Elements

Several heterometallic nitrido complexes were prepared by reaction of the imido–nitrido titanium complex [{Ti(η⁵‐C₅Me₅)(μ‐NH)}₃(μ₃‐N)] ( 1 ) with amido derivatives of Group 13–15 elements. Treatment of 1 with bis(trimethylsilyl)amido [M{N(SiMe₃)₂}₃] derivatives of aluminum, gallium, or indium in toluene at 150–190 °C affords the single‐cube amidoaluminum complex [{(Me₃Si)₂N}Al{(μ₃‐N)₂(μ₃‐NH)Ti₃(η⁵‐C₅Me₅)₃(μ₃‐N)}] ( 2 ) or the corner‐shared double‐cube compounds [M(μ₃‐N)₃(μ₃‐NH)₃{Ti₃(η⁵‐C₅Me₅)₃(μ₃‐N)}₂] [M=Ga ( 3 ), In ( 4 )]. Complexes 3 and 4 were also obtained by treatment of 1 with the trialkyl derivatives [M(CH₂SiMe₃)₃] (M=Ga, In) at high temperatures. The analogous reaction of 1 with [{Ga(NMe₂)₃}₂] at 110 °C leads to [{Ga(μ₃‐N)₂(μ₃‐NH)Ti₃(η⁵‐C₅Me₅)₃(μ₃‐N)}₂] ( 5 ), in which two [GaTi₃N₄] cube‐type moieties are linked through a gallium–gallium bond. Complex 1 reacts with one equivalent of germanium, tin, or lead bis(trimethylsilyl)amido derivatives [M{N(SiMe₃)₂}₂] in toluene at room temperature to give cube‐type complexes [M{(μ₃‐N)₂(μ₃‐NH)Ti₃(η⁵‐C₅Me₅)₃(μ₃‐N)}] [M=Ge ( 6 ), Sn ( 7 ), Pb ( 8 )]. Monitoring the reaction of 1 with [Sn{N(SiMe₃)₂}₂] and [Sn(C₅H₅)₂] by NMR spectroscopy allows the identification of intermediates [RSn{(μ₃‐N)(μ₃‐NH)₂Ti₃(η⁵‐C₅Me₅)₃(μ₃‐N)}] [R=N(SiMe₃)₂ ( 9 ), C₅H₅ ( 10 )] in the formation of 7 . Addition of one equivalent of the metalloligand 1 to a solution of lead derivative 8 or the treatment of 1 with a half equivalent of [Pb{N(SiMe₃)₂}₂] afford the corner‐shared double‐cube compound [Pb(μ₃‐N)₂(μ₃‐NH)₄{Ti₃(η⁵‐C₅Me₅)₃(μ₃‐N)}₂] ( 11 ). Analogous antimony and bismuth derivatives [M(μ₃‐N)₃(μ₃‐NH)₃{Ti₃(η⁵‐C₅Me₅)₃(μ₃‐N)}₂] [M=Sb ( 12 ), Bi ( 13 )] were obtained through the reaction of 1 with the tris(dimethylamido) reagents [M(NMe₂)₃]. Treatment of 1 with [AlCl₂{N(SiMe₃)₂}(OEt₂)] affords the precipitation of the singular aluminum–titanium square‐pyramidal aggregate [{{(Me₃Si)₂N}Cl₃Al₂}(μ₃‐N)(μ₃‐NH)₂{Ti₃(η⁵‐C₅Me₅)₃(μ‐Cl)(μ₃‐N)}] ( 14 ). The X‐ray crystal structures of 5 , 11 , 13 , 14 , and [AlCl{N(SiMe₃)₂}₂] were determined.     

Zur Reaktivität von Titanocenkomplexen [Ti(Cp′)2(η2‐Me3SiC≡CSiMe3)] (Cp′ = Cp,Cp*) gegenüber Benzoldicarbonsäuren

On the Reactivity of Titanocene Complexes [Ti(Cp′)₂(η²‐Me₃SiC≡CSiMe₃)] (Cp′ = Cp, Cp*) towards Benzenedicarboxylic Acids Titanocene complexes [Ti(Cp′)₂(BTMSA)] ( 1a , Cp′ = Cp = η⁵‐C₅H₅; 1b , Cp′ = Cp* = η⁵‐C₅Me₅; BTMSA = Me₃SiC≡CSiMe₃) were found to react with iodine and methyl iodide yielding [Ti(Cp′)₂(μ‐I)₂] ( 2a / b ; a refers to Cp′ = Cp and b to Cp′ = Cp*), [Ti(Cp′)₂I₂] ( 3a / b ) and [Ti(Cp′)₂(Me)I] ( 4a / b ), respectively. In contrast to 2a , complex 2b proved to be highly moisture sensitive yielding with cleavage of HCp* [{Ti(Cp*)I}₂(μ‐O)] ( 7 ). The corresponding reactions of 1a / b with p‐cresol and thiophenol resulted in the formation of [Ti(Cp′)₂{O(p‐Tol)}₂] ( 5a / b ) and [Ti(Cp′)₂(SPh)₂] ( 6a / b ), respectively. Reactions of 1a and 1b with 1,n‐benzenedicarboxylic acids (n = 2–4) resulted in the formation of dinuclear titanium(III) complexes of the type [{Ti(Cp′)₂}₂{μ‐1,n‐(O₂C)₂C₆H₄}] (n = 2, 8a / b ; n = 3, 9a / b ; n = 4, 10a / b ). All complexes were fully characterized analytically and spectroscopically. Furthermore, complexes 7 , 8b , 9a ·THF, 10a / b were also be characterized by single‐crystal X‐ray diffraction analyses.     

Katalytische Carbonylierung von Aceton-oxim an Bisoximato-diruthenium-Komplexen: Ein einfacher Zugang zu wasserfreiem Acetonin. Isolierung und Molekülstruktur von [Ru2(CO)5(Me2CNO)2(Me2CNOH)]

Catalytic Carbonylation of Acetone Oxime at Bisoximatodiruthenium Complexes: A Simple Access to Anhydrous Acetonine. Isolation and Molecular Structure of [Ru₂(CO)₅(Me₂CNO)₂(Me₂CNOH)] In the presence of catalytic amounts of [Ru₂(CO)₄(Me₂CNO)₂(Me₂CNOH)₂] ( 1 ), acetone oxime reacts with carbon monoxide to give 2,3,4,5-tetrahydro-2,2,4,4,6-pentamethylpyrimidine (‘acetonine’). CO₂, and NH₃. The reaction proceeds presumably via carbonylation of Me₂C?NOH to the unstable intermediate Me₂C?N? OCHO which undergoes decarboxylation to give the corresponding imine Me₂C?NH. The final product is assumed to result from the cyclotrimerisation of Me₂C?NH with elimination of NH₃. Evidence for the intermediacy of the imine comes from the analogous reaction of acetophenone oxime, PhMeC?NOH, which gives the corresponding imine PhMeC?NH as a stable product. The isolation of the complex [Ru₂(CO)₅(Me₂CNO)₂(Me₂CNOH)] ( 2 ) suggests the carbonylation to take place at the bridging oximato ligand of 1 .