Theoretical insights of copper(I)–nitrene complexes

Abstract

Density functional theory has been used to study the geometries and character of the copper–nitrene complexes L n Cu N R ( 1, R = Me; 2, R = CO 2Me; 3, R = SO 2Me; 4, R = SO 2ph). Calculation results confirm that the copper–nitrene nitrogen bonds of the copper–nitrene complexes A2, B2, C2, and D2 (R=CO 2Me) show strong double-bonded character, and thus those of the copper–nitrene complexes A1, A3, A4, B1, B3, B4, C1, C3, C4, D1, D3, D4, E1, E2, E3, E4, F1, F2, F3, and F4 show single-bonded character. The copper–nitrene nitrogen bonds and the copper and nitrogen atoms of the bonds are the reactive center for the copper–nitrene complexes. The geometry, electronic structure, frontier orbitals (HOMO and LUMO), and molecular electrostatic potential (MEP) are discussed in detail.