|Title:||A combined gas-phase, solution-phase, and computational study of C−H activation by cationic iridium(III) complexes|
|Authors :||Hinderling, Christian|
Plattner, Dietmar A.
|Published in :||Journal of the American Chemical Society|
|Publisher / Ed. Institution :||American Chemical Society|
|License (according to publishing contract) :||Licence according to publishing contract|
|Type of review:||Peer review (Publication)|
|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|
|Appears in Collections:||Publikationen Life Sciences und Facility Management|
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