Matrix Infrared Spectra and Quantum Chemical Calculations of Ti, Zr, and Hf Dihydride Phosphinidene and Arsinidene Molecules.

Abstract

Laser ablated Ti, Zr, and Hf atoms react with phosphine during condensation in excess argon or neon at 4 K to form metal hydride insertion phosphides (H2P-MH) and metal dihydride phosphinidenes (HP═MH2) with metal phosphorus double bonds, which are characterized by their intense metal-hydride stretching frequencies. Both products are formed spontaneously on annealing the solid matrix samples, which suggests that both products are relaxed from the initial higher energy M-PH3 intermediate complex, which is not observed. B3LYP (DFT) calculations show that these phosphinidenes are strongly agostic with acute H-P═M angles in the 60° range, even smaller than those for the analogous methylidenes (carbenes) (CH2═MH2) and in contrast to the almost linear H-N═Ti subunit in the imines (H-N═TiH2). Comparison of calculated agostic and terminal bond lengths and covalent bond radii for HP═TiH2 with computed bond lengths for Al2H6 finds that these strong agostic Ti-H bonds are 18% longer than single covalent bonds, and the bridged bonds in dialane are 10% longer than the terminal Al-H single bonds, which show that these agostic bonds can also be considered as bridged bonds. The analogous arsinidenes (HAs═MH2) have 4° smaller agostic angles and almost the same metal-hydride stretching frequencies and double bond orders. Calculations with fixed H-P-Ti and H-As-Ti angles (170.0°) and Cs symmetry find that electronic energies increased by 36 and 44 kJ/mol, respectively, which provide estimates for the agostic/bridged bonding energies.