Synthesis and Characterization of Tetrahydrofurfurylcyclopentadienyl Molybdenum Tricarbonyl Dimer: Evidence for 19-Electron Intramolecular "Solvento" Interactions.
The synthesis and characterization of a THF pendant, dimeric Mo cyclopentadienyl complex is reported and the structure characterized by NMR, FTIR, and UV-vis spectroscopies. The dimer was found to undergo metal-metal bond homolysis under either photochemical or electrochemical conditions to yield an odd-electron complex. Cyclic voltammetry under varying scan rate conditions from 25 to 10 000 mV/s demonstrates a dynamic equilibrium process that we assign to the formation of either an intramolecular 19-electron (18 + delta) complex or a bare 17-electron complex. Photolysis of the dimer in room temperature solution could be monitored as a loss of the dpi-dsigma transition at 503 nm by transient absorption spectroscopy. The recovery of the transient absorption signal at 410 nm follows first-order kinetics at a rate of 5 x 10(3) s(-1).
Gallagher
Michelle
M
Department of Chemistry, St. Joseph's University, Philadelphia, Pennsylvania 19131-1395, and Department of Chemistry, Binghamton University (SUNY), Binghamton, New York 13902-6016.
Dougherty
Pat
P
Tanner
Pamela S.
PS
Barbini
Denis C.
DC
Schulte
Jurgen
J
Jones
Wayne E.
WE