Fixation of Both O2 and CO2 from Air by a Crystalline Palladium Complex Bearing N-Heterocyclic Carbene Ligands

Crystals of the two-coordinate palladium(0) complex 1 bearing the new N-heterocyclic carbene ligand, ITmt, directly and rapidly fixed both O2 and CO2 from air to produce the corresponding palladium(II) peroxocarbonate complex 2. The present reaction consists of dioxygenation of the palladium(0) complex 1 to the palladium(II) peroxo complex 3 and the subsequent CO2 insertion to produce the peroxocarbonate complex 2. Reaction of the crystals of 1 with air was monitored by microscopic IR spectroscopy to confirm the sequence of the two-step solid-state reaction. The unique reactivity of solid 1 toward air was explained in terms of the structural features of the carbene ligand, ITmt.

该新型N-杂环卡宾配体ITmt的二维钯(0)配合物1能够直接且迅速地从空气中固定氧气和二氧化碳，生成相应的钯(II)过氧碳酸复合物2。当前反应过程包括将钯(0)配合物1的二氧化氧合为钯(II)过氧复合物3，并随后进行二氧化碳插入反应以生成过氧碳酸复合物2。通过微观红外光谱学对1的晶体与空气的反应进行监测，以确认两步固态反应的序列。对于固体1对空气的独特反应性，可从卡宾配体ITmt的结构特征进行解释。