Gemischtligandkomplexe des Nickel(0) und Kobalt(I) mit anionischen Liganden des Typs E(C6H5)3− (E  Ge,Sn, Pb)

Mixed Ligand Complexes of Nickel(0) and Cobalt(I) with the Anionic Ligands E(C₆H₅)₃^? (E ? Ge, Sn, Pb) Complexes of the general formula M^INi(PPh₃)₃(EPh₃)(THF)_x (E ? Ge[Ia], Sn[Ib], Pb[Ic]) and M^I₃Ni(PPh₃)(EPh₃)₃(THF)_x (E ? Ge[IIa], Sn[IIb]) are formed from (Ph₃P)₂Ni(C₂H₄) by substitution with M^IEPh₃. The analogous complexes of the ligand SiPh₃^? could not be prepared, because of the formation of SiPh₄ from LiSiPh₃ and coordinated PPh₃. Attempts to synthesize a nickel(II) complex of the ligand SnPh₃^? had no success, only possible decomposition products of these compounds, like (nBu₂PPh)₂Ni^II(Ph)Cl and Na_xNi°(PPh₃)_4?x(SnP₄)_x(THF)_Y, were isolated. NaCo^I(PPh₃)₂(SnPh₃)₂(THF)₇ (IV) was prepared by the reaction of Co(PPh₃)₃Cl and NaSnPh₃. ¹H-NMR and ¹¹⁹Sn Mössbauer spectra show a higher donor action of SnPh₃^? in IIb than in Ib. This causes a stronger π-back donation Ni → P in the case of IIb. IV is a paramagnetic compound, the vis-spectrum is discussed using simple crystal field theory.     

Oxydation von Nickel(0)-Komplexen mit cyclischen Carbonsäureamiden

Oxidation of Nickel(0) Complexes by Cyclic Imides of Dicarbonic Acids Normally, phthalimide (PI? H) or succinimide (SI? H) react with nickel(0) complexes — (dipy)Ni(COD) or (Ph₃P)₂Ni(C₂H₄) — by oxidative addition. The reaction of PI? H and the strong reductant (dipy)Ni(COD) is initiated by a one-electron transfer. Depending on the solvent, the resulting ion pair affords (dipy)Ni^I(PI) by spontaneous fragmentation or (dipy)Ni^II(H)(PI) by cage collaps. No interaction is found between the weak reductant (Ph₃P)Ni(C₂H₄) and PI? H. Phosphine-containing nickel(0) complexes are electrophilically attacked by the acid NH group of SI? H. Hydrido complexes of nickel(0), such as (Cy₃P)₂Ni(H)(SI), or secondary products of them, such as [(SI)Ni(THF)]₂NH, are formed. On the other hand, the reaction with (dipy)Ni(COD) affords only the binuclear substitution product [(dipy)Ni]₂(SI? H)(THF). In solution prolongated heating of (dipy)Ni(PI)(THF)_0,5 results in a partial decarbonylation. In contrast to the reaction of (dipy)Ni(COD) and cyclic carbonic acid anhydrides, no definite metalla rings but by an interaction with the solvent, benzamide is formed. With (dipy)Ni(COD) maleinimide does not react like on NH-acidic compound but like a polar olefine by substitution.     

Highly reduced organometallics: XI. Formal derivatives of the tricarbonylmetallates (6-) of chromium,molybdenum and tungsten

Reduction of W(CO)₃(PMTA) (PMTA = 1,1,4,7,7-pentamethyldiethylenetriamine) by six equivalents of potassium metal in liquid ammonia provides an incompletely characterized highly reduced carbonyltungstate ion which reacts with several electrophiles to provide derivatives containing only tungsten tricarbonyl units. These include W(CO)₃(NH₃)₃, [W₃(CO)₉(μ-OC₂H₅)(μ₃-OC₂H₅)₂]^3-, HW(CO)₃(SnPh₃)₃^2- and the unusual [(Ph₃Sn)₂{(Ph₂Sn)₂OEt}W(CO)₃]^?. The latter compound results from an unprecedented phenyl-tin cleavage in the reaction of triphenyltin chloride and the highly reduced carbonyltungstate ion. Triphenyltin derivatives of the unknown M(CO)₃^6- (M = Cr, Mo and W) have also been prepared by reacting M(CO)₃(SnPh₃)₃^3- with Brønsted acids and Ph₃SnCl. From these reactions the previously unknown HM(CO)₃(SnPh₃)₃^2- (M = Cr, Mo and W) and M(CO)₃(Ph₃Sn)₄^2- (M = Mo and W) have been isolated and characterized. The latter are the first compounds containing more than three triphenyltin units attached to one transition metal.     

Electrochemical Investigations Give Some Insights into the Coordination Chemistry of New Stable Iridium(+1), Iridium(0), and Iridium(−1) Complexes

The redox chemistry of the stable tetracoordinated 16 valence electron d⁸‐[Ir^+I(tropp^Ph)₂]⁺(PF₆)^? and pentacoordinated 18 valence d⁸‐[Ir^+I(tropp^Ph)₂Cl] complexes was investigated by cyclic voltammetry (tropp^Ph=dibenzotropylidenyl phosphine). The experiments were performed using a platinum microelectrode varying scan rates (100 mV/s–10 V/s) and temperatures (? 40 to 20 °C) in tetrahydrofuran, THF, or acetonitrile, ACN, as solvents. In THF, the overall two‐electron reduction of the 16 valence electron d⁸‐[Ir^+I(tropp^Ph)₂]⁺(PF₆)^? proceeds in two well separated slow heterogeneous electron transfer steps according to: d⁸‐[Ir^+I (tropp^Ph)₂]⁺+e^?→d⁹‐[Ir⁰(tropp^Ph)₂]+e^?→d¹⁰‐[Ir^?I(tropp^Ph)₂]^?, [k^s₁=2.2×10^?3 cm/s for d⁸‐Ir^+I/d⁹‐Ir⁰ and k^s₂=2.0×10^?3 cm/s for d⁹‐Ir⁰/d¹⁰‐Ir^?I]. In ACN, the two redox waves merge into one “two‐electron” wave [k^s_1,2=7.76×10^?4 cm/s for d⁸‐Ir^+I/d⁹‐Ir⁰ and d⁹‐Ir⁰/d¹⁰‐Ir^?I] most likely because the neutral [Ir⁰(tropp^Ph)₂] complex is destabilized. At low temperatures (ca. ? 40 °C) and at high scan rates (ca. 10 V/s), the two‐electon redox process is kinetically resolved. In equilibrium with the tetracoordianted complex [Ir^+I(tropp^Ph)₂]⁺ are the pentacoordinated 18 valence [Ir^+I(tropp^Ph)₂L]⁺ complexes (L=THF, ACN, Cl^?) and their electrochemical behavior was also investigated. They are irreversibly reduced at rather high negative potentials (? 1.8 to ? 2.4 V) according to an ECE mechanism 1) [Ir^+I(tropp^Ph)₂(L)]+e^?→[Ir⁰(tropp^Ph)₂(L)]; 2) [Ir⁰(tropp^Ph)₂(L)]→[Ir(tropp^Ph)₂]+L, iii) [Ir⁰(tropp^Ph)₂]+e^?→[Ir^?I(tropp^Ph)₂]^?. Since all electroactive species were isolated and structurally characterized, our measurements allow for the first time a detailed insight into some fundamental aspects of the coordination chemistry of iridium complexes in unusually low formal oxidation states.     

Organotin(IV) azido and mixed azidothiocyanato complex anions; A Mössbauer and vibrational spectroscopic study

Tetraphenylarsonium and tetramethylammonium salts of the complex anions Ph₃Sn(N₃)^?₂, Ph₃Sn(N₃)(NCS)^?, Me₂Sn(N₃)^2?₄ and Ph₂Sn(N₃)₂(NCS)^2?₂ have been synthesized, and the solid state configuration of the complex anions has been studied by Mössbauer and vibrational spectroscopies. Trigonal bipyramidal structures are advanced for the Ph₃Sn^IV derivatives, with equatorial SnC₃ and apical pseudohalide ligands, while the R₂Sn^IV compounds are assumed to be trans-octahedral species. The NCS^? ligands are observed to be N-bonded to Sn^IV. Conductance and PMR (for the Me₂Sn^IV compound) data suggest the presence of the complex anions also in solution phases.     

Synthesis and structure of organosilicon and organogermanium complexes of ytterbium (Ph3E)2Yb(THF)4 with Yb-Si and Yb-Ge bonds

Complexes (Ph₃Si)₂Yb(THF)₄ (1) and (Ph₃Ge)₂Yb(THF)₄ (2) were synthesised by the reactions of Ph₃SiCl or Ph₃GeCl with ytterbium in THF and characterised by X-ray diffraction. Compounds 1 and 2 have similar centrosymmetrical octahedral structures with a central Yb atom bonded to four oxygen atoms of THF molecules in equatorial positions and two Si (or Ge) atoms of SiPh₃ (or GePh₃) fragments in axial positions. In the crystal of 2 there are two symmetrically independent molecules with the same structure. The Yb-Si and Yb-Ge distances in 1 and 2 are 3.158(2) and 3.170(2), 3.141(2) Å, respectively.     

New heteroorganic betaines containing the (+)E15—C—E14—X(–) and (+)E15—C—E14(–) structural fragments (E15 = P,As; E14 = Si,Ge, Sn; X = C,S, O,NR)

The review surveys the data on the reactions of phosphorus and arsenic ylides with compounds containing E=X bonds (E = C, Si, Ge, or Sn; X = C or S), cyclic oligomers (R₂ES)_n (n = 2 or 3), and heavier analogs of carbenes. These reactions give rise to two new classes of heteroorganic betaines containing the ⁽⁺⁾E¹⁵—C—E¹⁴—X^(–) (I) and ⁽⁺⁾E¹⁵—C—E^14(–) (II) (E¹⁵ = P or As; E¹⁴ = Si, Ge, or Sn; X = C or S) structural fragments. Procedures for the synthesis of these compounds, their reactivities, the X-ray diffraction structures, and the electronic structures established by high-level quantum-chemical calculations are considered in detail. The carbon analogs of betaines of type I, viz., compounds bearing the ⁽⁺⁾P—C—C—X^(–) fragment (III), are also discussed. The latter were long considered as possible intermediates in the reactions of compounds containing the polar C=X bond (X = C, O, S, NR, etc.) with phosphorus ylides (classical Wittig and Corey—Chaykovsky reactions and related processes).     

Synthesis and structures of silicon-, germanium-, and tin-containing imido-alkyl molybdenum complexes (ArN)2Mo(CH2EMe3)2 (E = Si, Ge, Sn)

New silicon-, germanium-, and tin-containing imido-alkyl molybdenum complexes (ArN)₂Mo(CH₂EMe₃)₂ (Ar is 2,6-diisopropylphenyl; E = Si (1), Ge (2), Sn (3)) were prepared in the crystalline state in 58–66% yields by the reactions of the (ArN)₂MoCl₂(DME) complex with alkyllithium derivatives Me₃ECH₂Li (E = Si or Ge) or the Grignard reagents Me₃ECH₂MgCl (E = Ge or Sn). The structures of complexes 1–3 and the known analog (ArN)₂Mo(CH₂Bu^t)₂ (4) were established by X-ray diffraction analysis. Complexes 1–3 were found to be isostructural. The coordination environment about the Mo atom can be described as a distorted tetrahedron. Complex 4 has a similar structure. The Mo-C distance tends to decrease with increasing electron donating ability of the EMe₃ group.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 597–600, March, 2005.     

Reactions of silicon-, germanium- and tin-containing carbene complexes of tungsten Ph3E-CW(OBu)3 (E=Si, Ge, Sn) with hydrogen chloride: crystal structures of carbene complexes Ph3E-CHWCl2(OBu)2 (E=Si, Ge)

The novel organosilicon, -germanium and -tin-containing carbene complexes of tungsten of the type Ph₃E-CHWCl₂(OBu^t)₂ (E=Si, Ge, Sn) have been prepared by the reaction of heteroelement-containing carbene complexes of tungsten Ph₃E-CW(OBu^t)₃ (E=Si, Ge, Sn) with hydrogen chloride. The tin-containing carbene complex was identified in solution by ¹H NMR spectroscopy. Silicon- and germanium-containing carbene complexes were isolated in high yields as crystalline solids and characterized by elemental analysis, IR, ¹H NMR, ¹³C NMR and ²⁹Si NMR spectroscopy and X-ray diffraction studies. The geometry of the W atoms in the compounds can be described as a distorted square pyramid.     

Synthesis and characterization of titanium tetraisocyanide complexes, [CpTi(CNXyl)4E], E = I,SnPh3, and SnMe3

Oxidation of [CpTi(CO)₄]^? by I₂, Ph₃SnCl, and Me₃SnCl in the presence of four equivalents of CNXyl, Xyl = 2,6-dimethylphenyl, affords unprecedented titanium tetraisocyanide complexes, [CpTi(CNXyl)₄E], E = I, SnPh₃, SnMe₃. These have been isolated and characterized by spectroscopic methods as well as single-crystal X-ray crystallography. A by-product of the iodine reaction was the Ti(III) complex, [CpTi(CNXyl)₂I₂], which was also characterized by X-ray crystallography.     

Synthesis and structural characterization of new trinuclear cobalt(II) and nickel(II) complexes possessing five- and six-coordinated geometry

Tri-nuclear cobalt and nickel complexes ([(CoL)₂(OAc)₂Co]?·?THF (I) and [(NiL)₂(OAc)₂(THF)₂Ni]?·?THF (II)) have been synthesized by reaction of a new Salen-type bisoxime chelating ligand of 2,2′-[ethylenedioxybis(nitrilomethylidyne)]dinaphthol(H₂L) with cobalt(II) acetate tetrahydrate or nickel(II) acetate tetrahydrate, respectively. Complexes I and II were characterized by elemental analyses, IR, TG-DTA and ¹H-NMR etc. The X-ray crystal structures of I and II reveal that two acetate ions coordinate to three cobalt or nickel ions through M–O–C–O–M (M?=?Co or Ni) bridges and four μ-naphthoxo oxygen atoms from two [ML] units also coordinate to cobalt(II) or nickel(II). Complex I has two distorted square-pyramidal coordination spheres and an octahedral geometry around Co1. In complex II all three nickel ions are six-coordinate.     

New rearrangement of triphenyl(triphenylsilylperoxy)germane catalyzed by nucleophiles

The peroxide Ph₃GeOOSiPh₃ rearranges in THF solution at ca. 20°C in the presence of fluoride ions or triethylamine to the germasiloxane, Ph₂(PhO)GeOSiPh₃, while thermal rearrangement of the same peroxide gives Ph₃GeOSi- (OPh)Ph₂. The reaction of tris(trimethylsilylmethyl)stannyllithium (I) with one equivalent of the germasiloxane Ph₂(PhO)GeOSiPh₃ in THF yields (Me₃SiCH₂)₃SnPh, (Ph₂GeX)_x and Ph₃SiOLi. Analogous products have been obtained in high yield in the reactions of I with the peroxides Ph₃GeOOSiPh₃ and Ph₃GeOOSiMe₃. It is assumed that the initial step of these reactions is rearrangement of the peroxides, catalyzed by (Me₃SiCH₂)₃Sn anions, with the formation of the germasiloxanes Ph₂(PhO)GeOSiR₃ (R = Ph or Me). The mechanism of this catalytic rearrangement of unsymmetrical peroxides is discussed.     

(Me2NH2)[(Ph3Sn)3(MoO4)2], ein Triorganozinnmolybdat mit Schichtstruktur

(Me₂NH₂)[(Ph₃Sn)₃(MoO₄)₂], a Triorganotin Molybdate with Layer Structure The reaction of [(Ph₃Sn)₂MoO₄] with (Me₂NH₂)Cl in an acetonitrile/water mixture leads to the formation of (Me₂NH₂)[(Ph₃Sn)₃(MoO₄)₂] ( 1 ). ( 1 ) crystallizes in the space group Pca2₁ with a = 1967.0(4), b = 1353.1(2) and c = 2176.6(5) pm. In the crystal structure of 1 Ph₃SnO₂ bipyramides and MoO₄ tetrahedra are linked by corner sharing to give a layer structure. Additionally the layers are connected by O···H···N hydrogen bridges between MoO₄ groups and [Me₂NH₂]⁺ ions to give a 3D network structure.     

A Nickel Complex Containing a Pyramidalized,Ambiphilic Pincer Germylene Ligand

Reaction of N-heterocyclic carbene (NHC)-stabilized PGeP-type germylene Ge{o-(PiPr₂)C₆H₄}₂⋅^MeIiPr ( 1 ) (^MeIiPr=1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) with Ni(cod)₂ gave pincer germylene complex Ni[Ge{o-(PiPr₂)C₆H₄}₂](^MeIiPr) ( 2 ), in which the Ge center of 2 is significantly pyramidalized. Theoretical calculation on 2 predicted the ambiphilicity of the germanium center, which was confirmed by reactivity studies. Thus, complex 2 reacted with both Lewis base ^MeIMe (^MeIMe=1,3,4,5-tetramethylimidazol-2-ylidene) and Lewis acid BH₃⋅SMe₂ at the germanium center to afford the adducts Ni[Ge{o-(PiPr₂)C₆H₄}₂⋅^MeIMe](^MeIiPr) ( 3 ) and Ni[Ge{o-(PiPr₂)C₆H₄}₂⋅BH₃](^MeIiPr) ( 4 ), respectively. Furthermore, the former was slowly converted to dinuclear complex Ni₂[Ge{o-(PiPr₂)C₆H₄}₂]₂(^MeIMe)₂ ( 5 ) at room temperature. Complex 5 can be regarded as a dimer of the ^MeIMe analog of 2 with a Ni-Ge-Ge-Ni linkage.     

Nickelocene chemistry : III. Reactions of Bromo(η5-cyclopentadienyl)triphenylphosphinenickel with phosphorus,arsenic and sulphur ylids

The phosphorus ylids Ph₃PCHR (R = Me, Et, Prⁿ, Prⁱ, Bu_n, Cl, and OMe), and the ylids Ph₃AsCH₂, Me₂SCH₂, and Me₂S(O)CH₂ react with [Ni(η⁵-C₅H₅)Br(PPh₃)] at room temperature to give the complexes [Ni(Ph₃PCHR)(η⁵-C₅H₅(PPh₃)] Br, [Ni(Ph₃AsCH₂)(η⁵-C₅H₅)(PPh₃)]Br, [Ni(Me₂SCH₂)(η⁵-C₅H₅)(PPh₃)]Br and [Ni{Me₂S(O)CH₂} (η⁵-C₅H₅)(PPh₃)]Br, respectively. These are readily converted into the corresponding hexafluorophosphate salts on reaction with ammonium hexafluorophosphate. Under more forcing conditions the stabilised ylid Ph₃PCHCOPh gives a product believed to be the complex [Ni(Ph₃PCHCOPh)₂(η⁵-C₅H₅)]Br, isolated and characterised as its PF₆^? salt.     

Binukleare Nickel(II)‐Komplexe mit Oxalamidinaten als Brückenliganden: Synthese und Strukturen von Verbindungen mit planarer,tetraedrischer, tetragonal‐pyramidaler und oktaedrischer Koordination

Binuclear Nickel(II) Complexes with Oxalamidinates as Bridging Ligands: Synthesis and Struktures of Compounds with Planar, Tetrahedral, Tetragonal‐pyramidal, and Octahedral Coordination Oxalamidines R¹–NH–C(=NR²–C(=NR²)–NH–R¹ react selectively with Ni(acac)₂ under formation of the planar complexes [(acac)Ni(oxalamidinate)Ni(acac)]. Two crystal structures of the binuclear complexes with R = R′ = Ph ( 1 ) or p‐tolyl ( 2 ) show that the bridging oxalamidinates bind as bidendate ligands at each Nickel(II) atom. In contrast, the more sterically demanding fragment (Ph₃P)NiBr can only coordinate at sterically less demanding oxalamidinates to form complexes of the type [(Ph₃P)NiBr]₂(oxalamidinate) with tetrahedral coordination of Ni^II found by X‐ray analyses. Oxalamidines containing additional donor atoms in the side arms react very different, but in each case under formation of binuclear complexes, such as [(acac)₂Ni]₂( H₂E ) ( 8 ) (with R¹: –(CH₂)₃PPh₂, R²: p‐tolyl) in which the oxalamidine acts as bidentate neutral P,N‐ligand and the Ni^II atom has an octahedral environment. H₂F (with R¹: –(CH₂)₃PPh₂, R²: Mesityl), however, yields the planar complex [(acac)Ni]₂( F ) ( 9 ) with dianionic oxalamidinate under elimination of acetylacetone. There is no coordination of the donor groups of the side arms in the solid state of complex 9 , in contrast to the analogous binuclear complex [(acac)Ni]₂( H ) 10 (R¹: –CH₂–CH₂‐2‐pyridyl, R²: Mesityl). In this complex a distorted tetragonal‐pyramidal coordination of Ni^II is achieved. 2 reacts with an excess of LiCH₃ under elimination of the oxalamidinate to form the cluster compound Li₄(THF)₄Ni₂Me₈ in very good yields, while 9 yields the THF poorer cluster Li₂(THF)₂Li₂Ni₂Me₈ under similar conditions.     

Absorption,electrochemical, theoretical,and 73Ge NMR spectral characterization of the germanium neo-pentane analogue (Me3Ge)4Ge

The germanium-based neo-pentane analogue (Me₃Ge)₄Ge has been characterized by UV/visible spectroscopy, cyclic voltammetry, and ⁷³Ge NMR spectroscopy as well as by density functional theory (DFT) calculations. The absorption maximum for (Me₃Ge)₄Ge is blue-shifted relative to those for other related branched oligogermanes (Ph₃Ge)₃GeH and (Ph₃Ge)₃GePh, and this species is also the most difficult to oxidize among these three compounds. DFT calculations indicate the HOMO of (Me₃Ge)₄Ge is stabilized relative to those for both tetragermanes by ca. 0.5 eV and therefore the theoretical and experimental results are in agreement. The ⁷³Ge NMR spectrum of (Me₃Ge)₄Ge exhibits two resonances and the feature corresponding to the central formally zero-valent germanium atom is shifted far upfield and was observed at δ ?339 ppm.     

Untersuchungen an Polyhalogeniden. XXII [1]. Dimethyldiphenylammoniumpolyiodide (Me2Ph2N)In mit n = 3, 13/3, 6, 8: Darstellung und strukturelle Charakterisierung eines Triiodids (Me2Ph2N)I3, Tridecaiodids (Me2Ph2N)3I13, Dodecaiodids (Me2Ph2N)2I12 und Hexadecaiodids (Me2Ph2N)2I16

Studies of Polyhalides. 22. On Dimethyldiphenylammoniumpolyiodides (Me₂Ph₂N)I_n with n = 3, 13/3, 6, and 8: Preparation and Crystal Structures of a Triiodide (Me₂Ph₂N)I₃, Tridecaiodide (Me₂Ph₂N)₃I₁₃, Dodecaiodide (Me₂Ph₂N)₂I₁₂, and Hexadecaiodide (Me₂Ph₂N)₂I₁₆ The new compounds [(CH₃)₂(C₆H₅)₂N]I₃, [(CH₃)₂(C₆H₅)₂N]₃I₁₃, [(CH₃)₂(C₆H₅)₂N]₂I₁₂ and [(CH₃)₂(C₆H₅)₂N]₂I₁₆ have been prepared by the reaction of dimethyldiphenylammonium iodide [(CH₃)₂(C₆H₅)₂N]I with iodine I₂ in ethanol. Their crystal structures have been determined by single crystal X-ray diffraction methods. The structure of the triiodide may be described as a layerlike packing of pairs of nearly linear symmetric anions and tetraedral cations. The tridecaiodide forms zig-zag chains of iodide ions and iodine molecules with the iodide ion also weakly coordinated by two pentaiodide groups. The dodecaiodide is built from two pentaiodide-groups, which are bridged by an iodine molecule and connected with secondary bonds forming double chains. The hexadecaiodide ion forms layers built up from two heptaiodide groups and one iodine molecule. Thus the dimethyldiphenylammonium cation stabilizes a unique series of polyiodides of extraordinary composition and structure.     

Pseudohalogeno-Metallverbindungen. LXXV. Pentacarbonylrhenium-und Triphenylphosphangold-Komplexe mit Pseudohalogeniden: (OC)5ReX,Ph3PAuX (X = ONC(CN)2, o-MeC6H4SO2C(CN)2,o-MeC6H4SO2NCN,Ph2(S)PNCN)

Pseudohalogeno Metal Compounds. LXXV. Pentacarbonylrhenium and Triphenylphosphinegold Complexes of Pseudohalide Anions: (OC)₅ReX, Ph₃PAuX (x = ONC(CN)₂, o-MeC₆H₄SO₂C(CN)₂, o-MeC₆H₄SO₂NCN, Ph₂(S)PNCN) The pseudohalides (X^?) nitrosodicyanmethanide, o-tosyldicyanmethanide, o-tosylcyanamide and diphenylthiophosphinylcyanamide react with the Organometallic Lewis Acids (OC)₅Re⁺ (as (OC)₅ReFBF₃) and Ph₃PAu⁺ (as Ph₃PAuNO₃) to give the neutral title complexes (OC)₅Re—X and Ph₃PAu? X, respectively. X-ray diffraction shows that nitroso-dicyanmethanide is coordinated through the nitroso N-atom to the Re(CO)₅ fragment. Cyanide-N-coordination is observed for the complexes with o-tosyldicyanmethanide and o-tosylcyanamide whereas diphenylthiophosphinylcyanamide is S-coordinated to the gold atom. Spectroscopic data (IR, NMR) of 1–6 are described.     

Tris(triphenylphosphan)nickel(0)-Komplexe mit Nitril-Liganden

Tris(triphenylphosphane)nickel(0) Complexes with Nitrile Ligands . Synthesis, properties and reaction behaviour of (Ph₃P)₃Ni(η¹-NCR) (R = PhCH₂, 2-MeC₆H₄, Me₃Si) complexes as well as the X-ray structure of (Ph₃P)₃Ni(η¹-NCSiMe₃) are described. With NC(CH₂)_nBr (n = 1, 2) instead of the analogous nitrile complexes (Ph₃P)₂NiBr₂ and CH₃CN or C₂H₅CN respectively are formed.