Copper(i) coordination polymers and mononuclear copper(i) complexes built from poly(1,2,4-triazolyl)borate ligands and tri-organophosphinesElectronic supplementary information available: conductivity data for compounds 1–14. See http://www.rsc.org/suppdata/dt/b2/b200200k/

Abstract

New copper(I) triorganophosphine derivatives [Cu(R3P)n{(tz)2BH2}] and [Cu(R3P)n{(tz)3BH}] (n = 1 or 2) have been synthesised from the reaction of CuCl with PR3 (R = phenyl, cyclohexyl, benzyl, o-, m-, or p-tolyl) or PMePh2 and potassium dihydrobis(1,2,4-triazolyl)borate, K[H2B(tz)2], or potassium hydrotris(1,2,4-triazolyl)borate, K[HB(tz)3]. The complexes obtained have been characterized by elemental analyses and FT-IR in the solid state, and by NMR (1H and 31P{1H}) spectroscopy and conductivity measurements in solution. The solution data are consistent with partial dissociation of the sterically hindered complexes by way of breaking of Cu–P and Cu–N bonds. Single crystal structural characterizations were undertaken for several of them. The structurally authenticated arrays fall into four different types: (a) discrete mononuclear [Cu(R3P)2{(tz)2BH2}] with a four-coordinate CuP2(N2) coordination sphere, (b) one-dimensional polynuclear [Cu(R3P){(tz)BH2(tz)}](∞/∞) with a four-coordinate CuP(N3) coordination sphere due to coordination by way of both N(2) and N(4) in one of the heterocyclic rings, (c) discrete mononuclear [Cu(R3P){(tz)3BH}] with a CuP(N3) coordination sphere, (d) one-dimensional polynuclear [Cu(R3P)2{(tz)BH(tz)(tz)}](∞/∞)with a four-coordinate CuP2(N2) coordination sphere in which one of the ligand tz rings is uncoordinated and the other two bridge through N(4) to successive copper atoms.