000099793 001__ 99793
000099793 005__ 20230519145413.0
000099793 0247_ $$2doi$$a10.1139/cjc-2020-0061
000099793 0248_ $$2sideral$$a123358
000099793 037__ $$aART-2021-123358
000099793 041__ $$aeng
000099793 100__ $$aCurto, S.G.
000099793 245__ $$aReactions of pop-pincer rhodium(I)-aryl complexes with small molecules: Coordination flexibility of the ether diphosphine
000099793 260__ $$c2021
000099793 5060_ $$aAccess copy available to the general public$$fUnrestricted
000099793 5203_ $$aReactions of the aryl complexes Rh(aryl){3-P, O, P-[xant(PiPr2)2]} (1; aryl = 3, 5-Me2C6H3 (a), C6H5 (b), 3, 5-Cl2C6H3 (c), 3-FC6H4 (d); xant(PiPr2)2 = 9, 9-dimethyl-4, 5-bis-(diisopropylphosphino)xanthene) with O2, CO, and MeO2CC''CCO2Me have been performed. Under 1 atm of O2, the pentane solutions of complexes 1 afford the dinuclear peroxide derivatives [Rh(aryl){2-P, P-xant(PiPr2)2}]2(-O2)2 (2a–2d) as yellow solids. In solution, these species are unstable. In dichloromethane, at room temperature, they are transformed into the dioxygen adducts Rh(aryl)(2-O2){3-P, O, P-[xant(PiPr2)2]} (3a–3d), as a result of the rupture of the double peroxide bridge and the reduction of the metal center. Complex 3b decomposes in benzene, at 50 °C, to give diphosphine oxide, phenol, and biphenyl. Complexes 1 react with CO to give the square-planar mono carbonyl derivatives Rh(aryl)(CO){2-P, P-[xant(PiPr2)2]} (4a–4d), which under carbon monoxide atmosphere evolve to benzoyl species Rh{C(O)aryl}(CO){2-P, P-[xant(PiPr2)2]} (5a–5d), resulting from the migratory insertion of CO into the Rh-aryl bond and the coordination of a second CO molecule. The transformation is reversible; under vacuum, complexes 5 regenerate the precursors 4. The addition of the activated alkyne to complexes 1b and 1d initially leads to the alkyne intermediates Rh(aryl){2-C(CO2Me)''C(CO2Me)}{3-P, O, P-[xant(PiPr2)2]} (6b, 6d), which evolve to the alkenyl derivatives Rh{(E)-C(CO2Me)=C(CO2Me)aryl}{3-P, O, P-[xant(PiPr2)2]} (7b, 7d). The diphosphine adapts its coordination mode to the stability requirements of the different complexes, coordinating cis-2-P, P in complexes 2, fac-3-P, O, P in compounds 3, trans-2-P, P in the mono carbonyl derivatives 4 and 5, and mer-3-P, O, P in products 6 and 7.
000099793 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E06-17R$$9info:eu-repo/grantAgreement/ES/DGA/LMP148-18$$9info:eu-repo/grantAgreement/ES/MECD/FPU17-04813$$9info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/CTQ2017-82935-P
000099793 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000099793 590__ $$a1.051$$b2021
000099793 592__ $$a0.253$$b2021
000099793 594__ $$a1.9$$b2021
000099793 591__ $$aCHEMISTRY, MULTIDISCIPLINARY$$b155 / 180 = 0.861$$c2021$$dQ4$$eT3
000099793 593__ $$aChemistry (miscellaneous)$$c2021$$dQ3
000099793 593__ $$aCatalysis$$c2021$$dQ3
000099793 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000099793 700__ $$0(orcid)0000-0001-9491-7167$$ade las Heras, L.A.
000099793 700__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, M.A.
000099793 700__ $$0(orcid)0000-0003-0381-0917$$aOliván, M.
000099793 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, E.
000099793 700__ $$0(orcid)0000-0003-1974-5507$$aVélez, A.$$uUniversidad de Zaragoza
000099793 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000099793 773__ $$g99, 2 (2021), 127-136$$pCan. j. chem.$$tCANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE$$x0008-4042
000099793 8564_ $$s371478$$uhttps://zaguan.unizar.es/record/99793/files/texto_completo.pdf$$yPostprint
000099793 8564_ $$s672983$$uhttps://zaguan.unizar.es/record/99793/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000099793 909CO $$ooai:zaguan.unizar.es:99793$$particulos$$pdriver
000099793 951__ $$a2023-05-18-13:57:00
000099793 980__ $$aARTICLE