Reactivity of Cu(I) Nacnac Complexes Toward Polypnictogen Compounds

The nacnac Cu(I) compound [LCu(MeCN)] (2) (L = [{N(C6H3Me2-2,6)C(Me)}2CH]-) was reacted with complexes containing aromatic cyclo-E5 ([Cp*Fe(eta5-E5)], E = P (1a), As (1b), Cp* = eta5-C5Me5), cyclo-P4 ([Cp‴Co(eta4-P4)] (3), Cp‴ = eta5-C5H2tBu3) and cyclo-E3 ligands ([Cp‴Ni(eta3-E3)], E = P (4a), As (4b)) yielding the heterometallic complexes [(Cp*Fe)(mu,eta5:2-E5)(LCu)] (E = P (5a), As (5b)), [(Cp*Fe)(mu3,eta5:2:1-E5)(LCu)2] (E = P (6a), As (6b)), [(Cp‴Co)(mu,eta4:2-P4)(LCu)] (7), [(Cp‴Co)(mu3,eta4:2:1-P4)(LCu)2] (8), and [(Cp‴Ni)(mu,eta3:2-E3)(LCu)] (E = P (9a), As (9b)). These complexes are rare examples of the coordination of a group 11 metal to aromatic cyclo-En (E = P, As; n = 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.