doi:10.1039/c6dt03010fengIturmendi, AmaiaSanz Miguel, Pablo J.Popoola, Saheed A.Al-Saadi, Abdulaziz A.Iglesias, ManuelOro, Luis A.Dimethylphosphinate bridged binuclear Rh(i) catalysts for the alkoxycarbonylation of aromatic C-H bondsART-2016-102703A 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.2016http://zaguan.unizar.es/record/6431610.1039/c6dt03010fhttp://zaguan.unizar.es/record/64316oai:zaguan.unizar.es:64316info:eu-repo/grantAgreement/ES/DGA/E07info:eu-repo/grantAgreement/ES/MINECO/Consolider-Ingenio/CSD2009-0050Dalton Transactions 45, 42 (2016), 16955-16965All rights reservedhttp://www.europeana.eu/rights/rr-f/info:eu-repo/semantics/openAccess