000109394 001__ 109394
000109394 005__ 20230519145447.0
000109394 0247_ $$2doi$$a10.1021/jacs.0c11010
000109394 0248_ $$2sideral$$a122577
000109394 037__ $$aART-2021-122577
000109394 041__ $$aeng
000109394 100__ $$0(orcid)0000-0002-7806-8959$$aVarela-Izquierdo, V.
000109394 245__ $$aRhodium complexes in p-C bond formation: Key role of a hydrido ligand
000109394 260__ $$c2021
000109394 5060_ $$aAccess copy available to the general public$$fUnrestricted
000109394 5203_ $$aOlefin hydrophosphanation is an attractive route for the atom-economical synthesis of functionalized phosphanes. This reaction involves the formation of P-C and H-C bonds. Thus, complexes that contain both hydrido and phosphanido functionalities are of great interest for the development of effective and fast catalysts. Herein, we showcase the excellent activity of one of them, [Rh(Tp)H(PMe3)(PPh2)] (1), in the hydrophosphanation of a wide range of olefins. In addition to the required nucleophilicity of the phosphanido moiety to accomplish the P-C bond formation, the key role of the hydride ligand in 1 has been disclosed by both experimental results and DFT calculations. An additional Rh-H··· C stabilization in some intermediates or transition states favors the hydrogen transfer reaction from rhodium to carbon to form the H-C bond. Further support for our proposal arises from the poor activity exhibited by the related chloride complex [Rh(Tp)Cl(PMe3)(PPh2)] as well as from stoichiometric and kinetic studies.
000109394 536__ $$9info:eu-repo/grantAgreement/ES/AEI-FEDER/CTQ2017-83421-P$$9info:eu-repo/grantAgreement/ES/DGA-FEDER/E08-17R$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/FPI fellowship$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/Jdc contract
000109394 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000109394 590__ $$a16.383$$b2021
000109394 592__ $$a5.728$$b2021
000109394 594__ $$a25.2$$b2021
000109394 591__ $$aCHEMISTRY, MULTIDISCIPLINARY$$b16 / 180 = 0.089$$c2021$$dQ1$$eT1
000109394 593__ $$aBiochemistry$$c2021$$dQ1
000109394 593__ $$aColloid and Surface Chemistry$$c2021$$dQ1
000109394 593__ $$aCatalysis$$c2021$$dQ1
000109394 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000109394 700__ $$0(orcid)0000-0003-1115-6759$$aGeer, A.M.
000109394 700__ $$0(orcid)0000-0002-2549-4487$$aNavarro, J.
000109394 700__ $$0(orcid)0000-0003-4500-1974$$aLopez, J.A.$$uUniversidad de Zaragoza
000109394 700__ $$0(orcid)0000-0002-7188-8014$$aCiriano, M.A.
000109394 700__ $$0(orcid)0000-0003-3306-0635$$aTejel, C.
000109394 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000109394 773__ $$g143, 1 (2021), 349-358$$pJ. Am. Chem. Soc.$$tJournal of the American Chemical Society$$x0002-7863
000109394 8564_ $$s1243394$$uhttps://zaguan.unizar.es/record/109394/files/texto_completo.pdf$$yPostprint
000109394 8564_ $$s2707345$$uhttps://zaguan.unizar.es/record/109394/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000109394 909CO $$ooai:zaguan.unizar.es:109394$$particulos$$pdriver
000109394 951__ $$a2023-05-18-14:39:54
000109394 980__ $$aARTICLE