Synthesis, reactivity and structural characterization of some heterometallic complexes containing naked arsenic ligands†

The reactions of [Co2(µ-As2)(CO)6] with [Mo2Cp2(CO)4] (Cp = η5-C5H5) and with [(OC)4CoMCp(CO)3] [M = Mo or W] gave, respectively, the known product [Mo2(µ-As2)Cp2(CO)4] 1 and the new heterobimetallic complexes [(OC)3Co(µ-As2)MCp(CO)2] [M = Mo 2 or W 3]. The mixed-metal complexes have been treated with PPh3 to give the substituted complexes [(Ph3P)(OC)2Co(µ-As2)MCp(CO)2] [M = Mo 4 or W 5]. Complex 2 reacted with [Cr(CO)5]·THF to give [(OC)3Co{µ-As2[Cr(CO)5]2}MoCp(CO)2] 6. Reaction of [MoWCp2(CO)4] with [Co2(µ-As2)(CO)6] does not lead to the complex [MoW(µ-As2)Cp2(CO)4] although this can be obtained by co-thermolysis of [Mo2Cp2(CO)6] and [W2Cp2(CO)6] with grey arsenic which affords three bimetallic products, [MM′(µ-As2)Cp2(CO)4] (M = M′ = Mo 1; M = Mo, M′ = W 7; M = M′ = W), and four trimetallic products, [M2M′(µ3-As)Cp3(CO)6] (M = M′ = Mo; M = Mo, M′ = W 8; M = W, M′ = Mo 9; M = M′ = W). The new heterometallic complexes 2, 3, 5, 6 and 9 have been characterized by X-ray diffraction analyses.

[1]  Gotthelf Wolmershäuser,et al.  [Cp4Fe4(E2)2] Clusters with Triangulated Dodecahedral Fe4E4 Skeletons (E = P, As) , 1995 .

[2]  Wei Chen,et al.  Coordination of the (μ-η2-As2) ligand to group 6 transition metal carbonyl fragments and crystal structures of Cp2Cr2(CO) 4As2[M(CO)5]2 (M Cr, W) , 1995 .

[3]  B. Nuber,et al.  Komplexinduzierter abbau von As4S4 synthese von molybdän-schwefel-komplexen und molybdän-arsen-tetrahedranen , 1992 .

[4]  O. Scherer,et al.  [(C5Me4R)Co(As2)]-Molekülbausteine☆ , 1992 .

[5]  Lijuan Li,et al.  High-field NMR study of vertex rotation in (C5HnMe5-n)MCo2(CO)8CR clusters (M = molybdenum, tungsten): x-ray crystal structure of (C5Me5)MoCo2(CO)8CCO2-iso-Pr , 1991 .

[6]  B. Nuber,et al.  Photolytische und thermische Umsetzungen von μ3-As[WCp(CO)2]3 mit Fe(CO)5 und Fe2(CO)9 ; Röntgenstrukturanalysen der Cluster FeW2Cp2(CO)7[μ3-As-WCp(CO)3], Fe2WCp(CO)8H[μ3-As-WCp(CO)3] und Fe2WCp(CO)8H[μ3-As-FeCp(CO)2] , 1991 .

[7]  T. Mak,et al.  Synthesis and thermolysis of di- and triarsenic complexes of chromium. Crystal structure of [CpCr(CO)2]2As2 , 1991 .

[8]  D. Fenske,et al.  Synthesen und Kristallstrukturen von [Pd9As8(PPh3)8] und [Pd9Sb6(PPh3)8] , 1991 .

[9]  O. Scherer.  Complexes with Substituent‐free Acyclic and Cyclic Phosphorus, Arsenic, Antimony, and Bismuth Ligands , 1990 .

[10]  A. Rheingold,et al.  Arsenic-sulfur heterocycle formation via metal coordination. Synthesis and molecular structure of cyclo-(CH3AsS)n (n = 3, 4), [(CO)3Mo][.eta.3-cyclo-(CH3As)6S3], and the triple-decker-sandwich complex [.eta.5-(C5H5)2Mo2(.eta.2,.mu.-As3)(.eta.2,.mu.-AsS)] , 1990 .

[11]  A. Rheingold,et al.  Structural chemistry of transition metal complexes containing arsenic-arsenic bonds , 1990 .

[12]  D. Fenske,et al.  Pd Clusters Containing As and PPh3 Ligands: The Structures of [Pd9As6 (PPh3)8], [Pd2(As2)(PPh3)4], and [Pd20As12 (PPh3)12] , 1989 .

[13]  H. Sitzmann,et al.  Hexaarsabenzene as Complex Ligand , 1989 .

[14]  M. Ziegler,et al.  Darstellung und Charakterisierung von Tetrahedranen des Typs Cp3M3As(CO)6 und Cp2M2As2(CO)4 (Cp = C5H5, M = Mo, W) sowie von Derivaten dieser Tetrahedrane , 1988 .

[15]  H. Vahrenkamp,et al.  Mehrfacher Metallaustausch bei μ3-Methylidin-Tricobalt-Clustern , 1986 .

[16]  O. Scherer,et al.  (E2)2-einheiten (E = P, As) als clusterbausteine , 1986 .

[17]  W. Herrmann,et al.  Mehrfachbindungen zwischen Hauptgruppenelementen und Übergangsmetallen, XII. Erzeugung und Komplexstabilisierung von Arsiniden‐ und Diarsen‐Fragmenten durch metallinduzierten Abbau von Monoarsan , 1985 .

[18]  W. Herrmann,et al.  Arsanediyl (Arsinidene) and Diarsene Complexes by Metal‐Induced Degradation of Monoarsane , 1984 .

[19]  H. Brunner,et al.  Ligand Extrusion from the As4S4‐Cage by [C5Me5(CO)2Mo]2: Formation of (C5Me5)2Mo2(CO)4(μ,η2‐As2), C5Me5(CO)2Mo(η3‐As3), and (C5Me5)2Mo2As2S3 , 1984 .

[20]  H. Vahrenkamp,et al.  Darstellung von mehrkernkomplexen aus As2Co2(CO)6 , 1983 .

[21]  A. Rheingold,et al.  The synthesis and structural characterization of [η-C5H5Mo(CO)2]2[μ-catena-(CH3As)5]. An example of a ring → chain conversion upon coordination , 1983 .

[22]  D. I. Stuart,et al.  An empirical method for correcting diffractometer data for absorption effects , 1983 .

[23]  H. Vahrenkamp,et al.  Hetero‐Cluster: Metallaustausch über zweikernige (Cyclopentadienyl)metallcarbonyle , 1982 .

[24]  R. Hoffmann,et al.  Perpendicular and parallel acetylene complexes , 1982 .

[25]  T. Egolf,et al.  The reactivity of complexed carbocycles : XII. Neutral dimetallic complexes with bridging cyclooctatetraene. X-ray structure of μ-[1–4:5–8η-cyclooctatetraene]cyclopentadienylcobalt-tricarbonylmolybdenum (CoMo) , 1981 .

[26]  H. Vahrenkamp,et al.  Direct Metal Exchange in Carbonylcobalt Clusters , 1981 .

[27]  H. Vahrenkamp,et al.  Heteronuclear Cobalt Clusters by Metal Exchange , 1978 .

[28]  B. Penfold,et al.  Structural studies of derivatives of methinyltricobalt enneacarbonyls. IV. Crystal structure of hexacarbonoctacobalt tetracosacarbonyl, Co8(CO)24C6 , 1971 .

[29]  M. Churchill,et al.  Co8(CO)24C6, a bis(tricobalt nonacarbonyl)/dicobalt hexacarbonyl derivative of 2,4-hexadiyne from the reaction of dicobalt octacarbonyl with hexachlorocyclopropane , 1970 .

[30]  Foster,et al.  Organometallic pnicogen complexes. III. Preparation and structural characterization of the triarsenic-cobalt atom cluster system As3Co(CO)3. The first known X3-transition metal analog of group VA tetrahedral X4 molecules , 1969 .

[31]  J. Waser,et al.  The structure of arsenobenzene , 1961 .

[32]  David A. Brown.  Metal‐Metal Bonding in Dicobalt Hexacarbonyl Diphenylacetylene , 1960 .

[33]  W. G. Sly.  The Molecular Configuration of Dicobalt Hexacarbonyl Diphenylacetylene , 1959 .

[34]  J. Burns.  The Crystal Structure of Arsenomethane , 1957 .