合成了一种新的含有S、O未配位原子的高分子顺二羰基铑配合物 ,用IR和XPS数据研究了其分子内羰基取代反应 ,结果表明在遇热且无CO保护下S、O与铑形成的弱的S→Rh、O→Rh键可取代强的Rh→Cπ键 ,形成稳定的四配位结构 ,从而保护了铑不因末端羰基脱落而分解 ,提高了它的稳定性 ;其分子内取代反应是可逆的 ,在CO气氛下该结构又能够回复到二配位结构 A new cis-dicarbonyl rhodium complex containing S, O uncoordinated atoms was synthesized. The intramolecular carbonyl substitution reaction was studied by IR and XPS data. The results showed that the reaction of S, The weak S → Rh and O → Rh bonds formed by O and rhodium can replace the strong Rh → Cπ bond to form a stable tetracoordinate structure, thus protecting the rhodium from being decomposed by the exfoliation of the terminal carbonyl and enhancing its stability ; Its intramolecular substitution reaction is reversible, and the structure can revert to the two-coordinate structure under CO atmosphere