Abstract
Raman spectroscopy has been used to investigate the previously reported organocyanocobalt complexes which are formed from the reaction of hydridopentacyanocobaltate(III) with 1,3-butadiene. These complexes are postulated intermediates in the Co(CN) 5 3−-catalyzed hydrogenation of butadiene. The Raman spectrum of σ-(2-butenyl)pentacyanocobaltate(III), which is formed in the presence of an excess of CN −, confirms that both cis and trans isomers of this intermediate are present in solution. In the presence of a deficiency of CN −, only one complex, syn-π-(1-methylally)tetracyanocobaltate(III), is formed, and its Raman spectrum is also reported for the first time. When the initial CN/Co ratio is 5.0, both σ- and π-bonded complexes are present in solution, with the σ complex predominating.
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