Reactivity of Cu(I) Nacnac Complexes Toward Polypnictogen Compounds

The nacnac Cu(I) compound [LCu(MeCN)] (2) (L = [{N(C6H3Me2-2,6)C(Me)}(2)CH](-)) was reacted with complexes containing aromatic cyclo-E-5 ([Cp*Fe(eta(5)-E-5)], E = P (1a), As (1b), Cp* = eta(5)-C5Me5), cyclo-P-4 ([Cp'''Co(eta(4)-P-4)] (3), Cp''' = eta(5)-(C5H2Bu3)-Bu-t) and cyclo-E-3 ligands ([Cp'''Ni(eta(3)-E-3)], E = P (4a), As (4b)) yielding the heterometallic complexes [(Cp*Fe)(mu,eta(5:2)-E-5)(LCu)] (E = P (5a), As (5b)), [(Cp*Fe)(mu(3),eta(5:2:1)-E-5)(LCu)(2)] (E = P (6a), As (6b)), [(Cp'''Co)(mu,eta(4:2)-P-4)(LCu)] (7), [(Cp'''Co)(mu(3),eta(4:2:1)-P-4)(LCu)(2)] (8), and [(Cp'''Ni)(mu,eta(3:2)-E-3)(LCu)] (E = P (9a), As (9b)). These complexes are rare examples of the coordination of a group 11 metal to aromatic cyclo-E-n (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.

Automated summary

The article investigates the reaction of nacnac Cu(I) compound with complexes containing aromatic cyclo-E-n ligands, resulting in the formation of various heterometallic complexes. These complexes were characterized comprehensively and their dynamic behavior in solution was studied using VT NMR spectroscopy, with electronic structures elucidated by DFT calculations.