Syntheses, molecular structures and electrochemical behavior of two isomeric Ru(PhNpy)2(PPh3)2 complexes

Chakravarty, Akhil R. ; Albert Cotton, F. ; Shamshoum, Edwar S. (1984) Syntheses, molecular structures and electrochemical behavior of two isomeric Ru(PhNpy)2(PPh3)2 complexes Inorganica Chimica Acta, 86 (1). pp. 5-11. ISSN 0020-1693

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Official URL: http://linkinghub.elsevier.com/retrieve/pii/S00201...

Related URL: http://dx.doi.org/10.1016/S0020-1693(00)83306-X

Abstract

The title compounds, isomers of Ru(PhNpy)2(PPh3)2 (PhNpy = the anion of 2-(N-anilino)-pyridine), having C1 and C2 symmetry, were prepared by reacting RuCl2(PPh3)3 with LiPhNpy in toluene. The crystal and molecular structures of these compounds have been determined from three-dimensional X-ray study. Both compounds crystallize in the monoclinic space group P21/c with the following unit cell dimensions: C1-isomer: A = 13.852(3), B = 18.872(3), C = 18.206(3), β = 84.32(5), V = 4736(2) and Z = 4. C2-isomer: A = 11.166(9), B = 20.404(8), C = 20.716(16), β = 97.14(7), V = 4683(10) and Z = 4. The structures were refined to R = 0.053 (Rw = 0.083) for the C1-isomer and R = 0.055 (Rw = 0.063) for the C2-isomer. In the C1-isomer, the coordinating atoms N-py, N-Ph and PPH3 are all in cis-arrangement. In the C2-isomer, the py-rings are trans to each other. The complexes are six-coordinate with four-membered chelate rings. The N---Ru---N angle in the chelate rings is ca. 62° in each case. The Ru---P bond lengths lie in the range 2.286(3)-2.337(1) Å. The average Ru---N(py), and Ru---N(Ph) bond lengths are 2.083 Å and 2.171 Å, respectively. Dichloromethane solutions of the C1 and C2 isomers display two quasireversible oxidation waves at 0.480, 1.175 V and 0.290, 1.040 V, respectively. The responses have one-electron stoichiometry and are assignable to RuIII/RuII and RuIV/RuIII couples.

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