NDLI: Group 4 metal complexes with new chiral pincer NHC-ligands: synthesis, structure and catalytic activity

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Group 4 metal complexes with new chiral pincer NHC-ligands: synthesis, structure and catalytic activity

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Deng, Xuebin Zi, Guofu Walter, Marc D. Hou, Guohua Zhao, Ning
Description	Author Affiliation: Zhao N ( Department of Chemistry, Beijing Normal University, Beijing 100875, China. gzi@bnu.edu.cn.)
Abstract	Chiral group 4 NHC–metal complexes were prepared in good yields by amine elimination from $M(NR_{2})_{4}$ (M = Ti, Zr, Hf; R = Me, Et) and chiral pincer NHC-ligands, L4 (L4a and L4b), L5 and L6, which are derived from (S,S)-diphenyl-1,2-ethanediamine. Treatment of $M(NR_{2})_{4}$ with 1 equiv. of L4 in THF gives, after recrystallization from a benzene solution, the chiral titanium amides $(L4)Ti(NMe_{2})(Br)(THF)$ (7) and $(L4)Ti(NMe_{2})(Cl)(THF)$ (11), zirconium amides $(L4)Zr(NMe_{2})(Br)(THF)$ (8), $(L4)Zr(NEt_{2})(Br)(THF)$ (10), $(L4)Zr(NMe_{2})(Cl)(THF)$ (12) and $(L4)Zr(NEt_{2})(Cl)(THF)$ (14), and hafnium amides $(L4)Hf(NMe_{2})(Br)(THF)$ (9) and $(L4)Hf(NMe_{2})(Cl)(THF)$ (13), respectively. Similarly, the reactions of L5 or L6 with 1 equiv. of $M(NR_{2})_{4}$ yield the titanium amide $(L6)Ti(NMe_{2})(Cl)(THF)$ (16), the zirconium amides $(L5)Zr(NMe_{2})(Cl)(THF)$ (15), $(L6)Zr(NMe_{2})(Cl)(THF)$ (17) and $(L6)Zr(NEt_{2})(Cl)(THF)$ (19), and the hafnium amide $(L6)Hf(NMe_{2})(Cl)(THF)$ (18), respectively. Complexes 7–19 were characterized by various spectroscopic techniques and elemental analyses. The molecular structures of 10 and 14–19 were also established by X-ray diffraction analyses, which represent the first example of the structurally characterized group 4 chiral NHC–metal complex. Furthermore, 7–19 are active catalysts for the polymerization of rac-lactide in the presence of isopropanol, leading to the heterotactic-rich polylactides.
ISSN	14779226
Issue Number	22
Volume Number	43
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2014-06-14
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Coordination Complexes Chemical Synthesis Hafnium Chemistry Heterocyclic Compounds Methane Analogs & Derivatives Titanium Zirconium Catalysis Crystallography, X-Ray Ligands Molecular Structure Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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