Reversible CO2 binding triggered by metal–ligand cooperation in a rhenium(I) PNP pincer-type complex and the reaction with dihydrogen

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作者：

M Vogt，A Nerush，Y Diskin-Posner，Y Ben-David，D Milstein

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摘要：

Herein we report the reversible binding of CO2to a very rare dearomatized PNP pincer complex (cis-[Re(PNPtBu*)(CO)2]2). The [1,3]-addition of CO2to the pincer complex is triggered by metal–ligand cooperationviaan aromatization/dearomatization sequence to formcis-[Re(PNPtBu–COO)(CO)2] (3)viaRe–O and C–C bond formation. The reversible binding was demonstrated by the exchange reaction of13CO2/CO2from the isotopically labelled compoundcis-[Re(PNPtBu–13COO)(CO)2] (3a). Furthermore, complex3reacts with H2to give free CO2and the aromatized hydride complexcis-[Re(PNPtBu)(CO)2H] (4), which undergoes the reverse reaction to re-form3under CO2pressure at elevated temperature. Alternatively,4reacts, in a low temperature pathway,viathe insertion of CO2into the Re–H bond to give the formate complexcis-[Re(PNPtBu)(CO)2(OOCH)] (5)]. Remarkably, complex5catalyses efficiently the dehydrogenation of formic acid under base-free conditions.

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关键词：

heavy metals fish Black Sea Bulgaria

DOI：

10.1039/c4sc00130c

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年份：

2014