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首页> 外文期刊>European journal of inorganic chemistry >Octahedral Alkylbis(phenoxy-imine)tin(IV)Complexes:Effect of Substituents on the Geometry of the Complexes and Their Reactivity Toward Ionizing Species and Ethylene
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Octahedral Alkylbis(phenoxy-imine)tin(IV)Complexes:Effect of Substituents on the Geometry of the Complexes and Their Reactivity Toward Ionizing Species and Ethylene

机译：八面体烷基双（苯氧基-亚胺）锡（IV）配合物：取代基对配合物几何形状及其对电离物种和乙烯的反应性的影响

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摘要

The synthesis and characterization of the organo-tin compounds L2SnR2[L=N-(3,5-dichlorosahcyhdene)aniline;R=CH3(1),R=CH2Ph(2)]and L'2SnR2[3:L'=N-(3-tert-butyl-salicylidene)aniline,R=CH2Ph]are described herein.NMR studies showed a highly symmetric structure for complex 1,with the alkyl groups in a trans configuration,and the presence of at least two isomers in fluxional equilibrium for compounds 2 and 3.Single-crystal X-ray characterization for compound 2 showed an octahedral geometry with the alkyl groups in trans relationship.The reactivity of the synthesized compounds toward ionizing agents was studied by NMR spectroscopy.For compounds 1 and 2 formation of cationic species through alkyl abstraction by B(C6F5)3 was observed.For compound 3,a cationic species was obtained by reaction with 1 equiv.of[C(C6H5)3]~+[B(C6F5)4]-;in this species a eta~n coordination of the benzyl group with the metal centre was recognized by NMR solution study.All the obtained cationic species promoted ethylene oligomerization under mild conditions,producing oligomers with saturated end groups and methyl branches.Oligoethylene end-group NMR analysis and deuteriolysis experiments excluded the migratory-insertion mechanism.
机译：有机锡化合物L2SnR2 [L = N-（3,5-dichlorosahcyhdene）苯胺; R = CH3（1），R = CH2Ph（2）]和L'2SnR2 [3：L'= N -（3-叔丁基-水杨基亚基）苯胺，R = CH2Ph]。NMR研究表明，配合物1具有高度对称的结构，烷基呈反式构型，并且存在至少两种异构体。化合物2和3的平衡。化合物2的单晶X射线表征显示烷基与八面体呈反式关系的八面体几何形状。通过NMR光谱研究合成的化合物对电离剂的反应性。化合物1和2的形成对于化合物3，通过与1当量的[C（C6H5）3]〜+ [B（C6F5）4]-反应，得到阳离子种类。通过NMR溶液的研究，该物种的苄基与金属中心发生了η配位配位。在温和条件下进行低聚，生成带有饱和端基和甲基支链的低聚物。低乙烯端基的NMR分析和氘化实验排除了迁移插入的机理。

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