Bicyclic cyclopalladated complexes derived from N-benzyl-substituted Schiff's bases
作者:Katsuma Hiraki、Shingo Ibaraki、Masayoshi Onishi、Yuka Ono、Junko K. Kawashima、Masako Ando
DOI:10.1016/s0022-328x(97)00377-x
日期:1997.12
2-Benzylamino-2-penten-4-one (Hacac-bn) reacts with Pd(MeCO2)2 and [Pd(MeCO2)2(SPr2i)2] in benzene at 50°C to give an N,O-chelated complex, [Pd(acac-bn)2] and a bicyclic cyclopalladatedcomplex, [Pd(acac-NCH2C6H4)(SPr2i)], respectively. Diisopropyl sulfide ligand in the latter complex is replaced easily by PPh3, giving [Pd(acac-NCH2C6H4)(PPh3)]. N-(Salicylidene)benzylamine (Hsal-bn) also reacts similarly with
2-苄基氨基-2-戊烯-4-酮(Hacac-bn)在50°C下与Pd(MeCO 2)2和[Pd(MeCO 2)2(SPr 2 i)2 ]在苯中反应,得到N, O-螯合的配合物[Pd(acac-bn)2 ]和双环环钯配合物[Pd(acac-NCH 2 C 6 H 4)(SPr 2 i)]。后者络合物中的二异丙基硫醚配体很容易被PPh 3取代,得到[Pd(acac-NCH 2 C 6 H 4)(PPh 3)]。ñ-(水杨基)苄胺(Hsal-bn)在50°C下也与Pd(MeCO 2)2和[Pd(MeCO 2)2(SPr 2 i)2 ]类似反应,得到[Pd(sal-bn)2 ]。和[Pd(sal-NCH 2 C 6 H 4)(SPr 2 i)]。ñ - (3,5-二Dichlorosalicylidene)苄胺(Hdcsal-BN)与[钯(梅科发生反应2)2(SPR 2我)2 ]和Pd(梅科2)2
Dinuclear iminophenoxide copper complexes in <i>rac</i>-lactide polymerisation
作者:Pargol Daneshmand、Leena Pinon、Frank Schaper
DOI:10.1039/c8dt02140f
日期:——
prepared. All complexes were characterized by single crystal X-ray diffraction studies and crystallized as dinuclear penta-coordinated complexes. Homoleptic complexes L2Cu were inactive in lactide polymerization at room temperature. Most heteroleptic complexes showed modest to good activities with full conversion in less than 6 h at room temperature. Complexes with R′ = H showed poor molecular weight control
由甲醇铜与ROH和LH(ROH =二甲基氨基乙醇或吡啶基甲醇,R'= H)反应制得双核双(R'-(R'-亚氨基甲基)苯氧基)铜络合物L 2 Cu 2(μ-OR)2,4,6 - t Bu,1,3-Cl,R′′=苄基,环己基,二苯甲基和2,6-二甲基苯基)。均质L 2 Cu的形成使制备过程复杂化,在24种可能的组合中仅能制备9种。所有配合物均通过单晶X射线衍射研究表征,并结晶为双核五配位配合物。同感复合物L 2铜在室温下对丙交酯聚合反应中无活性。大多数杂合剂复合物在室温下不到6小时内即可表现出中等至良好的活性,并具有完全转化的能力。R'= H的配合物显示出较差的分子量控制,R'= Cl的配合物在聚合反应中没有活性。在含吡啶基甲醇盐的配合物中,只有一种醇盐会引发链增长。所有复合物均生成无规聚合物。