ic001007k_si_001.pdf (960.37 kB)
Electronic and Structural Variation among Copper(II) Complexes with Substituted Phenanthrolines
journal contribution
posted on 2001-03-09, 00:00 authored by Patrick M. Bush, Joyce P. Whitehead, Courtney C. Pink, Erin C. Gramm, Judith L. Eglin, Stephen P. Watton, Laura E. PenceA series of copper(II) complexes with substituted phenanthroline ligands has been synthesized and characterized
electronically and structurally. The compounds that have been prepared include the monosubstituted ligand
complexes of the general formula [Cu(5-R-phen)2(CH3CN)](BF4)2, where R = NO2, Cl, H, or Me, and the
disubstituted ligand complex [Cu(5,6-Me2-phen)2(CH3CN)](BF4)2. The complexes [Cu(5-NO2-phen)2(CH3CN](BF4)2 (1), [Cu(5-Cl-phen)2(CH3CN)](BF4)2 (2), [Cu(o-phen)2(CH3CN)](BF4)2 (3), and [Cu(5-Me-phen)2(CH3CN)](BF4)2 (4) each crystallize in the space group C2/c with compounds 1, 2, and 4 comprising an isomorphous
set. The disubstituted complex [Cu(5,6-Me2-phen)2(CH3CN)](BF4)2 (5) crystallizes in the space group P21/c. Each
structure is characterized by a distorted trigonal bipyramidal arrangement of ligands around the central copper
atom with approximate or exact C2 symmetry. The progression from electron-withdrawing to electron-donating
substituents on the phenanthroline ligands correlates with less accessible reduction potentials for the bis-chelate
complexes.
