Studies on the Coordination Patterns of Diamine-Bridged Tetraphenoxy Ligands with Group 3 and 4 Metals
Yongjie Chen1, Liye Qu1,2, Thierry Roisnel3, Marie Cordier3, Dan Yuan1（袁丹）*, Yingming Yao1（姚英明）*, Evgueni Kirillov2*
1Key Laboratory of Organic Synthesis ofJiangsu Province, College of Chemistry, Chemical Engineeringand Materials Science, Dushu Lake Campus, SoochowUniversity, Suzhou 215123, People’s Republic of China
2Univ Rennes, CNRS, ISCR (Institut desSciences Chimiques de Rennes), Rennes F-35700, France
3Centre de Crystallographie, Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes), Rennes F-35700, France
Inorg. Chem. 2024, 63, 12774−12784
Abstract: Alkane elimination reactions between the diamino- and dianilino-bridged tetrakis(phenolate) proligands 1a,b-H4 and precursors M(CH2SiMe3)3(THF)2, M(CH2C6H4-o-NMe2)3 (M = Sc and Y), and Hf(CH2Ph)4 were investigated. The diamino-bridged 1a-H4 afforded nonsymmetric complex 2a-Y2 incorporating two metal centers in different coordination environments. This one and other dinuclear compounds 2b-Sc2, 2a-Hf2, and 2b-Hf2 were characterized by NMR spectroscopy, elemental analysis, and X-ray diffraction study (for 2a-Y2 and 2b-Sc2) and turned out to be symmetric in solution. Compound 2a-Y2, upon treatment with 2 equiv of 2-phenylpyridine, afforded symmetric bis(aryl) product 3a-Y2, which was authenticated by NMR spectroscopy and X-ray crystallography. The mechanism of its formation was studied by DFT computations and presumably involves a cooperative reorganization process within the nonsymmetric parent 2a-Y2 to afford a symmetric isomer prior to its reaction with 2-phenylpyridine.
链接：//pubs.acs.org/doi/10.1021/acs.inorgchem.4c01111
