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Mosher PJ, Yap GP, Crutchley RJ. A donor--acceptor--donor bridging ligand in a class III mixed-valence complex. Inorg Chem. 2001;40(6):1189-95doi: 10.1021/ic001268u.
Mosher, P. J., Yap, G. P., & Crutchley, R. J. (2001). A donor--acceptor--donor bridging ligand in a class III mixed-valence complex. Inorganic chemistry, 40(6), 1189-95. https://doi.org/10.1021/ic001268u
Mosher, P J, et al. "A donor--acceptor--donor bridging ligand in a class III mixed-valence complex." Inorganic chemistry vol. 40,6 (2001): 1189-95. doi: https://doi.org/10.1021/ic001268u
Mosher PJ, Yap GP, Crutchley RJ. A donor--acceptor--donor bridging ligand in a class III mixed-valence complex. Inorg Chem. 2001 Mar 12;40(6):1189-95. doi: 10.1021/ic001268u. PMID: 11300817.
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Inorg Chem. 2001 Mar 12;40(6):1189-95. doi: 10.1021/ic001268u.

A donor--acceptor--donor bridging ligand in a class III mixed-valence complex.

Inorganic chemistry

P J Mosher, G P Yap, R J Crutchley

Affiliations

  1. Ottawa-Carleton Chemistry Institute, Carleton University, Ontario, Canada K1S 5B6.

PMID: 11300817 DOI: 10.1021/ic001268u

Abstract

The novel mononuclear and dinuclear complexes [Ru(trpy)(bpy)(apc)][PF(6)] and [(Ru(trpy)(bpy))(2)(mu-adpc)][PF(6)](2) (bpy = 2,2'-bipyridine, trpy = 2,2':6',2' '-terpyridine, apc(-) = 4-azo(phenylcyanamido)benzene, and adpc(2)(-) = 4,4'-azodi(phenylcyanamido)) were synthesized and characterized by (1)H NMR, UV-vis, and cyclic voltammetry. Crystallography showed that the dinuclear Ru(II) complex crystallizes from diethyl ether/acetonitrile solution as [(Ru(trpy)(bpy))(2)(mu-adpc)][PF(6)](2).2(acetonitrile).2(diethyl ether). Crystal structure data are as follows: crystal system triclinic, space group P1, with a, b, and c = 12.480(2), 13.090(3) and 14.147(3) A, respectively, alpha, beta, and gamma = 79.792(3), 68.027(3), and 64.447(3) degrees, respectively, V = 1933.3(6) A(3), and Z = 1. The structure was refined to a final R factor of 0.0421. The mixed-valence complex with metal ions, separated by a through-space distance of 19.5 A, is a class III system, having the comproportionation constant K(c) = 1.3 x 10(13) and an intervalence band at 1920 nm (epsilon(max) = 10 000 M(-1) cm(-1)), in dimethylformamide solution. The results of this study strongly suggest that the bridging ligand adpc(2-) can mediate metal-metal coupling through both hole-transfer and electron-transfer superexchange mechanisms.

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