Mechanistic versatility at Ir(PSiP) pincer catalysts: triflate proton shuttling from 2-Butyne to Diene and [3]Dendralene motifs

Andrés, José L. ; Suárez, Elizabeth ; Martín, Marta ; Sola, Eduardo

Resumen: The 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.

Idioma: Inglés

DOI: 10.1021/acs.organomet.2c00375

Año: 2022

Publicado en: Organometallics 41, 18 (2022), 2622-2630
ISSN: 0276-7333

Factor impacto JCR: 2.8 (2022)

Categ. JCR: CHEMISTRY, ORGANIC rank: 16 / 52 = 0.308 (2022) - Q2 - T1
Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 16 / 42 = 0.381 (2022) - Q2 - T2

Factor impacto CITESCORE: 6.6 - Chemistry (Q1)

Factor impacto SCIMAGO: 0.868 - Inorganic Chemistry (Q1) - Physical and Theoretical Chemistry (Q1) - Organic Chemistry (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA/E50-20D
Financiación: info:eu-repo/grantAgreement/ES/MINECO/BES-2013-063359
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2012-31774

Tipo y forma: Artículo (Versión definitiva)