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Homolytic N-H activation of ammonia: hydrogen transfer of parent iridium ammine, amide, imide, and nitride species.


ABSTRACT: The redox series [Ir(n)(NHx)(PNP)] (n = II-IV, x = 3-0; PNP = N(CHCHPtBu2)2) was examined with respect to electron, proton, and hydrogen atom transfer steps. The experimental and computational results suggest that the Ir(III) imido species [Ir(NH)(PNP)] is not stable but undergoes disproportionation to the respective Ir(II) amido and Ir(IV) nitrido species. N-H bond strengths are estimated upon reaction with hydrogen atom transfer reagents to rationalize this observation and are used to discuss the reactivity of these compounds toward E-H bond activation.

SUBMITTER: Scheibel MG 

PROVIDER: S-EPMC4597254 | biostudies-literature | 2015 Oct

REPOSITORIES: biostudies-literature

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Homolytic N-H activation of ammonia: hydrogen transfer of parent iridium ammine, amide, imide, and nitride species.

Scheibel Markus G MG   Abbenseth Josh J   Kinauer Markus M   Heinemann Frank W FW   Würtele Christian C   de Bruin Bas B   Schneider Sven S  

Inorganic chemistry 20150720 19


The redox series [Ir(n)(NHx)(PNP)] (n = II-IV, x = 3-0; PNP = N(CHCHPtBu2)2) was examined with respect to electron, proton, and hydrogen atom transfer steps. The experimental and computational results suggest that the Ir(III) imido species [Ir(NH)(PNP)] is not stable but undergoes disproportionation to the respective Ir(II) amido and Ir(IV) nitrido species. N-H bond strengths are estimated upon reaction with hydrogen atom transfer reagents to rationalize this observation and are used to discuss  ...[more]

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