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
作者:Dmitry M. Lyubov、Lapo Luconi、Andrea Rossin、Giulia Tuci、Anton V. Cherkasov、Georgy K. Fukin、Giuliano Giambastiani、Alexander A. Trifonov
DOI:10.1002/chem.201303853
日期:2014.3.17
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
中性ÿ III由三齿Ñ支持二烷基配合物-,N,N-单阴离子methylthiazole-或苯并噻唑配体amidopyridinate已经制备和完全表征。关于它们在溶液中的稳定性的研究表明,通过空前的金属-配体烷基迁移和随后的噻唑开环,含苯并噻唑的系统中的配位球逐渐重排。从导致由三阴离子Ñ稳定二聚体钇物种的产生二烷基前体的尝试来合成氢基物种-,N,N -,S -金属配位体氢化物迁移并带有化学选择性噻唑开环并随后通过分子间将残留的YH基团分子间加成至第二当量的开环中间体的亚氨基片段而形成二聚体的结果。DFT计算被用来阐明该过程的热力学和动力学,以支持实验证据。最后,所有分离的钇配合物,特别是通过用路易斯酸Ph 3 C + [B(C 6 F 5)4 ]活化制备的阳离子形式。被发现是用于分子内加氢/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。