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Título: | Generation and tunable cyclization of formamidinate ligands in carbonyl complexes of Mn(I): An experimental and theoretical study |
Autor: | Ruiz, Javier CSIC ORCID; Sol, Daniel CSIC ORCID; García, Lucía; Mateo, María A.; Vivanco, Marilín; Maelen, Juan F. van der CSIC ORCID | Fecha de publicación: | 2019 | Editor: | American Chemical Society | Citación: | Organometallics 38(4): 916-925 (2019) | Resumen: | 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. | Versión del editor: | https://doi.org/10.1021/acs.organomet.8b00898 | URI: | http://hdl.handle.net/10261/210828 | DOI: | 10.1021/acs.organomet.8b00898 | Identificadores: | doi: 10.1021/acs.organomet.8b00898 e-issn: 1520-6041 issn: 0276-7333 |
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