Manish Chandra

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

Abstract 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(η6-C10H14)(μ-Cl)Cl}2], [{Ru(η6-C6Me6)(μ-Cl)Cl}2], [RuCl(η5-C5H5)(PPh3)2] and [{Rh(η5-C5Me5)(μ-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)(η6-C10H14)RuCl](PF6)2, [RuH(CO)(PPh3)2(bppz)(η6-C6Me6)Cl2Ru](PF6)2, [RuH(CO)(PPh3)2(bppz)(η5-C5H5)(PPh3)Ru](PF6)2 and [RuH(CO)(PPh3)2(bppz)Rh(η5-C5Me5)Cl](PF6)2 in quantitative yield. The reaction products have been characterized by elemental analyses, IR, 1H-, 1H–1H-COSY, 13C-, 31P-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 η2-coordination of the ligand tptz with the metal center. Crystal data: monoclinic, P21/n, a=17.810(6) A, b=22.233(9) A, c=12.156(4) A, β=90.06(3)°, Z=4, R=0.078.

Synthetic, spectral and structural aspects of some Rh(III) pentamethylcyclopentadiene complexes containing N,N′-donor bridging ligands

Abstract Reactions of the chloro-bridged dimeric rhodium complex [{(η5-C5Me5)Rh(μ-Cl)Cl}2] with the N,N′-donor bridging ligands pyridine-2-carbaldehyde azine (paa), p-phenylene-bis(picoline)aldamine (pbp) or p-biphenylene-bis(picoline)aldamine (bbp) in 1:1 molar ratio in methanol led in the formation of cationic binuclear complexes [(η5-C5Me5)ClRh(μ-L)RhCl(η5-C5Me5)]2+ (L=paa, pbp or bbp) in high yield. It was further observed that reactions of the chloro-bridged dimeric rhodium complex [{(η5-C5Me5)Rh(μ-Cl)Cl}2], with an excess of the above mentioned ligands also, resulted in binuclear complexes. The reaction products have been characterized by microanalyses and spectroscopic studies (IR, 1H-, 13C-NMR, ESMS/FAB mass and electronic spectra). Molecular structure of the representative binuclear complex [(η5-C5Me5)ClRh(μ-paa)RhCl(η5-C5Me5)](BF4)2 has been confirmed by single crystal X-ray analysis. Crystal data: monoclinic, P21/n, a=10.2050(7), b=15.4470(7), c=24.959(2) A, β=97.904(6)°, V=3897.1(5) A3, Z=4, R=0.0609.