ELECTRONIC AND STERIC CONTROL OF REACTIONS OF BENZYLMAGNESIUM CHLORIDE WITH SUBSTITUTED METAL-CARBONYLS Academic Article uri icon

abstract

  • Kinetic studies are reported for nucleophilic addition of benzylmagnesium chloride to a series of LM-(CO)z complexes, LM(CO)z + C6H5CH2MgCl+ LM(CO)z-1 C(CH2C6H5)O-MgCl+, where L = CO, phosphine, or phosphite, M = Fe (x = 4) or W, Mo, or Cr (x = 5). Nucleophilic reaction occurs at the cis carbonyl ligand of LM(CO)5 complexes except when L is the very bulky ligand tri-o-tolylphosphine. For LFe(CO)4 complexes, however, addition is to the trans carbonyl group. Electronic properties of the CO ligand as indicated by the CO stretching force constant or frequency dominate CO reactive sites within a molecule and also reaction rates for Grignard addition to CO ligands trans to a substituent. Reaction rates of addition to cis carbonyl groups are governed by the steric requirements of L. The limitations inherent in applying a force constant/reactivity correlation are discussed. 1973, American Chemical Society. All rights reserved.

published proceedings

  • JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

altmetric score

  • 3

author list (cited authors)

  • DARENSBOURG, M. Y., CONDER, H. L., DARENSBOURG, D. J., & HASDAY, C.

citation count

  • 61

complete list of authors

  • DARENSBOURG, MY||CONDER, HL||DARENSBOURG, DJ||HASDAY, C

publication date

  • September 1973