New 17-electron, chromium-, molybdenum- and tungsten-centered radicals containing a cyclopentadienylide ligand

INOR 128

John H Brownie1, Michael C Baird, bairdmc@chem.queensu.ca1, William E. Geiger, wgeiger@zoo.uvm.edu2, and Derek R Laws, dlaws@uvm.edu2. (1) Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, ON K7L 3N6, (2) Department of Chemistry, University of Vermont, Cook Physical Sciences Building, Burlington, VT 05405
We have previously described the synthesis of the new aromatic ligand methyldiphenylphosphonium cyclopentadienylide (C5H4PMePh2), and have shown that it forms complexes of the type (η5-C5H4PMePh2)M(CO)3 (M = Cr, Mo, W) via coordination of the cyclopentadienyl-like ring (Brownie, J. H.; Baird, M. C.; Schmider, H. Organometallics 2007, 26, 1433). We have now investigated the single electron oxidation chemistry of these compounds (cyclic voltammetry, bulk electrolysis, oxidation by [Cp2Fe][B(C6F5)4] and [Ph3C][B(C6F5)4)]), finding that the corresponding 17-electron, metal-centered radicals [(η5-C5H4PMePh2)M(CO)3]+ are formed and dimerize to give the dicationic, metal-metal bonded complexes [(η5-C5H4PMePh2)3]2[B(C6F5)4)]2. The structures and chemistry of the new 17-electron complexes and their dimers will be discussed and compared with those of the previously studied Cp and arene analogues.
 

Organometallic Synthesis
1:30 PM-5:20 PM, Sunday, August 19, 2007 BCEC -- 212, Oral

Division of Inorganic Chemistry

The 234th ACS National Meeting, Boston, MA, August 19-23, 2007