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P-H activation of secondary phosphanes on a parent amido diiridium complex

AuthorsMena, Inmaculada CSIC ORCID; Casado, Miguel A. CSIC ORCID; Polo, Víctor; García-Orduña, P. CSIC ORCID; Lahoz, Fernando J. CSIC ORCID; Oro, Luis A. CSIC ORCID
Issue Date2014
PublisherRoyal Society of Chemistry (UK)
CitationDalton Transactions 43(4): 1609-1619 (2014)
AbstractSelected 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. This journal is © The Royal Society of Chemistry.
Identifiersdoi: 10.1039/C3DT52911H
issn: 1477-9226
e-issn: 1477-9234
Appears in Collections:(ISQCH) Artículos
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