title: Terminal phosphanido rhodium complexes mediating catalytic P-P and P-C bond formation.
abstract: Complexes with terminal phosphanido (M-PR2) functionalities are believed to be crucial intermediates in new catalytic processes involving the formation of P-P and P-C bonds. We showcase here the isolation and characterization of mononuclear phosphanide rhodium complexes ([RhTp(H)(PR2)L]) that result from the oxidative addition of secondary phosphanes, a reaction that was also explored computationally. These compounds are active catalysts for the dehydrocoupling of PHPh2 to Ph2P-PPh2. The hydrophosphination of dimethyl maleate and the unactivated olefin ethylene is also reported. Reliable evidence for the prominent role of mononuclear phosphanido rhodium species in these reactions is also provided.
authors.affiliation: Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, 50009-Zaragoza (Spain).
authors.forename: Ana M
authors.initials: AM
authors.lastname: Geer
authors.forename: Ángel L
authors.initials: ÁL
authors.lastname: Serrano
authors.forename: Bas
authors.initials: B
authors.lastname: de Bruin
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Ciriano
authors.forename: Cristina
authors.initials: C
authors.lastname: Tejel
keywords: P ligands; PH bonds; homogeneous catalysis; hydrotris(pyrazolyl)borate; rhodium