Boryl transfer reactivity of a POCOP-supported Ir-diboryl: Reduction of CO2 to CO and borylation of other small molecules
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2016 Elsevier B.V. Reactions of a trivalent diboryl Ir complex Ir-(Bpin)2 supported with a POCOP-type pincer ligand with a series of small molecules have been explored (pin = pinacolate). Ir-(Bpin)2 deoxygenated CO2 to make Ir-CO and O(Bpin)2. Attempts to deoxygenate other carbonyl compounds were not successful. The reaction with CO led to loss of B2pin2 by reductive elimination and its replacement on Ir with CO. Ir-(Bpin)2 did not react with p-trifluoromethylbenzaldehyde, acetone, ethyl acetate or benzonitrile. The reaction with ethyl formate resulted in formal dehydroethoxylation of this substrate, with formation of Ir-CO and HBpin and EtOBpin. Finally, treatment of Ir-(Bpin)2 with ethylene resulted in diboration of ethylene to produce pinB-CH2CH2-Bpin and Ir-(C2H4).