000119587 001__ 119587
000119587 005__ 20230622083322.0
000119587 0247_ $$2doi$$a10.1039/d1dt01946e
000119587 0248_ $$2sideral$$a125856
000119587 037__ $$aART-2021-125856
000119587 041__ $$aeng
000119587 100__ $$aKaratas M.O.
000119587 245__ $$aIridium(i) complexes bearing hemilabile coumarin-functionalised N-heterocyclic carbene ligands with application as alkyne hydrosilylation catalysts
000119587 260__ $$c2021
000119587 5060_ $$aAccess copy available to the general public$$fUnrestricted
000119587 5203_ $$aA 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.
000119587 536__ $$9info:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00$$9info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R
000119587 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000119587 590__ $$a4.569$$b2021
000119587 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b7 / 46 = 0.152$$c2021$$dQ1$$eT1
000119587 592__ $$a0.864$$b2021
000119587 593__ $$aInorganic Chemistry$$c2021$$dQ1
000119587 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000119587 700__ $$aAlici B.
000119587 700__ $$0(orcid)0000-0002-1735-6439$$aPassarelli V.$$uUniversidad de Zaragoza
000119587 700__ $$aÖzdemir I.
000119587 700__ $$0(orcid)0000-0002-3327-0918$$aPérez-Torrente J.J.$$uUniversidad de Zaragoza
000119587 700__ $$0(orcid)0000-0003-4460-8678$$aCastarlenas R.
000119587 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000119587 773__ $$g50, 32 (2021), 11206-11215$$pDalton Trans.$$tDalton Transactions$$x1477-9226
000119587 8564_ $$s1737611$$uhttps://zaguan.unizar.es/record/119587/files/texto_completo.pdf$$yPostprint
000119587 8564_ $$s2623871$$uhttps://zaguan.unizar.es/record/119587/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000119587 909CO $$ooai:zaguan.unizar.es:119587$$particulos$$pdriver
000119587 951__ $$a2023-06-21-15:03:14
000119587 980__ $$aARTICLE