000064316 001__ 64316
000064316 005__ 20200221144234.0
000064316 0247_ $$2doi$$a10.1039/c6dt03010f
000064316 0248_ $$2sideral$$a102703
000064316 037__ $$aART-2016-102703
000064316 041__ $$aeng
000064316 100__ $$aIturmendi, Amaia$$uUniversidad de Zaragoza
000064316 245__ $$aDimethylphosphinate bridged binuclear Rh(i) catalysts for the alkoxycarbonylation of aromatic C-H bonds
000064316 260__ $$c2016
000064316 5060_ $$aAccess copy available to the general public$$fUnrestricted
000064316 5203_ $$aA variety of binuclear rhodium(I) complexes featuring two bridging dimethylphosphinate ligands ((CH3)2PO2-) have been prepared and tested in the alkoxycarbonylation of aromatic C–H bonds. The complex [Rh(µ-¿O,O'-(CH3)2PO2)(cod)]2 has been prepared by a reaction of [Rh(µ-MeO)(cod)]2 with 2 equivalents of dimethylphosphinic acid. Binuclear complexes [Rh(µ-¿O,O'-(CH3)2PO2)(CO)L]2 (L = PPh3, P(OMe)Ph2 and P(OPh)3) were obtained by carbonylation of the related mononuclear complexes [Rh(¿O-(CH3)2PO2)(cod)(L)], which were prepared in situ by the reaction of [Rh(µ-¿O,O'-(CH3)2PO2)(cod)]2 with 2 equivalents of L. Conversely, if L = IPr, the reaction of [Rh(µ-¿O,O'-(CH3)2PO2)(CO)L]2 with carbon monoxide affords the mononuclear complex [Rh(¿O-(CH3)2PO2)(CO)2IPr]. The subsequent reaction with trimethylamine N-oxide gives the corresponding binuclear complex [Rh(µ-¿O,O'-(CH3)2PO2)(CO)(IPr)]2 by abstraction of one of the carbonyl ligands. Complexes [Rh(µ-¿O,O'-(CH3)2PO2)(cod)]2 and [Rh(¿O-(CH3)2PO2)(cod)(L)] (L = IPr, PPh3, P(OMe)Ph2, P(OPh)3) are active precatalysts in the alkoxycarbonylation of C–H bonds, with the ligand system playing a key role in the catalytic activity. The complexes that feature more labile Rh–L bonds give rise to better catalysts, probably due to the more straightforward substitution of L by a second carbonyl ligand, since a more electrophilic carbonyl carbon atom is more susceptible toward aryl migration. In fact, complexes [Rh(µ-¿O,O'-(CH3)2PO2)(CO)2]2 and [Rh(µ-Cl)(CO)2]2, generated in situ from [Rh(µ-¿O,O'-(CH3)2PO2)(cod)]2 and [Rh(µ-Cl)(cod)2]2, respectively, are the most active catalysts tested in this work.
000064316 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E07$$9info:eu-repo/grantAgreement/ES/MINECO/Consolider-Ingenio/CSD2009-0050
000064316 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000064316 590__ $$a4.029$$b2016
000064316 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b7 / 46 = 0.152$$c2016$$dQ1$$eT1
000064316 592__ $$a1.229$$b2016
000064316 593__ $$aInorganic Chemistry$$c2016$$dQ1
000064316 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000064316 700__ $$0(orcid)0000-0002-8220-6031$$aSanz Miguel, Pablo J.$$uUniversidad de Zaragoza
000064316 700__ $$aPopoola, Saheed A.
000064316 700__ $$aAl-Saadi, Abdulaziz A.
000064316 700__ $$0(orcid)0000-0003-3144-5320$$aIglesias, Manuel$$uUniversidad de Zaragoza
000064316 700__ $$0(orcid)0000-0001-7154-7239$$aOro, Luis A.$$uUniversidad de Zaragoza
000064316 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000064316 7102_ $$12010$$2X$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cProy. investigación HWA
000064316 773__ $$g45, 42 (2016), 16955-16965$$pDalton Trans.$$tDalton Transactions$$x1477-9226
000064316 8564_ $$s724301$$uhttps://zaguan.unizar.es/record/64316/files/texto_completo.pdf$$yPostprint
000064316 8564_ $$s134288$$uhttps://zaguan.unizar.es/record/64316/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000064316 909CO $$ooai:zaguan.unizar.es:64316$$particulos$$pdriver
000064316 951__ $$a2020-02-21-13:20:21
000064316 980__ $$aARTICLE