Journal of the American Chemical Society p. 5397 - 5403 (1988)
Update date:2022-08-17
Topics:
Stolzenberg, Alan M.
Stershic, Matthew T.
Reactions of NiI(OEiBC)- with alkyl halides were investigated in bulk solution and by electrochemical means.With the exception of factor F430, the Ni hydrocorphinoid prosthetic group of methyl coenzyme M reductase, Ni(OEiBC) is the only tetrapyrrole to date that has been reduced to an isolable nickel(I) complex.NiI(OEiBC)- reacts with CH3I in a 2:1 stoichiometry to afford neutral NiII(OEiBC) in quantitative yield and CH4 and I- in lesser yields.The nickel(I) complex also reacts with methyl p-toluenesulfonate to afford CH4.Ni(OEiBC) mediates electrocatalytic reductions of alkyl halides and of methyl p-toluenesulfonate.Evidence is presented for a transient alkyl-NiIII(OEiBC) intermediate, which is reducible at potentials positive of the NiII/NiI couple.The current/potential curves of the electrocatalytic reductions were analyzed to obtain relative rate constants for a series of alkyl halides.The reactivity trends I > Br > tosyl >/= Cl and CH3 > n-C4H9 > sec-C4H9 > t-C4H9 are consistent with a nucleophilic, Sn2-like mechanism.Estimates of the second-order rate constant for reaction of NiI(OEiBC)- and CH3I suggest that the nucleophilicity of the nickel(I) complex is comparable to that of the "supernucleophile" vitamin B12s.
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