000120082 001__ 120082
000120082 005__ 20240319081018.0
000120082 0247_ $$2doi$$a10.1021/acs.organomet.2c00375
000120082 0248_ $$2sideral$$a130767
000120082 037__ $$aART-2022-130767
000120082 041__ $$aeng
000120082 100__ $$aAndrés, José L.
000120082 245__ $$aMechanistic versatility at Ir(PSiP) pincer catalysts: triflate proton shuttling from 2-Butyne to Diene and [3]Dendralene motifs
000120082 260__ $$c2022
000120082 5060_ $$aAccess copy available to the general public$$fUnrestricted
000120082 5203_ $$aThe five-coordinate hydrido complex [IrH(OTf)(PSiP)] (1) catalytically transforms 2-butyne into a mixture of its isomer 1,3-butadiene, and [3]dendralene and linear hexatriene dimerization products: (E)-4-methyl-3-methylene-1,4-hexadiene and (3Z)-3,4-dimethyl-1,3,5-hexatriene, respectively. Under the conditions of the catalytic reaction, benzene, and 363 K, the hexatriene further undergoes thermal electrocyclization into 2,3-dimethyl-1,3-cyclohexadiene. The reactions between 1 and the alkyne substrate allow isolation or nuclear magnetic resonance (NMR) observation of catalyst resting states and possible reaction intermediates, including complexes with the former PSiP pincer ligands disassembled into PSi and PC chelates, and species coordinating allyl or carbene fragments en route to products. The density functional theory (DFT) calculations guided by these experimental observations disclose competing mechanisms for C–H bond elaboration that move H atoms either classically, as hydrides, or as protons transported by the triflate. This latter role of triflate, previously recognized only for more basic anions such as carboxylates, is discussed to result from combining the unfavorable charge separation in the nonpolar solvent and the low electronic demand from the metal to the anion at coordination positions trans to silicon. Triflate deprotonation of methyl groups is key to release highly coordinating diene products from stable allyl intermediates, thus enabling catalytic cycling.
000120082 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E50-20D$$9info:eu-repo/grantAgreement/ES/MINECO/BES-2013-063359$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2012-31774
000120082 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000120082 590__ $$a2.8$$b2022
000120082 592__ $$a0.868$$b2022
000120082 591__ $$aCHEMISTRY, ORGANIC$$b16 / 52 = 0.308$$c2022$$dQ2$$eT1
000120082 593__ $$aInorganic Chemistry$$c2022$$dQ1
000120082 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b16 / 42 = 0.381$$c2022$$dQ2$$eT2
000120082 593__ $$aPhysical and Theoretical Chemistry$$c2022$$dQ1
000120082 593__ $$aOrganic Chemistry$$c2022$$dQ1
000120082 594__ $$a6.6$$b2022
000120082 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000120082 700__ $$0(orcid)0000-0003-3697-4168$$aSuárez, Elizabeth
000120082 700__ $$0(orcid)0000-0001-7819-670X$$aMartín, Marta
000120082 700__ $$0(orcid)0000-0001-5462-6189$$aSola, Eduardo
000120082 773__ $$g41, 18 (2022), 2622-2630$$pOrganometallics$$tOrganometallics$$x0276-7333
000120082 8564_ $$s3963347$$uhttps://zaguan.unizar.es/record/120082/files/texto_completo.pdf$$yVersión publicada
000120082 8564_ $$s2935050$$uhttps://zaguan.unizar.es/record/120082/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000120082 909CO $$ooai:zaguan.unizar.es:120082$$particulos$$pdriver
000120082 951__ $$a2024-03-18-15:53:29
000120082 980__ $$aARTICLE