Cobalticenium salts. II. Synthesis and structure of cobalticenium (triphenylphosphine)trihalogenocobaltates(II), [Cp2Co][Co(PPh3)X3] (X = Cl,Br,I)

The synthesis of cobalticenium (triphenylphosphine)trihalogenocobaltates(II), [Cp2-Co][Co(PPh3)X3] (X = Cl,Br,I), which were first found as by-products in the reaction of cobaltocene with triphenylphosphonium halides, is reported. The nature of the green complexes was derived from analytical and spectroscopic data and confirmed by X-ray analysis of the iodo complex. Oxidation of solutions of the iodo complex by oxygen gives the compound [Cp2Co][Co(OPPh3)I3]. [Cp2Co][Co(PPh3)I3] is cubic (a = 18.272 A), space group Pa3, with eight formula units in the cell. The structure consists of discrete ions [Ph3PCoI3]− and [CpCoCp]+, both lying on a threefold axis. The apparent threefold symmetry of the cobalticenium cations is due to disorder of the π-cyclopentadienyl ligands about the threefold axes. The substituents of P and Co in the [Ph3PCoI3]− anion are in staggered configuration; the metal atom is approximately tetrahedrally surrounded by 3 I (at 2.557 A) and 1 P (at 2.368 A), the latter distance being larger than in other phosphinecobalt complexes.

[1]  F. Jellinek,et al.  Triphenylphosphonium and triethylphosphonium halides , 2010 .

[2]  F. Jellinek,et al.  Cobalticenium salts. I: Reaction of cobaltocene with hydrogen halides and with triphenylphosphonium halides , 2010 .

[3]  J. Ibers,et al.  The bonding of molecular nitrogen. I. The crystal and molecular structure of hydridodinitrogentris(triphenylphosphine)cobalt(I) , 1969 .

[4]  N. Yasuoka,et al.  The structure of the allene–metal complex, iodobis(triphenylphosphine)allenerhodium , 1969 .

[5]  P. Orioli,et al.  Square pyramidal structure of a five-co-ordinate cobalt (II) complex with the tripod ligand tris-(2-diphenylphosphinoethyl)amine , 1969 .

[6]  W. Horrocks,et al.  Crystal and molecular structure of tetraphenylarsonium triiodo(triphenylphosphine)nickelate(II), [(C6H5)4As][Ni(C6H5)3PI3] , 1968 .

[7]  J. Ibers.  The structure of bis[tri-n-butylphosphine)tricarbonylcobalt] , 1968 .

[8]  A. R. Manning,et al.  The crystal structures of bis(tricarbonyltributylphosphinecobalt) and bis(tricarbonyltriethylphosphinecobalt)mercury , 1968 .

[9]  A. C. Skapski,et al.  trans-Bis(triphenylphosphine)methyldi-iodorhodium(III): a square-pyramidal complex , 1968 .

[10]  N. A. Bailey,et al.  Crystal and molecular structures of two crystallographic modifications of trans-di-iodobis(dimethylphenylphosphine)palladium(II) , 1968 .

[11]  J. Ibers,et al.  Structure of IrIO2(CO)(P(C6H5)3)2.CH2Cl2, the oxygen adduct of a synthetic irreversible molecular oxygen carrier , 1967 .

[12]  H. M. Powell,et al.  The crystal and molecular structure of the pentaco-ordinate complex tricarbonyl(triphenylphosphine)-σ-tetrafluoroethylcobalt(I) , 1967 .

[13]  T. Blundell,et al.  A distorted trigonal bipyramidal co-ordination of cobalt in tris-(o-diphenylphosphinophenyl)phosphinochlorocobalt(II) tetraphenylborate , 1967 .

[14]  R. Drago,et al.  Hydrogen-Bonding Interaction of Chloroform with Metal Complexes. Chloroform Nuclear Magnetic Resonance Contact Shifts , 1966 .

[15]  J. A. Bertrand,et al.  Five-Coordinate Complexes. I. The Crystal and Molecular Structure of Dibromotris(diphenylphosphine)cobalt (II) and Related Compounds , 1966 .

[16]  G. N. Mar.  Isotropic Shifts of Some Ionic Complexes of Cobalt(II) and Nickel(II) : Evidence for Ion Pairing , 1964 .

[17]  J. Daly.  729. The crystal and molecular structure of triphenylphosphorus , 1964 .

[18]  F. H. Moore.  Analytic constants for atomic scattering factors , 1963 .

[19]  P. G. Owston,et al.  633. The crystal structure of trans-dimesitylbis(diethylphenylphosphine)cobalt(II) , 1963 .

[20]  C. Furlani,et al.  Über einige Abkömmlinge des Dicyclopentadienylkobalts , 1962 .

[21]  F. Cotton,et al.  Magnetic Investigations of Spin-free Cobaltous Complexes. VI.1 Complexes Containing Phosphines and the Position of Phosphines in the Spectrochemical Series , 1961 .

[22]  F. Cotton,et al.  442. The effect of complex-formation by phosphine oxides on their P–O stretching frequencies , 1960 .

[23]  H. A. Levy,et al.  HIGH-SPEED COMPUTATION OF THE ABSORPTION CORRECTION FOR SINGLE CRYSTAL DIFFRACTION MEASUREMENTS , 1957 .