Investigation of the stability of the M-H-B bond in borane sigma complexes [M(CO)5(eta1-BH2R.L)] and [CpMn(CO)2(eta1-BH2R.L)] (M=Cr, W; L=tertiary amine or phosphine): substituent and Lewis base effects

Chemistry. 2007;13(24):6920-31. doi: 10.1002/chem.200601883.

Abstract

We investigated the influence of a substituent and a Lewis base on boron upon the thermodynamic stability of metal complexes of borane-Lewis base adducts, [M(CO)5(eta1-BH(2)R.L)] (M=Cr, W) and [CpMn(CO)2(eta1-BH2R.L)], where R=Cl, I, m-C6H4F, Ph, H, Me, Et; L=PMe3, PPh3, NMe3, quinuclidine. In these compounds, the stability of the metal-borane linkage was enhanced by increasing the electron-releasing ability of the substituent on boron. A stronger base L additionally stabilized the complexes. The strength of the borane-metal interaction is thus mainly ascribed to the electron donation from the BH sigma orbital to metal rather than the back-donation into the BH sigma* orbital. This result supports the bonding model for the B-H-M linkage in the borane complexes suggested by MO calculations, where the borane-to-metal electron donation is predominant while the metal back-donation into the BH sigma* orbital is negligible. Such a stability trend of the borane complexes makes a sharp contrast to that of many silane and dihydrogen complexes.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amines / chemistry*
  • Boranes / chemical synthesis
  • Boranes / chemistry*
  • Boron / chemistry*
  • Carbon Monoxide / chemistry*
  • Chromium Compounds / chemical synthesis
  • Chromium Compounds / chemistry*
  • Hydrogen / chemistry*
  • Hydrogen-Ion Concentration
  • Magnetic Resonance Spectroscopy
  • Manganese Compounds / chemical synthesis
  • Manganese Compounds / chemistry
  • Models, Molecular
  • Molecular Conformation
  • Phosphines / chemistry*
  • Protons
  • Temperature
  • Thermodynamics

Substances

  • Amines
  • Boranes
  • Chromium Compounds
  • Manganese Compounds
  • Phosphines
  • Protons
  • Carbon Monoxide
  • Hydrogen
  • phosphine
  • Boron