99793 20230519145413.0 doi 10.1139/cjc-2020-0061 sideral 123358 ART-2021-123358 eng Curto, S.G. Reactions of pop-pincer rhodium(I)-aryl complexes with small molecules: Coordination flexibility of the ether diphosphine 2021 Access copy available to the general public Unrestricted Reactions 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. info:eu-repo/grantAgreement/ES/DGA/E06-17R info:eu-repo/grantAgreement/ES/DGA/LMP148-18 info:eu-repo/grantAgreement/ES/MECD/FPU17-04813 info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/CTQ2017-82935-P info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 1.051 2021 CHEMISTRY, MULTIDISCIPLINARY 155 / 180 = 0.861 2021 Q4 T3 0.253 2021 Chemistry (miscellaneous) 2021 Q3 Catalysis 2021 Q3 1.9 2021 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion de las Heras, L.A. (orcid)0000-0001-9491-7167 Esteruelas, M.A. (orcid)0000-0002-4829-7590 Oliván, M. (orcid)0000-0003-0381-0917 Oñate, E. (orcid)0000-0003-2094-719X Vélez, A. Universidad de Zaragoza (orcid)0000-0003-1974-5507 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 99, 2 (2021), 127-136 Can. j. chem. CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE 0008-4042 371478 http://zaguan.unizar.es/record/99793/files/texto_completo.pdf Postprint 672983 http://zaguan.unizar.es/record/99793/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:99793 articulos driver 2023-05-18-13:57:00 ARTICLE