Stereochemical studies of the carbon dioxide insertion reactions into the tungsten-alkyl bond Academic Article uri icon

abstract

  • Unequivocal demonstration of the a-carbon stereochemistry in the carbon dioxide insertion reaction has been accomplished by the conversion of threo-W(CO)5CHDCHDPh- with CO2 to threo-W(CO)5O2CCHDCHDPh- indicating that a high degree of retention of configuration at the carbon was involved. A similar observation has been noted for the phosphine substituted derivative threo-cis-W(CO)4[PMe3]CHDCHDPh- which reacts with carbon dioxide to afford threo-cis-W-(CO)4[PMe3]O2CCHDCHDPh-. For comparative purposes, migratory CO insertion induced by carbon monoxide transformed threo-W-W(CO)5CHDCHDPh- to threo-W(CO)5C(O)CHDCHDPh-. Hence, threo-W(CO)5CHDCHDPh- undergoes both insertion of carbon monoxide and carbon dioxide to afford 1,1- and 1,2-addition products, respectively, with retention of configuration at the a-carbon atom. 1985, American Chemical Society. All rights reserved.

published proceedings

  • Journal of the American Chemical Society

author list (cited authors)

  • Darensbourg, D. J., & Grotsch, G.

publication date

  • January 1, 1985 11:11 AM