two new seven-coordinate anionic complexes of molybdenum(II), binuclear [(μ-Cl)2Mo(μ-Cl)(SnCl3)(CO)3}2]2− and mononuclear [MoCl3(GeCl3)(CO)3]2−, have been synthesized and characterized by single-crystal X-ray diffraction studies. The binuclear complex exhibits a unique mode of reactivity towards norbornene. In a strictly anhydrous atmosphere the binuclear complex effectively initiates the ring-opening
钼(II)的两个新的七配位阴离子络合物,双核[(μ-Cl)2 Mo(μ-Cl)(SnCl 3)(CO)3 } 2)2−和单核[MoCl 3(GeCl 3)(CO)3 ] 2−,已经通过单晶X射线衍射研究合成并表征。双核复合物对降冰片烯具有独特的反应方式。在严格的无水气氛中,双核络合物有效地引发了降冰片烯的开环易位聚合反应,但是在水存在下,降冰片烯被有效地转化为双降冰片基醚(C 7 H 11)2 O.
Mechanism of initiation of the ring-opening polymerization and addition oligomerization of norbornene using unicomponent metathesis catalysts
作者:D. Theodore Laverty、John J. Rooney
DOI:10.1039/f19837900869
日期:——
formed during ring-openingpolymerization of norbornene in benzene solvent using several unicomponent metal halide catalysts (W, Mo, Re, Ru, Os and Ir) were extensively investigated. Dimers and trimers were observed in all cases but were only substantial relative to polymer yields for WCl6 and ReCl5. The rate of formation of the dimers exactly paralleled that of the ring-openedpolymer, in marked contrast