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Reactions of Octacarbonyldicobalt with Tetraphenyl Derivatives of Goup 5A, including Tetraphenyldibismuthane. Synthesis and Crystal and Molecular Structure of Tricarbonyl(diphenylbismuthido)(triphenylphosphine)cobalt(I),
Calderazzo, Fausto,Poli, Rinaldo,Pelizzi, Giancarlo
, p. 2535 - 2540 (1984)
Tetraphenyldibismuthane reacts with to give the product of oxidative addition, , which was isolated as its triphenylphosphine adduct, . crystallises in the orthorhombic space group Pbca, with a=26.105(13), b=21.066(10), c=10.845(3) Angstroem, Z=8, R=0.0522, and R'=0.0497.The molecular structure consists of discrete units, the geometry around cobalt being that of a distorted trigonal bipyramid with three equatorial carbonyl groups and the BiPh2 and PPh3 ligands occupying the axial positions.The reactivity of towards E2Ph4 was compared along the series from E= arsenic to bismuth.Oxidative addition (E=Bi) and substitutive oxidative addition (E= As or Sb) reactivity patterns were encountered.No tendency of terminal BiPh2 to become bridging with CO substitution was observed.The unique behaviour of BiPh2 as a ligand is explained in terms of the low availability of the second lone pair on bismuth for bonding, in spite of the considerable ?-donation from bismuth to cobalt suggested for terminal BiPh2 by the i.r. spectra.
