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首次对 Co2 ( CO) 8和有机膦配体〔PPh3 、P( OPh) 3 〕的固相合成反应进行了研究 .对产物做了元素分析 ,IR、1HNMR、3 1PNMR、MS等波谱表征 ,并对产物的立体结构和反应机理进行推测 .产物〔cis-Co( CO) 3 ( PPh3 ) 2 〕+ 〔Co( CO) 4〕-中的阳离子结构对称性为 Cs,不同于液相条件下反应产物的阳离子结构对称性 D3 h.这种结构的差异导致 P原子所受的反位影响不同 ,因而固相和液相反应产物的 3 1PNMR化学位移 δ值不同 .产物〔Co( CO) 3 P( OPh) 3 〕2 的对称性为D3 d,与液相反应产物立体结构相同 ,但反机理不同 .反应物 Co2 ( CO) 8在固态和在溶液中的结构差异 ,Co-Co键在反应中断裂与否以及 CO的流变性是影响产物结构的主要因素 .
The solid-phase reaction of Co2 (CO) 8 and the organophosphine ligand [PPh3, P (OPh) 3] was studied for the first time.The elemental analysis, IR, 1HNMR, 31PNMR, The stereostructure and reaction mechanism of the product were inferred.The symmetry of the cation in the product [cis-Co (CO) 3 (PPh3) 2] + [Co (CO) 4] - is Cs, The symmetry of the cation structure of the product D3 h. The difference in the structure results in different transversal effects on the P atom, so the 3P NMR chemical shifts δ of the solid and liquid reaction products are different. The product [Co (CO) 3 P (OPh) 3] 2 is D3d, which has the same stereostructure as that of the liquid reaction but different anti-mechanism. The structural difference of Co2 (CO) 8 in the solid and in solution, Whether the fracture or not, and the rheological properties of CO 2 are the main factors that affect the product structure.