The formation of pentacyanohydridorhodate(III): kinetic and spectral evidence for the oxidative addition of hydrogen cyanide to the intermediate tetracyanorhodate(I)
- 1 January 1972
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 19,p. 2089-2094
- https://doi.org/10.1039/dt9720002089
Abstract
In the reaction of NaCN with [Rh(CO)2Cl]2 evidence has been found for the formation of a transient intermediate which is probably Rh(CN)4 3–; the u.v.–visible spectrum of the intermediate is reported. The decay of the intermediate, studied by the stopped-flow method, has been identified as the oxidative addition of HCN to Rh(CN)4 3– to form Rh(CN)5H3–; the pH dependence and isotope effect of D2O on the rate constant have been examined. The oxidative addition of alkyl halides to Rh(CN)4 3–, Rh(CN)3CO2–, and Rh(CN)2(CO)2 – is reported and the mechanism of formation of acyl rhodium(III) compounds Rh(CN)5(COCH3)3– is discussed.Keywords
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