Copper(I) coordination polymers and mononuclear copper(I) complexes built from poly(1,2,4-triazolyl)borate ligands and tri-organophosphines

New copper(I) triorganophosphine derivatives [Cu(R3P)(n){(tz)(2)BH2}] and [Cu(R3P)(n){(tz)(3)BH}] (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 (H-1 and P-31{H-1}) 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)(2)BH2}] with a four-coordinate CuP2(N-2) coordination sphere, (b) one-dimensional polynuclear [Cu(R3P){(tz)BH2(tz)}]((infinity/infinity))with a four-coordinate CuP(N-3) 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)(3)BH}] with a CuP(N-3) coordination sphere, (d) one-dimensional polynuclear [Cu(R3P)(2){(tz)BH(tz)(tz)}]((infinity/infinity))with a four-coordinate CuP2(N-2) coordination sphere in which one of the ligand tz rings is uncoordinated and the other two bridge through N(4) to successive copper atoms.