Theoretical Study on Novel Mixed Valence, P-H Functional P-Ligands, and Their Tautomerization.

ABSTRACT The synthesis of a novel mixed valence P-ligand system (II/I) with a PP bond bearing phosphonite and PH phosphanyl subunits was achieved via the reaction of a Li/Cl phosphinidenoid complex with a phosphite-substituted ketone. Density functional theory (DFT) calculations provide insight into bonding features of the novel R(H)PP(OR′)2 ligand system and its tautomer RP = PH(OR′)2. Wiberg bond index, Mayer bond order, and electron density at bond critical points are reported for both the free and ligated forms, pointing to a high degree of PP double bond character of the free ligand with a significant bond order decrease in end-on pentacarbonyltungsten complexation. [ABSTRACT FROM AUTHOR]