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Trapping of an NiII Sulfide by a CoI Fulvene Complex

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journal contribution
posted on 20.04.2017, 18:33 by Nathaniel J. Hartmann, Guang Wu, Trevor W. Hayton
The reaction of [LtBuNiII(SCPh3)] (LtBu = {(2,6-iPr2C6H3)­NC­(tBu)}2CH) with Cp*2Co yields a NiI cobaltocenium thiolate complex, [LtBuNiI(SCH2Me4C5)­Co­(Cp*)] (1), along with HCPh3. Formation of this complex is proposed to occur via the reaction of a transient NiII sulfide, [Cp*2Co]­[LtBuNiII(S)], with a CoI fulvene complex, [CoCp*­(C5Me4CH2)]. The latter complex is formed in situ by reaction of [Cp*2Co]+ with [CPh3]. Control experiments, as well as cyclic voltammetry measurements of 1, are used to support the proposed mechanism.