Anhui Laboratory of Molecule-Based Materials, School of Chemistry and Materials Science, Anhui Normal University, Wuhu, Anhui 241000, P. R. China.
Dalton Trans. 2011 Oct 7;40(37):9447-53. doi: 10.1039/c1dt10622h. Epub 2011 Aug 17.
Simple silylamine elimination reactions of calix[4]-pyrrole R(2)C(C(4)H(2)NH) (R = Me (1), {-(CH(2))(5)-}(0.5) (2)) with 2 equiv. of (Me(3)Si)(2)NLn(μ-Cl)Li(THF)(3) (Ln = Nd, Sm, Dy) in reflux toluene, afforded the novel dinuclear alkali metal-free trivalent lanthanide amido complexes (η(5):η(1):η(5):η(1)-R(8)-calix[4]-pyrrolyl){LnN(SiMe(3))(2)}(2) (R = Me, Ln = Nd (3), Sm (4), Dy (5); R = {-(CH(2))(5)-}(0.5), Ln = Nd (6), Sm(7)). The complexes were fully characterized by elemental analyses, spectroscopic analyses and single-crystal X-ray analyses. X-ray diffraction studies showed that each lanthanide metal was supported by bispyrrolyl anions in an η(5) fashion and along with three nitrogen atoms from N(SiMe(3))(2) and two other pyrroyl rings in η(1) modes formed the novel bent-sandwiched lanthanide amido bridged trivalent lanthanide amido complexes, similar to ansa-cyclopentadienyl ligand-supported lanthanide amides with respect to each metal center. The catalytic activities of these organolanthanide complexes as single component l-lactide polymerization catalysts were studied.
杯[4]吡咯R(2)C(C(4)H(2)NH)（R = Me（1），{-(CH(2))(5)-}(0.5)（2））与 2 当量的(Me(3)Si)(2)NLn(μ-Cl)Li(THF)(3)（Ln = Nd、Sm、Dy）在回流甲苯中的简单硅烷消除反应，得到了新型双核无碱金属三价镧系酰胺配合物（η(5)：η(1)：η(5)：η(1)-R(8)-杯[4]吡咯基）{LnN(SiMe(3))(2)}(2)（R = Me，Ln = Nd（3），Sm（4），Dy（5）；R = {-(CH(2))(5)-}(0.5)，Ln = Nd（6），Sm(7)）。这些配合物通过元素分析、光谱分析和单晶 X 射线分析进行了充分的表征。X 射线衍射研究表明，每个镧系金属都以η(5)方式被双吡咯阴离子支撑，并与来自 N(SiMe(3))(2)的三个氮原子和η(1)方式的另外两个吡咯环一起形成了新型弯曲夹心式镧系酰胺桥连三价镧系酰胺配合物，类似于环戊二烯基配体支撑的镧系酰胺，每个金属中心都是如此。这些有机镧系金属配合物作为单组分 l-丙交酯聚合催化剂的催化活性进行了研究。
