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Rhodium catalyzed P-P and P-C bond formation

AutorTejel, Cristina ; Geer, Ana M. ; Ciriano, Miguel A.
Fecha de publicación2015
CitaciónEuCOMC XXI (2015)
ResumenComplexes with a terminal phosphanido (M‐PR2) functionality bound to a single late transition metal center have been proposed as intermediates in relevant processes such as dehydrocoupling and hydrophosphanation reactions. The former provides an easy way to diphosphanes, phosphacycles and unique oligophosphanes. The later represents an atom‐economical route to a very important class of compounds such as organophosphanes. Moreover, safety, selectivity and 'green synthesis' are major advantages of dehydrocoupling and hydrophosphination catalysis. First, we will showcase the isolation of mononuclear hydrido phosphanido rhodium complexes resulting from the oxidative‐addition of secondary phosphanes, a key step postulated in both processes, but rarely observed. Then, the nucleophilicity of the terminal phosphanido group in [RhTp(H)(PMe3)(PPh2)] was tested by reaction with activated olefins, which results in effective catalytic hydrophosphanation reactions under mild conditions. Second, effective catalytic dehydrocoupling of secondary phosphanes was achieved employing terminal phosphanido rhodium complexes such as 1. More importantly, the hydrophosphanation of ethylene was also observed, a surprising result since non‐activated olefins are essentially absent in this type of reactions. Finally, reliable evidence for the prominent role of mononuclear rhodium phosphanido species in these catalytic P‐P and P‐C bond formation reactions will also be provided, as well as mechanistic information that could help to the development of new catalysts for the ‘green syntheses’ of phosphanes and diphosphanes.
DescripciónResumen del trabajo presentado a la XXI EuCheMS International Conference on Organometallic Chemistry celebrada en Bratislava (Slovakia) del 5 al 9 de julio de 2015.
URIhttp://hdl.handle.net/10261/156003
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