SPECTROELECTROCHEMICAL STUDIES OF COPPER(I) COMPLEXES WITH BINAPHTHYRIDINE AND BIQUINOLINE LIGANDS - CRYSTAL-STRUCTURE DETERMINATION OF YRIDO[2,3-B-3',2'-J][1,10]PHENANTHROLINE)COPPER(I) TETRAFLUOROBORATE

The electrochemical and spectral properties of some copper(I) polypyri dyl complexes based on 6,7-dihydrodibenzo-[b.j][1,10]phenanthroline, d mbiq, and ihydrodipyrido[2,3-b:3',2'-j][1,10]phenanthroline, dmbinap, are reported. These complexes are [Cu(dmbiq)(2)](+), 1; [Cu(dmbiq)(PPh (3))(2)](+), 2; [Cu(dmbinap)2](+), 3; and [Cu(dmbinap)(PPh(3))(2)](+), 4. 3 and 4 may be reduced to form ligand-based radical anion species. The resonance Raman spectra of 3(.-) and 4(.-) are almost identical a nd correspond closely to the spectrum of dmbinap(.-) and the reported spectra of complexes containing 2,2'-biquinoline radical anion moietie s. Reduction processes for 1 and 2 are irreversible. For 1 the electro nic spectral changes arising from reduction suggest demetallation of t he complex. The structure of [Cu(C18H12N4)(2)][BF4]. CH2Cl2 (3[BF4]. C H2Cl2) was determined by single-crystal X-ray diffraction. It crystall ized in the monoclinic space group P2(1)/c with cell dimensions a = 14 .059(7) Angstrom, b = 15.058(6) Angstrom, c = 16.834(9) Angstrom,beta = 111.56(5) degrees, Z = 4, rho(calcd) = 1.611 g/cm(3), and R(F-0) = 0 .0497.