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首页> 外文期刊>Chemistry: A European journal >Metal-to-Ligand Alkyl Migration Inducing Carbon–Sulfur Bond Cleavage in Dialkyl Yttrium Complexes Supported by Thiazole- Containing Amidopyridinate Ligands: Synthesis, Characterization, and Catalytic Activity in the Intramolecular Hydroamination Reaction
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Metal-to-Ligand Alkyl Migration Inducing Carbon–Sulfur Bond Cleavage in Dialkyl Yttrium Complexes Supported by Thiazole- Containing Amidopyridinate Ligands: Synthesis, Characterization, and Catalytic Activity in the Intramolecular Hydroamination Reaction

机译：金属到配体的烷基迁移诱导含噻唑的酰胺基吡啶鎓配体支持的二烷基钇配合物中二硫键的碳-硫键断裂：分子内加氢反应中的合成，表征和催化活性

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摘要

Neutral Y~(III) dialkyl complexes supported by tridentate N~-,N,N monoanionic methylthiazole– or benzothiazole– amidopyridinate ligands have been prepared and completely characterized. Studies on their stability in solution revealed progressive rearrangement of the coordination sphere in the benzothiazole-containing system through an unprecedented metal-to-ligand alkyl migration and subsequent thiazole ring opening. Attempts to synthesize hydrido species from the dialkyl precursor led to the generation of a dimeric yttrium species stabilized by a trianionic N~-,N,N~-,S~- ligand as the result of metal-to-ligand hydride migration with chemoselective thiazole ring opening and subsequent dimerization through intermolecular addition of the residual Y-H group to the imino fragment of a second equivalent of the ring-opened intermediate. DFT calculations were used to elucidate the thermodynamics and kinetics of the process, in support of the experimental evidence. Finally, all isolated yttrium complexes, especially their cationic forms prepared by activation with the Lewis acid Ph_3C~+[B(C_6F_5)_4]~-, were found to be good candidate catalysts for intramolecular hydroamination/cyclization reactions. Their catalytic performance with a number of primary and secondary amino alkenes was assessed.
机译：制备并完全表征了由三齿N〜-，N，N单阴离子甲基噻唑或苯并噻唑酰胺基吡啶配体支撑的中性Y〜（III）二烷基配合物。关于它们在溶液中的稳定性的研究表明，通过空前的金属到配体的烷基迁移和随后的噻唑开环，在含苯并噻唑的体系中配位球逐渐重排。尝试从二烷基前体合成氢化物物种，导致生成三聚体N〜-，N，N〜-，S〜-配体稳定的二聚钇物种，这是金属与配体氢化物与化学选择性噻唑迁移的结果通过分子间将残余的YH基团分子间加成到第二当量的开环中间体的亚氨基片段上来进行开环和随后的二聚化。 DFT计算用于阐明该过程的热力学和动力学，以支持实验证据。最后，发现所有分离的钇配合物，特别是通过用路易斯酸Ph_3C〜+ [B（C_6F_5）_4]-活化而制备的阳离子形式，都是分子内加氢/环化反应的良好候选催化剂。评估了它们在许多伯氨基和仲氨基烯烃中的催化性能。

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