Li, Ti(III), and Ti(IV) trisamidotriazacyclononane complexes. Syntheses, reactivity, and structures.
Li, Ti(III), and Ti(IV) trisamidotriazacyclononane complexes. Syntheses, reactivity, and structures.
复制标题
Li、Ti(III) 和 Ti(IV) 三酰胺三氮杂环壬烷配合物。
作者：
A. R. Dias;Ana M. Martins;J. Ascenso;Humberto S. Ferreira;M. Duarte;R. Henriques
介绍了1，4，7-(NHPhSiMe(2))(3)-1，4，7-triazacyclononane(H(3)N(3)-TACN)及其锂、钠衍生物的制备方法。锂衍生物Li(3)N(3)-Tacn(THF)(2)的四氢呋喃加合物的X-射线结构表明，其中一个大环悬臂被弯曲以允许其锂离子与两个Tacn胺配位。在溶液中，一个流动过程使所有悬而未决的臂在磁性上相等。Li(3)N(3)-Tacn或Na(3)N(3)-Tacn分别与TiCl4和TiCl3(Thf)(3)反应生成[Ti(N(3)-Tacn)]，5与各种氧化剂反应生成阳离子络合物[Ti(N(3)-Tacn)]X，6(X=I，Cl，SCN，Pf(6)，BPh(4))，它们以对映体lambda(lambdalambdalambda)/delta(deltadeltadelta)，形式存在，可在溶液中相互转化。5和6(X=I，BPh(4))的分子结构表明六个氮给电子体与钛配位。由于TaN悬挂臂长度较短，配体的六齿键合模式主要是通过N-Si-N角的锐化来实现的。[Ti(N(3)-Tacn)]I，6a与W(CO)(6)反应合成了[Ti(N(3)-Tacn)][W(CO)(5)I]，7.
The preparations of 1,4,7-(NHPhSiMe(2))(3)-1,4,7-triazacyclononane (H(3)N(3)-tacn) and its lithium and sodium derivatives are described. The X-ray structure of the THF adduct of the lithium derivative, Li(3)N(3)-tacn(THF)(2), shows that one of the macrocycle pendant arms is bent to allow the coordination of the its lithium ion to two tacn amines. In solution, a fluxional process makes all the pending arms magnetically equivalent. The reactions of Li(3)N(3)-tacn or Na(3)N(3)-tacn with either TiCl(4) and TiCl(3)(THF)(3) led to the formation of [Ti(N(3)-tacn)], 5. The oxidation of 5 with various oxidizing reagents gave cationic complexes [Ti(N(3)-tacn)]X, 6 (X = I, Cl, SCN, PF(6), BPh(4)), that exist as a pair of enantiomers, lambda(lambdalambdalambda)/delta(deltadeltadelta), which interconvert in solution. The molecular structures of 5 and 6 (X = I, BPh(4)) show the coordination of the six nitrogen donor set to the titanium. Due to the short length of the tacn pendant arms, the hexadentate bonding mode of the ligand is mainly achieved through the sharpening of the N-Si-N angles. The reaction of [Ti(N(3)-tacn)]I, 6a, with W(CO)(6) led to the synthesis of [Ti(N(3)-tacn)][W(CO)(5)I], 7.