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Kinetic and electrochemical study of nitrile adducts of tetrachloro-bis(1,2-bis(diphenylphosphine)methane)dirhenium(II)

✍ Scribed by Grant N. Holder; Tonia A. Leach; Cassandra T. Eagle; Lawrence A Bottomley

Publisher: Springer
Year: 1995
Tongue: English
Weight: 404 KB
Volume: 20
Category: Article
ISSN: 0340-4285
DOI: 10.1007/bf00139143

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✦ Synopsis

The addition of two nitrile ligands to the complex Re2C14-(dppm)2 (dppm = 1,2-bis(diphenylphosphine)methane) in CH2C12 solution has been investigated electrochemically. Upon addition of one equivalent of nitrile NCR (R = aromatic or aliphatic group) to the CHzC1E/0.1M tetra-Nbutylammonium hexafluorophosphate (TBAH) solution, RezC14(dppm)2(NCR ) is formed immediately, without dissociation of chloride; electrochemical investi-gation indicates this nitrile addition is reversible upon oxidation of the dirhenium complex. On addition of two or more equivalents of nitrile, a slow ligand substitution takes place with addition of a second nitrile and concomitant loss of a chloride ion to form [RezC13-(dppm)z(NCR)2]+. The rate of addition of nitrile to RezC14(dppm)z(NCR ) appears to depend on the electrondonating or electron-withdrawing abilities of the ligand. The change from monoadduct to diadduct was followed with differential pulse voltammetry for various concentrations of added nitrile. The addition was found to be first order in nitrile.

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