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Terminal-phosphanido rhodium complexes

Autor Geer, Ana M. ; Serrano, Ángel L. ; Ciriano, Miguel A. ; Tejel, Cristina
Fecha de publicación 2014
Citación XXXII GEQO (2014)
Resumen[Work hypothesis and objective]: Complexes 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. From a mechanistic point of view, both, outer- and inner-sphere mechanisms have been considered. Nonetheless, the most widely established pathway involves the nucleophilic attack of the phosphanido ligand to an uncoordinated olefin. Consequently, an in-depth understanding of the reactivity of phosphanido ligands may aid in the development of the above mentioned and new catalytic transformations. [Results]: We will showcase reactions that give isolable rhodium complexes with a terminal phosphanido ligand, which result from the oxidative-addition of the PH bond in secondary phosphanes to rhodium. Such type of complexes has been spectroscopically detected in very few instances, but there are not isolated examples up to date, despite the key role of this activation reaction in dehydrocoupling and hydrophosphanation processes. Moreover, we have found that the nucleophilicity of the phosphanide ligand promotes the formation of P-C bonds with activated substrates, which results in effective catalytic hydrophospanation reactions. In addition, we will describe catalytic dehydrocoupling of secondary phosphanes in the presence of ethylene as hydrogen acceptor and the X-ray structure of the resting state of the catalyst. We will also discuss the formation of an unusual rhodaphosphetane under stoichiometric conditions, which involves an alternative mechanism for P-C bond formation.
Descripción Trabajo presentado a la XXXII Conference Expert Group Meeting on Organometallic Chemistry celebrada en Tarragona (España) del 17 al 19 de septiembre de 2014.
URI http://hdl.handle.net/10261/112058
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