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Cationic (η5-C5Me4R)RhIII Complexes with Metalated Aryl Phosphines Featuring η4-Phosphorus plus Pseudo-Allylic Coordination

AutorEspada, María F.; Esqueda Oliva, Ana Cristina ; Campos, Jesús ; Rubio, Miguel ; López-Serrano, Joaquín ; Álvarez, Eleuterio ; Maya, Celia ; Carmona, Ernesto
Fecha de publicación2018
EditorAmerican Chemical Society
CitaciónOrganometallics 37: 11- 21 (2018)
ResumenIn this contribution we study experimentally and computationally some electrophilic cationic (η-CMeR)Rh complexes containing a cyclometalated bis(aryl) phosphine, PR′Ar. The phosphine Ar groups feature methyl substituents at the 2- and 6-positions of the aromatic rings, allowing the formation of the complexes [(η-CMeR)Rh(CP)] (3), where the metalated phosphine exhibits η coordination to rhodium through phosphorus and the carbon atoms of the adjoining pseudo-allylic functionality. The solution and solid-state structures of complexes 3 have been studied by NMR and X-ray methods and their electronic properties investigated with the aid of DFT calculations. The Lewis acid behavior of complexes 3 has also been addressed, concentrating on reactivity toward CO, H,and hydrosilanes. Some catalytic Si-H/Si-D exchange and hydrosilylation reactions are also reported.
URIhttp://hdl.handle.net/10261/169573
Identificadoresdoi: 10.1021/acs.organomet.7b00688
issn: 1520-6041
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