Generation and tunable cyclization of formamidinate ligands in carbonyl complexes of Mn(I): An experimental and theoretical study

A subtle change in the substituents at the nitrogen atoms in the N,N′-diarylformamidine complexes of formula fac-[Mn(RN═C(H)NHR)(bipy)(CO)3]+ (1a, R = phenyl; 1b, R = 4-dimethylaminophenyl) produces, upon deprotonation, either the monodentate formamidinate complex fac-[Mn(PhN═C(H)NPh)(bipy)(CO)3] (2a) or metallacylic complex 3b, which features a carbamoyl residue arising from nucleophilic attack to a vicinal carbonyl ligand. Complexes type 3 are also formed when using N-aryl-N′-alkyl-formamidines as well as N,N′-dialkylformamidines. Quantum Theory of Atoms in Molecules computations show the existence of a weak bond critical point of mainly noncovalent electrostatic type between the uncoordinated nitrogen atom of the formamidinate and a carbonyl ligand in 2a, which appears to be an isolable intermediate species that precedes the formation of metallacyclic complexes 3.This work was supported by the Spanish Ministerio de Economía y Competitividad (Projects CTQ2015-66959-P and MAT2016-78155-C2-1-R) and the Principado de Asturias grant GRUP-IN-14-060. D.S. thanks the Principado de Asturias for a scholarship