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Title

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

AuthorsRuiz, Javier ; Sol, Daniel; García, Lucía; Mateo, María A.; Vivanco, Marilín; Maelen, Juan F. van der
Issue Date2019
PublisherAmerican Chemical Society
CitationOrganometallics 38(4): 916-925 (2019)
AbstractA 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.
Publisher version (URL)https://doi.org/10.1021/acs.organomet.8b00898
URIhttp://hdl.handle.net/10261/210828
Identifiersdoi: 10.1021/acs.organomet.8b00898
e-issn: 1520-6041
issn: 0276-7333
Appears in Collections:(CINN) Artículos
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