氨的均裂N-H活化：铱氨、酰胺、酰亚胺和氮化物母体的氢转移
Homolytic N-H activation of ammonia: hydrogen transfer of parent iridium ammine, amide, imide, and nitride species.
作者信息
Scheibel Markus G, Abbenseth Josh, Kinauer Markus, Heinemann Frank W, Würtele Christian, de Bruin Bas, Schneider Sven
机构信息
Institut für Anorganische Chemie, Georg-August-Universität , Tammannstraße 4, 37077 Göttingen, Germany.
Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander University Erlangen-Nürnberg (FAU) , Egerlandstr. 1, 91058 Erlangen, Germany.
出版信息
Inorg Chem. 2015 Oct 5;54(19):9290-302. doi: 10.1021/acs.inorgchem.5b00829. Epub 2015 Jul 20.
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.
研究了氧化还原系列[Ir(n)(NHx)(PNP)]（n = II-IV，x = 3-0；PNP = N(CHCHPtBu2)2）的电子、质子和氢原子转移步骤。实验和计算结果表明，Ir(III)亚氨基物种[Ir(NH)(PNP)]不稳定，会歧化为相应的Ir(II)氨基和Ir(IV)氮化物物种。通过与氢原子转移试剂反应估算N-H键强度，以解释这一现象，并用于讨论这些化合物对E-H键活化的反应性。
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