doi:10.1021/acs.organomet.6b00330engMartínez De Salinas, S.Díez, J.Falvello, L.R.González, J.Gamasa, M.P.Lastra, E.Intramolecular C-C Coupling Reactions of Alkynyl, Vinylidene, and Alkenylphosphane Ligands in Rhodium(III) ComplexesART-2016-96343Electrophilic attack with methyl trifluoromethanesulfonate or tetrafluoroboric acid, to new alkynyl rhodium complexes containing alkenylphosphanes, leads to butenynyl coupling products or to the unprecedented rhodaphosphacycle complexes Rh(¿5-C5Me5){¿4-(P, C, C, C)-iPr2PCH2C(=CH2)C(CH2R)C=C(R)}]BF4] (R = Ph (11a), p-tol (11b)). These complexes 11a, b can be explained as a result of the coupling of three organic fragments in the molecule, the alkynyl, the vinylidene, generated in situ by reaction with HBF4 (A), and the C-C double bond from the alkenylphosphane. DFT computational studies on the formation of complex 11a suggest the 2 + 2] intramolecular cycloaddition between the double bond of the allylphosphane and the Ca-Cß of the vinylidene A as the most plausible pathway for this reaction.2016http://zaguan.unizar.es/record/7536610.1021/acs.organomet.6b00330http://zaguan.unizar.es/record/75366oai:zaguan.unizar.es:75366info:eu-repo/grantAgreement/ES/MICINN/CSD2007-00006info:eu-repo/grantAgreement/ES/MINECO/CTQ2011-28641info:eu-repo/grantAgreement/ES/MINECO/MAT2015-68200-C2-1-POrganometallics 35, 17 (2016), 2793-2805All rights reservedhttp://www.europeana.eu/rights/rr-f/info:eu-repo/semantics/openAccess