- P-H activation of secondary phosphanes on a parent amido diiridium complex
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Selected secondary phosphanes (H-PR2; R = Ph, Cy, iPr) smoothly react with a parent amido-bridged diiridium cyclooctadiene complex affording mixed amido/(bis)phosphido dinuclear species. A careful investigation of the reaction profile, carried out by experimental and theoretical tools, revealed that, after an initial amido/phosphido exchange, at low temperatures a second molecule of secondary phosphane adds to the dinuclear system through an oxidative addition process leading to a hydrido amido/bis(phosphido) mixed-valence complex [IrIII/IrI]. These species rearrange above -10 °C into the most stable isomer that arises from a migration of the hydrido moiety to one of the CH fragments of a coordinated cod molecule, a transformation facilitated by the formation of an intermetallic bond. Further heating of these species reductively eliminates ammonia affording bis(phosphido)-metal-metal bonded complexes. The Royal Society of Chemistry.
- Mena, Inmaculada,Casado, Miguel A.,Polo, Victor,Garcia-Orduna, Pilar,Lahoz, Fernando J.,Oro, Luis A.
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supporting information
p. 1609 - 1619
(2014/01/06)
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- Niobium/rhodium bimetallic complexes: synthesis, structure, and catalytic hydrosilylation of acetophenone and benzaldehyde
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Reactions of a new imido phosphido complex, Cp2Nb(=NBu t)(PPh2) (1), with olefin complexes of rhodium afford two types of compounds. With [(μ-C1)Rh(C2H4) 2]2, an imido/phosphido-
- Leelasubcharoen, Somying,Zhizhko, Pavel A.,Kuzmina, Lyudmila G.,Churakov, Andrei V.,Howard, Judith A. K.,Nikonov, Georgii I.
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p. 4500 - 4506
(2009/12/06)
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