Zhu Shan, Wu Weikang, Hong Dongjing, Chai Fuxiang, Huang Zeming, Zhu Xiancui, Zhou Shuangliu, Wang Shaowu
Laboratory of Functionalized Molecular Solids, Ministry of Education, Anhui Laboratory of Molecule-Based Materials, College of Chemistry and Materials Science, Anhui Normal University, Wuhu, Anhui 241000, PR China.
Anhui Laboratory of Clean Catalytic Engineering, Anhui Laboratory of Functional Coordinated Complexes for Materials Chemistry and Application, College of Chemical and Environmental Engineering, Anhui Polytechnic University, Wuhu, Anhui 241000, PR China.
Inorg Chem. 2024 Aug 12;63(32):14860-14875. doi: 10.1021/acs.inorgchem.4c00981. Epub 2024 Jul 29.
The pincer rare-earth dialkyl complexes [-RE(CHSiMe) (RE = Lu(), Yb(), Er(), Y(), Dy())] with the indol-2-yl-based NCN pincer ligand were synthesized by the reactions of the proligand ( = 1-MeNCHCH-3-(2-PrCHN═CH)CHN) with RE(CHSiMe)(THF). These complexes exhibited a variety of reactivities toward organic compounds such as amines, triphenylphosphine ylide, -phenylimidazole, pyridine derivatives, and -carborane leading to -bond metathesis, migration insertion, and redox reaction products. The reactions of the dialkyl rare-earth metal complexes with -carborane afforded the novel NCN pincer-ligated carboryne-based metallacyclopropanes which reacted with diphenyl ketone to give insertion products of the RE-C and one of the RE-C bonds, while the reaction of the carboryne-based metallacyclopropanes with diphenyldiazomethane produced the di--metallacyclopentanes via the insertions of the N═N bond of the diphenyldiazomethane into two RE-C bonds and the RE-C bond. The reactions of the dialkyl complexes with 2 equiv of 2,2'-bipyridine afforded the pincer-ligated bis(2,2'-bipyridyl monoanionic radical) complexes via the homolytic redox reaction.
通过前体配体（=1-MeNCHCH-3-(2-PrCHN═CH)CHN）与RE(CHSiMe)(THF)（RE = Lu(III)、Yb(III)、Er(III)、Y(III)、Dy(III)）反应，合成了带有吲哚-2-基的NCN钳形配体的钳形稀土二烷基配合物。这些配合物对有机化合物如胺、三苯基膦叶立德、α-苯基咪唑、吡啶衍生物和碳硼烷表现出多种反应活性，生成了σ键复分解、迁移插入和氧化还原反应产物。二烷基稀土金属配合物与碳硼烷反应得到了新型的NCN钳形配位的基于碳硼炔的金属环丙烷，其与二苯甲酮反应生成RE-C和其中一个RE-C键的插入产物，而基于碳硼炔的金属环丙烷与二苯基重氮甲烷反应通过二苯基重氮甲烷的N═N键插入两个RE-C键和RE-C键生成二-σ-金属环戊烷。二烷基配合物与2当量的2,2'-联吡啶反应通过均裂氧化还原反应得到钳形配位的双(2,2'-联吡啶单阴离子自由基)配合物。
