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Title

Regiochemistry control by bipyridine substituents in the deprotonation of reI and MoII N-alkylimidazole complexes

AuthorsEspinal Viguri, Maialen; Fombona, Sergio; Álvarez, Daniel; Díaz, Jesús; Menéndez, M. Isabel; López, Ramón; Pérez, Julio ; Riera, Lucía
KeywordsCarbene ligands
Molybdenum
Substituent effects
Rhenium
Issue Date2019
PublisherWiley-VCH
CitationChemistry - A European Journal 25(39): 9253-9265 (2019)
AbstractCompounds containing N-alkylimidazoles (N-RIm) and 4,4'-disubstituted 2,2'-bipyridines (4,4'-R'2 bipy) coordinated to cationic {Mo(η3 -C4 H7 )(CO)2 } and {Re(CO)3 } fragments undergo deprotonation of the C2-H group of the N-RIm ligands in their reactions with KN(SiMe3 )2 . The resulting internal nucleophile adds either to one pyridyl ring, which becomes dearomatized and can undergo ring opening in the subsequent reaction with excess MeOTf, or to the metal center, yielding imidazol-2-yl complexes, which in turn add HOTf or MeOTf, affording N-heterocyclic carbene complexes. Which pathway is followed is dictated by the metal and the nature of the imidazole (R) and bipyridine (R') substituents. For ReI compounds, addition to pyridine is found with R'=tBu and OMe, whereas for R=Me and R'=NMe2 , imidazolyl formation is preferred. Coordination of 4,7-Cl2 -1,10-phenanthroline to MoII favors C-C coupling, in contrast to the analogous parent bipy or phenanthroline complexes, for which formation of the imidazol-2-yl complexes had been found. DFT calculations showed the theoretically expected products in each case, and following their predictions new types of products were obtained experimentally.
Publisher version (URL)https://doi.org/10.1002/chem.201901060
URIhttp://hdl.handle.net/10261/201848
DOI10.1002/chem.201901060
ISSN0947-6539
E-ISSN1521-3765
Appears in Collections:(CINN) Artículos
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