聚烯丙硫醇/丙烯酸甲酯羰基铑(Ⅰ)配合物的分子内取代反应

THE STUDY OF INTRAMOLECULAR SUBSTITUTION REACTION OF POLYMER COMPLEX OF CATIONIC RHODIUM COORDINATED WITH POLYALLYLMERRCAPTAN METHYNOLACRYLATE

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 。

A new kind of cis \|dicarbonyl rhodium complex,which contained S and O atoms as uncoordinated donors,has been synthesized.After studying its intramolecular substitution reaction through IR and XPS data,the result indicated that the weak S→Rh and the weaker O→Rh coordination bonds can replace the strong Rh\|Cπ back donation bond to form tetradentated complex with the elevation of temperature and without the protection of CO.So the rhodium complex will not decompose for the drop of the terminal carbonyls and its stability is enhanced.The intramolecular substitution reaction is reversible.In the atmosphere of CO,the tetradentated complex will recover to bidentate complex with cis \|dicarbonyl.