Abstract
The electrochemical behaviour of hydrides [CoHL4][L = P(OEt)3, PPh(OEt)2, or PPh2(OEt)] in CH2Cl2 and MeCN was examined and the relevant oxidation mechanisms elucidated by cyclic voltammetry and coulometry. Different behaviours were observed depending on the nature both of the solvent and of the phosphite ligands. In CH2Cl2 the stepwise oxidation of CoI to CoIII was observed, involving a first reversible one-electron oxidation step to [CoHL4]+, followed, at more positive potentials, by a second one-electron step, chemically irreversible, for all the phosphite ligands employed. In MeCN, for L = P(OEt)3 or PPh(OEt)2, the first reversible oxidation to cobalt(II) hydrides was followed by a second step complicated by associated chemical reactions involving the solvent to give cobalt(III) cations, [CoH(MeCN)L4]2+. For L = PPh2(OEt) the electrochemical behaviour was complicated by chemical reactions both of the starting cobalt(I) compound and of its oxidation products with the MeCN solvent. Preparative electrolysis allowed the synthesis of a new cobalt(II) derivative characterized as [CoH{P(OEt)3}]BPh4 by spectroscopic techniques.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callMore From: Journal of the Chemical Society, Dalton Transactions
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
