CHEMISTRY OF HYDRIDO CARBONYL-6B METALATES SUBSTITUTED BY P-DONOR LIGANDS - HW(CO)4PME3- HW(CO)4POME3- HW(CO)4PPH3- AND MU-H[WM(CO)10-X(P(OME)3)X] (M=CR,W - X=1,2) Academic Article uri icon

abstract

  • The synthesis of PPN+HW(CO)4PR3 (R = Me, OMe, Ph) was accomplished via careful protonation of W(CO)4PR32. The cis orientation of the hydride and P-donor ligands was affirmed by v(CO) infrared and carbon-13 nuclear magnetic resonance studies. Chemical characterizations included reactions with CO2, yielding the insertion product HCOOW(CO)4P, and with protic, main-group, and transition-metal Lewis acids. With trimethylaluminum the hydride was abstracted and the presumably 5-coordinate [W(CO)4P]0 resulting therefrom aggregated with unreacted HW(CO)4P to produce -H[W(CO)4P]2 (P = P(OMe)3, PMe3). The latter disubstituted binuclear bridging hydrides were also the products obtained from deliberate thermal or aerobic decomposition of these phosphine hydrides. Aggregation of HW-(CO)4P(OMe)3 with photochemically produced [W(CO)5]0 or [Cr(CO)6]0 readily occurred, yielding the monosubstituted binuclear bridging hydride anions. Tungsten-183 to proton coupling was interpreted in terms of the electronic and/or steric asymmetry of the hydride in these latter anions. 1982, American Chemical Society. All rights reserved.

published proceedings

  • ORGANOMETALLICS

author list (cited authors)

  • SLATER, S. G., LUSK, R., SCHUMANN, B. F., & DARENSBOURG, M.

citation count

  • 32

complete list of authors

  • SLATER, SG||LUSK, R||SCHUMANN, BF||DARENSBOURG, M

publication date

  • December 1982