Welcome to LookChem.com Sign In|Join Free

Article Doi

From to : Synthesis of Mixed Halide-Nitrile Complexes of Ruthenium, and Their Spectroelectrochemical Characterization in Multiple Oxidation States

DOI: 10.1039/DT9910002401

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2401 - 2412 (1991)

Update date:2022-08-05

Topics:

Authors:

Duff, Colleen M.Duff, Colleen M.

Heath, Graham A.Heath, Graham A.

Read Full Text PDF DownLoad Join now for total 90,000,000 free articles

Article abstract of DOI:10.1039/DT9910002401

A complete series of benzonitrile- and acetonitrile-substituted ruthenium halide complexes z (n = 0-6), ranging stepwise from 2- to 2+, has been prepared and characterized.Three series were established, having RCN/X = PhCN/Cl, PhCN/Br, and MeCN/Cl.The strategy of reductive substitution has been developed to prepare 2-, trans--, mer- and trans- in turn from 2- by systematic electrosynthetic routes, through detailed management of potential, temperature and RCN concentration.The monosubstituted pentahalogeno complexes are unstable and their preparation is only practicable via electrode-induced (RuIV -> RuIII) halide displacement from 2- at low temperature.At the divalent leve, exhaustive substitution to form + and 2+ from required more forcing chemical conditions (Ag+ and CF3SO3H respectively).Voltammetric studies between -65 and 20 deg C confirm that the family of mixed halide-nitrile monomeric complexes is rich in redox chemistry, spanning oxidation states V to II.Under reversible conditions, the various metal-based electrode potentials for z are a linear function of the stoichiometry parameter, n, increasing by 0.45 (RuV-RuIV) or 0.6 V (RuIV-RuIII and RuIII-RuII) per halide replaced by nitrile.By use of spectroelectrogeneration techniques, the optical charge-transfer spectra for every available member of each family have been recorded in multiple oxidation levels, defining the states RuIV for n = 0-2, RuIII for n = 0-5 and RuII for n = 2-6.For the present complexes, there are unmistakable complementary progressions in the halide-to-metal (X -> RuIII) and metal-to-ligand (RuII -> RCN) bands, in accord with the underlying trend in E1/2(RuIII-RuII).These measurements present an unusual opportunity to document and analyse the characteristic trends in appearence and location of both ligand-to-metal (RuIII) and metal-to-ligand (RuII) charge-transfer manifolds as a function of stoichiometry.

View More

Products guided by the article

Product name:mer-{RuBr3(C6H5CN)3}

Cas No:133932-90-8

133932-90-8

R&D Labs maybe for 133932-90-8

Relevant to this article

Hot Product