127754 20241125101127.0 doi 10.1039/D3DT01911J sideral 134968 ART-2023-134968 eng González-Lainez, Miguel (orcid)0000-0001-7341-0033 ß-(Z)-Selective alkyne hydrosilylation by a N,O-functionalized NHC-based rhodium(i) catalyst 2023 Access copy available to the general public Unrestricted Neutral and cationic cyclooctadiene rhodium(I) complexes with a lutidine-derived polydentate ligand having NHC and methoxy side-donor functions, [RhBr(cod)(κC-tBuImCH2PyCH2OMe)] and [Rh(cod)(κ2C,N-tBuImCH2PyCH2OMe)]PF6, have been prepared. Carbonylation of the cationic compound yields the dicarbonyl complex [Rh(CO)2(κ2C,N-tBuImCH2PyCH2OMe)]PF6 whereas carbonylation of the neutral compound affords a mixture of di- and monocarbonyl neutral complexes [RhBr(CO)2(κC-tBuImCH2PyCH2OMe)] and [RhBr(CO)(κ2C,N-tBuImCH2PyCH2OMe)]. These complexes efficiently catalyze the hydrosilylation of 1-hexyne with HSiMe2Ph with a marked selectivity towards the β-(Z)-vinylsilane product. Catalyst [RhBr(CO)(κ2C,N-tBuImCH2PyCH2OMe)] showed a superior catalytic performance, in terms of both activity and selectivity, and has been applied to the hydrosilylation of a range of 1-alkynes and phenylacetylene derivatives with diverse hydrosilanes, including HSiMe2Ph, HSiMePh2, HSiPh3 and HSiEt3, showing excellent β-(Z) selectivity for the hydrosilylation of linear aliphatic 1-alkynes. Hydrosilylation of internal alkynes, such as diphenylacetylene and 1-phenyl-1-propyne, selectively affords the syn-addition vinylsilane products. The β-(Z) selectivity of these catalysts contrasts with that of related rhodium(I) catalysts based on 2-picolyl-functionalised NHC ligands, which were reported to be β-(E) selective. An energy barrier ΔG‡ of 19.8 ± 2.0 kcal mol−1 (298 K) has been determined from kinetic studies on the hydrosilylation of 1-hexyne with HSiMe2Ph. DFT studies suggest that the methoxy-methyl group is unlikely to be involved in the activation of hydrosilane, and then hydrosilane activation is likely to proceed via a classical Si–H oxidative addition. info:eu-repo/grantAgreement/ES/DGA/E42-23R info:eu-repo/grantAgreement/ES/MICINN/PID2019-103965GB-I00/AEI/10.13039/501100011033 info:eu-repo/semantics/openAccess by http://creativecommons.org/licenses/by/3.0/es/ 3.5 2023 CHEMISTRY, INORGANIC & NUCLEAR 13 / 44 = 0.295 2023 Q2 T1 0.697 2023 Inorganic Chemistry 2023 Q1 6.6 2023 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Jiménez, M. Victoria (orcid)0000-0002-0545-9107 Passarelli, Vincenzo (orcid)0000-0002-1735-6439 Pérez-Torrente, Jesús J. Universidad de Zaragoza (orcid)0000-0002-3327-0918 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 52, 33 (2023), 11503-11517 Dalton Trans. Dalton Transactions 1477-9226 1243004 http://zaguan.unizar.es/record/127754/files/texto_completo.pdf Versión publicada 2545461 http://zaguan.unizar.es/record/127754/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:127754 articulos driver 2024-11-22-11:57:53 ARTICLE