Bio-catalysts and catalysts based on ruthenium(II) polypyridyl complexes imparting diphenyl-(2-pyridyl)-phosphine as a co-ligand

Reactions of the ruthenium complexes [Ru(kappa(3)-tpy)(PPh3)Cl-2], [Ru(kappa(3)-tptz)(PPh3)Cl-2] and [Ru(kappa(3)-tpy)Cl-3] [tpy = 2,2 ':6 ',2 ''-terpyridine; tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine] with diphenyl-(2-pyridyl)-phosphine (PPh2Py) have been investigated. The complexes [Ru(kappa(3)-tpy)(PPh3)Cl-2] and [Ru(kappa(3)-tptz)(PPh3)Cl-2] reacted with PPh2Py to afford [Ru(kappa(3)-tpy)(kappa(1)-P-PPh2Py)(2)Cl](+) (1) and [Ru(kappa(3)-tptz)(kappa(1)-P-PPh2Py)(2)Cl](+) (2), which were isolated as their tetrafluoroborate salts. Under analogous conditions, [Ru(kappa(3)-tpy)Cl-3] gave a neutral complex [Ru(kappa(3)-tpy)(kappa(1)-PPh2Py)Cl-2] (3). Upon treatment with an excess of NH4PF6 in methanol, 1 and 2 gave [Ru(kappa(3)-tpy)(kappa(1)-P-PPh2Py)(kappa(2)-P,N-PPh2Py)](PF6)(2) (4) and [Ru(kappa(3)-tptz)(kappa(1)-P-PPh2Py)(kappa(2)-P,N-PPh2Py)](PF6)(2) (5) containing both monodentate and chelated PPh2Py. Further, 4 and 5 reacted with an excess of NaCN and CH3CN to afford [Ru(kappa(3)-tpy)(kappa(1)-P-PPh2Py)(2)(CN)](PF6) (6), [Ru(kappa(3)-tpy)(kappa(1)-P-PPh2Py)(2)(NCCH3)](PF6)(2) (7), [Ru(kappa(3)-tptz)(kappa(1)-P-PPh2Py)(2)(CN)]PF6 (8) and [Ru(kappa(3)-tptz)(kappa(1)-P-PPh2Py)(2)(NCCH3)](PF6)(2) (9) supporting hemi labile nature of the coordinated PPh2Py. The complexes have been characterized by elemental analyses, spectral (IR, NMR, electronic absorption, FAB-MS), electrochemical studies and structures of 1, 2 and 3 determined by X-ray single crystal analyses. At higher concentration level (40 mu M) the complexes under investigation exhibit inhibitory activity against DNA-Topo II of the filarial parasite S. cervi and 3 catalyses rearrangement of aldoximes to amide under aerobic conditions. (C) 2011 Elsevier B. V. All rights reserved.