阳离子稀土金属双水杨醛缩乙二胺配合物

Cationic rare-earth metal SALEN complexes.

作者信息

Liu Qiancai, Meermann Christian, Görlitzer Hans W, Runte Oliver, Herdtweck Eberhardt, Sirsch Peter, Törnroos Karl W, Anwander Reiner

机构信息

Department of Chemistry, Technische Universität München, Lichtenbergstr. 4, D-85747, Garching, Germany.

出版信息

Dalton Trans. 2008 Nov 28(44):6170-8. doi: 10.1039/b808781d. Epub 2008 Oct 1.

DOI:10.1039/b808781d

PMID:18985250

Abstract

Complexes (Salpren(tBu,tBu))YN(SiHMe2)2 and (SALEN(tBu,tBu))LaN(SiHMe2)2 (SALEN(tBu,tBu) = Salcyc(tBu,tBu) and Salpren(tBu,tBu)) were prepared from Ln[N(SiHMe2)2]3(thf)2 and H2SALEN(tBu,tBu). The yttrium complex was characterized by X-ray crystallography revealing intrinsic solid-state structural features: the metal centre is displaced by 1.05 angstroms from the [N2O2] least squares plane of a highly bent Salpren(tBu,tBu) ligand (angle(Ph,Ph) dihedral angle of 80.4(1) degrees ) and is coordinated asymmetrically by the silylamide ligand exhibiting one significant Y---(HSi) beta-agostic interaction (Y-N1-Si1, 106.90(9) degrees; Y---Si1, 3.2317(6) angstroms). Complexes (SALEN(tBu,tBu))LnN(SiHMe2)2n (n = 1, Sc; n = 2, Y, La) react with ammonium tetraphenylborate to form the ion pairs [(SALEN(tBu,tBu))Ln(thf)n][BPh4]. The cationisation was proven by X-ray crystal structure analyses of [(Salpren(tBu,tBu))Sc(thf)2][B(C6H5)4].2(thf) and [(Salpren(tBu,tBu))Ln(thf)3][B(C6H5)4].4(thf) (Ln = Y, La), showing an octahedral and pentagonal-bipyramidal coordination geometry, respectively.

摘要

配合物（Salpren(tBu,tBu)）YN(SiHMe2)2 和（SALEN(tBu,tBu)）LaN(SiHMe2)2（SALEN(tBu,tBu) = Salcyc(tBu,tBu) 且 Salpren(tBu,tBu)）由 Ln[N(SiHMe2)2]3(thf)2 和 H2SALEN(tBu,tBu) 制备而成。钇配合物通过 X 射线晶体学进行表征，揭示了其内在的固态结构特征：金属中心从高度弯曲的 Salpren(tBu,tBu) 配体的 [N2O2] 最小二乘平面位移了 1.05 埃（Ph,Ph 二面角为 80.4(1) 度），并且由硅烷基酰胺配体不对称配位，表现出一种显著的 Y---(HSi) β-配位相互作用（Y-N1-Si1，106.90(9) 度；Y---Si1，3.2317(6) 埃）。配合物（SALEN(tBu,tBu)）LnN(SiHMe2)2n（n = 1，Sc；n = 2，Y，La）与四苯基硼酸铵反应形成离子对 [(SALEN(tBu,tBu))Ln(thf)n][BPh4]。通过对 [(Salpren(tBu,tBu))Sc(thf)2][B(C6H5)4].2(thf) 和 [(Salpren(tBu,tBu))Ln(thf)3][B(C6H5)4].4(thf)（Ln = Y，La）的 X 射线晶体结构分析证明了阳离子化，分别显示出八面体和五角双锥配位几何结构。