Gold(III) six-membered N^C^N pincer complexes : synthesis, structure, reactivity and theoretical calculations
Articolo
Data di Pubblicazione:
2010
Citazione:
Gold(III) six-membered N^C^N pincer complexes : synthesis, structure, reactivity and theoretical calculations / G. Alesso, M.A. Cinellu, S. Stoccoro, A. Zucca, G. Minghetti, C. Manassero, S. Rizzato, O. Swang, M. Kumer Ghosh. - In: DALTON TRANSACTIONS. - ISSN 1477-9226. - 39:42(2010 Nov), pp. 10293-10304.
Abstract:
The first six-membered gold(III) N^C^N pincer complex was obtained in good yield, under very mild
conditions, by transmetalation of [Hg(kC-NŸCŸN)Cl] (NŸCHŸN = 1,3-bis(pyridin-2-ylmethyl)benzene,
HL1) with Na[AuCl4]. The X-ray crystal structure of [Au(NŸCŸN)Cl][PF6] showed that the fused
six-membered metallacycles each exist in a strongly puckered boat conformation. As shown by the 1H
NMR spectra in various solvents, the same structure is also retained in solution: no inversion of the
six-membered metallacycles is observed in DMSO up to 95 ◦C. This correlates well with a reaction
barrier of 17.5 kcal/mole, as determined by quantum chemical calculations. The reactivity of the
present pincer complex is compared to that of the analogous 1,3-bis(2-pyridyl)benzene, HL2, derivative,
which has five-membered fused metallacycles. Sharp differences are found in the reactions with
phosphines, such as PPh3 and dppe (1,2-bis-diphenylphosphino-ethane), and with silver salts.
Theoretical calculations were carried out on the two pincer complexes in order to try to understand
these differences, and we found that the gold–chlorine bond is significantly stronger in the case of the
complex containing five-membered metallacyclic rings.
Tipologia IRIS:
01 - Articolo su periodico
Elenco autori:
G. Alesso, M.A. Cinellu, S. Stoccoro, A. Zucca, G. Minghetti, C. Manassero, S. Rizzato, O. Swang, M. Kumer Ghosh
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