Search for organometallic complexes with bishomoaromatic ligands

CHED 1439

Megan D. Kelly, mekelly@transy.edu, Division of Natural Sciences and Mathematics, Transylvania University, 300 North Broadway, Lexington, KY 40508 and Alan C. Goren, agoren@transy.edu, Department of Natural Sciences & Mathematics, Transylvania University, 300 North Broadway, Lexington, KY 40508.
The discovery that semibullvalene is a fluxional molecule which undergoes a very rapid, degenerate Cope rearrangement (J.Am.Chem.Soc,1969,91,3316) has stimulated both theoreticians and experimentalists to find a derivative in which the bishomoaromatic structure is a global energy minimum. Recent theoretical calculations (J.Am.Chem.Soc,2002,124,3469) proposed that 2,6-dicyano-4,8-diphenylsemibullvalene is bishomoaromatic at room temperature. This computational study has employed these fluxional molecules as ligands in novel transition-metals complexes. The ligands have included not only substituted semibullvalenes, but also substituted barbaralanes. Several transition metals in a variety of oxidation states have also been investigated. All the calculations for this study were carried out with the 6-31G* basis set using Becke's hybrid, three-parameter functional and the nonlocal correlation functional of Lee, Yang, and Parr (B3LYP).