Synthetic, spectral and structural aspects of some mono- and binuclear (homo/hetero) Ru(II) hydrido carbonyl complexes

Reactions of the poly-pyridyl bridging ligand 2,4,6-tris(2-pyridyl)-1,3,5-triazine; 2,3-bis(2-pyridyl)-pyrazine and 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (referred hereafter as tptz, bppz and bptz respectively) with [RuH(CO)Cl(PPh3)(3)] in methanol, gave highly stable cationic complexes with the formulation [RuH(CO)(PPh3)(2)(L)](+). Further, the mononuclear complex [RuH(CO)(PPh3)(2)(bppz)]PF6 reacted with K2PtCl4, [PdCl2(benzonitrile)(2)], [{Ru(eta(6)-C10H14)(mu-Cl)Cl}(2)], [{Ru(eta(6)-C6Me6)(mu-Cl)Cl}(2)] [RuCl(eta(5)-C5H5)(PPh3)(2)] and [{Rh(eta(5)-C5Me5)(mu-Cl)Cl}(2)] in methanol under refluxing conditions to give bppz bridged binuclear complexes with the formulation [RuH(CO)(PPh3)(2)(bppz)PtCl2]PF6, [RuH(CO)(PPh3)(2)(bppz)PdCl2]PF6, [RuH(CO)(PPh3)(2)(bppz)(eta(6)-C10H14)RuCl](PF6)(2), [RuH(CO)(PPh3)(2)(bppz)(eta(6)-C6Me6)Cl2Ru](PF6)(2), [RuH(CO)(PPh3)(2)(bppz)(eta(5)-C5H5)(PPh3)Ru](PF6)(2) and [RuH(CO)(PPh3)(2)(bppz)Rh(eta(5)-C5Me5)Cl](PF6)(2) in quantitative yield. The reaction products have been characterized by elemental analyses, R-1, H-1-, H-1-H-1-COSY, C-13-, P-31-NMR, ESMS, FAB mass spectroscopy, electronic spectra and cyclic voltammetry. Molecular structure of the representative mononuclear complex [RuH(CO)(PPh3)(2)(tptz)]BF4 has been confirmed by X-ray crystallography. Crystal structure determination revealed eta(2)-coordination of the ligand tptz with the metal center. Crystal data: monoclinic, P2(1)/n, a = 17.810(6) Angstrom, b = 22.233(9) Angstrom, c = 12.156(4) Angstrom, beta = 90.06(3)degrees, Z = 4, R = 0.078. (C) 2002 Elsevier Science B.V. All rights reserved.