Effect of ligand donor atom on the kinetics of O2 and CO binding in copper(I) complex systems

INOR 936

Heather R. Lucas, hlucas4@jhu.edu, Gerald J. Meyer, meyer@jhu.edu, and Kenneth D. Karlin, karlin@jhu.edu. Department of Chemistry, The Johns Hopkins University, 3400 North Charles Street, Baltimore, MD 21218
Our overall goal is to elucidate how changes in the ligand-copper complex, i.e., electronic properties, coordination number, donor-atom, collectively affect the dynamics of CO and/or O2 binding to Cu(I), following LCuI-CO photolysis. By utilizing the “flash-and-trap” method, kinetic and thermodynamic parameters for the reactions of O2 and CO with various mononuclear copper containing systems can be determined. This technique involves single wavelength excitation (λex=355 nm) into the MLCT band of [CuI(L)(CO)]+ resulting in CO photodissociation, which in turn reveals a labile coordination site whereupon O2 binds, producing a cupric-superoxo species; at this point, CO subsequently displaces dioxygen, reforming the ground state complex. [J. Am. Chem. Soc. 2003, 125, 11866.] Previous work will be briefly overviewed as background information, and new results presented, employing (1) TMPA {TMPA = tris(2-pyridyl)methyl]amine} ligands modified by substitution of one pyridyl arm with a different donor atom (N,S,O), and (2) tridentate ligands {BzPy1 = bis(2-picolyl)benzylamine}.
 

Spectroscopy of Inorganic Systems
9:00 AM-11:20 AM, Thursday, August 23, 2007 BCEC -- 211, Oral

Division of Inorganic Chemistry

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