Generation and tunable cyclization of formamidinate ligands in carbonyl complexes of Mn(I): An experimental and theoretical study
| Autor: | Javier Ruiz, María A. Mateo, Juan F. Van der Maelen, Daniel Sol, Marilín Vivanco, Lucía García |
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| Přispěvatelé: | Ministerio de Economía y Competitividad (España), Principado de Asturias |
| Rok vydání: | 2019 |
| Předmět: |
Denticity
010405 organic chemistry Chemistry Ligand Organic Chemistry Atoms in molecules 010402 general chemistry 01 natural sciences 0104 chemical sciences Inorganic Chemistry Residue (chemistry) Crystallography Deprotonation Nucleophile Critical point (thermodynamics) Physical and Theoretical Chemistry Vicinal |
| Zdroj: | Digital.CSIC. Repositorio Institucional del CSIC instname |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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