Reactivity of Cu(I) Nacnac Complexes Toward Polypnictogen Compounds.

The nacnac Cu(I) compound [LCu(MeCN)] () (L = [{N(CHMe-2,6)C(Me)}CH]) was reacted with complexes containing aromatic -E ([CpFe(η-E)], E = P (), As (), Cp = η-CMe), -P ([Cp‴Co(η-P)] (), Cp‴ = η-CHBu) and -E ligands ([Cp‴Ni(η-E)], E = P (), As ()) yielding the heterometallic complexes [(CpFe)(μ,η-E)(LCu)] (E = P (), As ()), [(CpFe)(μ,η-E)(LCu)] (E = P (), As ()), [(Cp‴Co)(μ,η-P)(LCu)] (), [(Cp‴Co)(μ,η-P)(LCu)] (), and [(Cp‴Ni)(μ,η-E)(LCu)] (E = P (), As ()). These complexes are rare examples of the coordination of a group 11 metal to aromatic -E (E = P, As; = 3-5) ligands. All products were comprehensively characterized by crystallographic and spectroscopic methods. Their dynamic behavior in solution was studied by VT (variable-temperature) NMR spectroscopy, and their electronic structures were elucidated by DFT calculations.