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C1 molecule activation by POCsp2OP-ligated nickel complexes
Zhongyi Liu1, Boris Vabre2, Daniel Chartrand2
1Tianjin Key Laboratory of Structure and Performance for Functional Molecules, College of Chemistry, Tianjin Normal University, 393 BinShui West Road, Tianjin, 300387, P. R. China. jjhao@tjnu.edu.cn.
None:
This contribution describes the reactivity of POCsp2OP-supported nickel siloxide (1) and arylamide (2) complexes (POCsp2OP = κP,κC,κP'-2,6-(i-Pr2PO)2C6H3, Ar = 2,6-iPr2-C6H3) toward CO, CO2, H2O, and isonitriles. The amide complex 2 activates CO to form the carbamoyl species 3, whereas the siloxide analogue 1 remains inert under identical conditions. Notably, 3 is also accessible via isonitrile insertion into 1, while the treatment of 2 with ArNC triggers pincer framework disassembly, yielding the doubly hydrogen-bonded phenolate complex 4. The two complexes exhibit contrasting CO2 activation modes: 2 undergoes irreversible Ni-N insertion to form the carbamate 6, whereas 1 engages in reversible CO2 binding to generate the dinuclear carbonate complex 7. These results demonstrate that the ligand rigidity and X-ligand identity synergistically control activation pathways, further highlighting the role of the supporting ligand in harmonizing stability and reactivity during small-molecule incorporation.
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