Title: A combined gas-phase, solution-phase, and computational study of C−H activation by cationic iridium(III) complexes
Authors : Hinderling, Christian
Feichtinger, Derek
Plattner, Dietmar A.
Chen, Peter
Published in : Journal of the American Chemical Society
Volume(Issue) : 119
Issue : 44
Pages : 10793
Pages to: 10804
Publisher / Ed. Institution : American Chemical Society
Issue Date: 1997
License (according to publishing contract) : Licence according to publishing contract
Type of review: Peer review (Publication)
Language : English
Subjects : C-H activation; Mechanism; Iridium
Subject (DDC) : 540: Chemistry
Abstract: A combination of electrospray ionization MS/MS techniques, isotopic labeling experiments in the gas-phase and solution, and ab initio calculations is used to study the C−H activation reactions of [Cp*Ir(PMe3)(CH3)]+ and [CpIr(PMe3)(CH3)]+. The reaction in the gas phase was found to proceed through a Cp or [Cp*Ir(η2-CH2PMe2)]+ intermediate. Quantitative collision-induced dissociation (CID) threshold measurements were used along with general models for ion−molecule reactions to construct potential energy diagrams which rationalize the gas-phase results. The comparison between the two complexes, and between the reactions in the gas phase and in solution, suggests that the reaction through the intermediacy of a metallaphosphacyclopropane could be favored over the conventional (and simpler) oxidative addition/reductive elimination mechanism when the Ir(III) complex is rendered more electron deficient.
Departement: Life Sciences and Facility Management
Organisational Unit: Institute of Chemistry and Biotechnology (ICBT)
Publication type: Article in scientific Journal
DOI : 10.1021/ja970995u
ISSN: 0002-7863
1520-5126
URI: https://digitalcollection.zhaw.ch/handle/11475/13740
Appears in Collections:Publikationen Life Sciences und Facility Management

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