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> Iridium(i) complexes bearing hemilabile coumarin-functionalised N-heterocyclic carbene ligands with application as alkyne hydrosilylation catalysts
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Iridium(i) complexes bearing hemilabile coumarin-functionalised N-heterocyclic carbene ligands with application as alkyne hydrosilylation catalysts
Karatas M.O.
;
Alici B.
;
Passarelli V.
(Universidad de Zaragoza)
;
Özdemir I.
;
Pérez-Torrente J.J.
(Universidad de Zaragoza)
;
Castarlenas R.
Resumen:
A set of iridium(i) complexes of formula IrCl(¿C, ¿2-IRCouR')(cod) or IrCl(¿C, ¿2-BzIRCouR')(cod) (cod = 1, 5-cyclooctadiene; Cou = coumarin; I = imidazolin-2-carbene; BzI = benzimidazolin-2-carbene) have beeen prepared from the corresponding azolium salt and [Ir(µ-OMe)(cod)]2 in THF at room temperature. The crystalline structures of 4b and 5b show a distorted trigonal bipyramidal configuration in the solid state with a coordinated coumarin moiety. In contrast, an equilibrium between this pentacoordinated structure and the related square planar isomer is observed in solution as a consequence of the hemilability of the pyrone ring. Characterization of both species by NMR was achieved at the low and high temperature limits, respectively. In addition, the thermodynamic parameters of the equilibrium, ¿HR and ¿SR, were obtained by VT 1H NMR spectroscopy and fall in the range 22-33 kJ mol-1 and 72-113 J mol-1 K-1, respectively. Carbonylation of IrCl(¿C, ¿2-BzITolCou7, 8-Me2)(cod) resulted in the formation of a bis-CO derivative showing no hemilabile behaviour. The newly synthesised complexes efficiently catalyze the hydrosilylation of alkynes at room temperature with a preference for the ß-(Z) vinylsilane isomer. © The Royal Society of Chemistry.
Idioma:
Inglés
DOI:
10.1039/d1dt01946e
Año:
2021
Publicado en:
Dalton Transactions
50, 32 (2021), 11206-11215
ISSN:
1477-9226
Factor impacto JCR:
4.569 (2021)
Categ. JCR:
CHEMISTRY, INORGANIC & NUCLEAR
rank: 7 / 46 = 0.152
(2021)
- Q1
- T1
Factor impacto SCIMAGO:
0.864 -
Inorganic Chemistry
(Q1)
Financiación:
info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R
Financiación:
info:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00
Tipo y forma:
Article (PostPrint)
Área (Departamento):
Área Química Inorgánica
(
Dpto. Química Inorgánica
)
Exportado de SIDERAL (2023-06-21-15:03:14)
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Notice créée le 2022-10-27, modifiée le 2023-06-22
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