SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF 5-CO-ORDINATE COPPER(I) AND SILVER(I) 2,2'6',2''-TERPYRIDINE COMPLEXES

Five-co-ordinate copper(I) and silver(I) 2,2':6',2''-terpyridine (terpy) complexes of the type [M(PPh(3))(2)(terpy)]ClO4 (M = Cu or Ag) have been prepared by the reaction of terpy with either [Cu(PPh(3))(2)(MeCN)(2)]ClO4 or [Ag(PPh(3))(2)]ClO4. The complexes have been characterised by spectroscopic methods and single-crystal X-ray diffraction analysis. In the crystal the complexes consist of discrete monomers of distorted trigonal-bipyramidal geometry, with the metal atoms co-ordinated to the distal terpyridine pyridyl rings [Cu-N 2.386(3). 2.535(4); Ag-N 2.614(2), 2.561(2)Angstrom A] in axial sites. The co-ordination spheres are completed by the binding of the central pyridyl nitrogen atoms [Cu-N(2) 2.102(3), Ag-N(2) 2.457(2) Angstrom A] and two PPh(3) phosphorus atoms, which together define the equatorial planes. The H-1 and {H-1}-C-13 NMR spectra of [Cu(PPh(3))(2)(terpy)]ClO4 and [Ag(PPh(3))(2)(terpy)]ClO4 show that for each of the complexes the five-co-ordinate nature of the compounds is also retained in solution with the distal pyridyl rings being equivalent on the NMR time-scale.