Group 4 metal complexes with new chiral pincer NHC-ligands: synthesis, structure and catalytic activity.
Chiral group 4 NHC-metal complexes were prepared in good yields by amine elimination from M(NR2)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(NR2)4 with 1 equiv. of L4 in THF gives, after recrystallization from a benzene solution, the chiral titanium amides (L4)Ti(NMe2)(Br)(THF) (7) and (L4)Ti(NMe2)(Cl)(THF) (11), zirconium amides (L4)Zr(NMe2)(Br)(THF) (8), (L4)Zr(NEt2)(Br)(THF) (10), (L4)Zr(NMe2)(Cl)(THF) (12) and (L4)Zr(NEt2)(Cl)(THF) (14), and hafnium amides (L4)Hf(NMe2)(Br)(THF) (9) and (L4)Hf(NMe2)(Cl)(THF) (13), respectively. Similarly, the reactions of L5 or L6 with 1 equiv. of M(NR2)4 yield the titanium amide (L6)Ti(NMe2)(Cl)(THF) (16), the zirconium amides (L5)Zr(NMe2)(Cl)(THF) (15), (L6)Zr(NMe2)(Cl)(THF) (17) and (L6)Zr(NEt2)(Cl)(THF) (19), and the hafnium amide (L6)Hf(NMe2)(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.
Department of Chemistry, Beijing Normal University, Beijing 100875, China. gzi@bnu.edu.cn.
Ning
N
Zhao
Guohua
G
Hou
Xuebin
X
Deng
Guofu
G
Zi
Marc D
MD
Walter
D002384:Catalysis; D056831:Coordination Complexes / Q000138:chemical synthesis* / Q000737:chemistry; D018360:Crystallography, X-Ray; D006195:Hafnium / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000737:chemistry*; D008024:Ligands; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D015394:Molecular Structure; D014025:Titanium / Q000737:chemistry*; D015040:Zirconium / Q000737:chemistry*
D056831:Coordination Complexes; D006571:Heterocyclic Compounds; D008024:Ligands; C030011:carbene; D015040:Zirconium; D014025:Titanium; D008697:Methane; D006195:Hafnium