Tris(diphenylphosphinomethyl)phenylborate (PhBPPh) is a facially-capping anionic ligand that creates appropriate pseudotetrahedral metal (M = Fe, Co) environments for the stabilization of terminal imido complexes. Application of this ligand in octahedral complexes is an emerging research area, with an emphasis to date on Ru(II) and Rh(III) chemistry. This poster will discuss the syntheses of [Et4N][M(CO)3(PhBPPh)] (M = Cr, Mo, W), the first group VI metal complexes of PhBPPh and rare zerovalent complexes of this ligand. Infrared spectroscopic studies suggest that PhBPPh is a weaker donor than hydrotris(1-pyrazolyl)borate (Tp) towards the zerovalent M(CO)3 units in these anions. This ligand donor ranking is apparently reversed towards [Mn(CO)3]+ fragments on the basis of the IR spectra of the zwitterionic, monovalent manganese complex Mn(CO)3(PhBPPh). The boron-bound phenyl substituents of [Et4N][M(CO)3(PhBPPh)] and Mn(CO)3(PhBPPh) are sufficiently electron-rich to bind group VI metal M(CO)3 fragments to afford bimetallics in which tris(diphenylphosphinomethyl)phenylborate acts as a bridging ligand. The crystal structures of these bimetallics that detail this new PhBPPh binding mode will be discussed.

Low valent metal complexes of tris(diphenylphosphinomethyl)phenylborate

249th National Meeting (2015)

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