New zirconium and zirconocene guanidinate complexes

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• 作者：Rafael Ferná ; ndez-Galá ; n ^{Rafael.fgalan@uclm.es} ; Antonio Antiñ ; olo ; ^{Antonio.Antinolo@uclm.es} ; Fernando Carrillo-Hermosilla ; Isabel Ló ; pez-Solera ; Antonio Otero ; Amparo Serrano-Laguna ; Elena Villaseñ ; or
• 关键词：Guanidine ; Lithium salts ; Zirconium ; Zirconocene complexes ; Coordination
• 刊名：Journal of Organometallic Chemistry
• 出版年：2012
• 期刊代码：64_0022328x
• 类别：ch
• 出版时间：15 July, 2012
• 卷：711
• 期：Complete
• 页码：35-42
• 文件大小：541 K

摘要

The guanidines (HNi-Pr)₂CNAr (Ar聽=聽4-t-BuC₆H₄ 1, 4-BrC₆H₄ 2 and 2,4,6-Me₃C₆H₂ 3) have been used in the synthesis of the lithium salts [Li{i-PrN(HNiPr)CNAr}(THF)]₂ 4-6 and [Li₂{(Ni-Pr)₂CNAr}] 7-9. Complexes [Zr{魏²,N,N鈥?(Ni-Pr)(NAr)CNH(i-Pr)}₂Cl₂] (Ar聽=聽4-t-BuC₆H₄ 10, 4-BrC₆H₄ 11, 2,4,6-Me₃C₆H₂ 12), which contain an asymmetrical monoanionic guanidinate ligand coordinated to the zirconium atom, were obtained by protonolysis of 1-3 in the presence of NEt₃ or by a metathesis reaction of 4-6 with ZrCl₄. The zirconocene complexes [Zr(畏⁵-C₅H₅)₂{魏²,N,N鈥?(Ni-Pr)(NAr)CNH(i-Pr)}Cl] (Ar聽=聽4-t-BuC₆H₄ 13, 4-BrC₆H₄ 14, 2,4,6-Me₃C₆H₂ 15) and [Zr(畏⁵-C₅H₅)₂{魏²,N,N鈥?(Ni-Pr)₂CNAr}] (Ar聽=聽4-t-BuC₆H₄ 16, 4-BrC₆H₄ 17, 2,4,6-Me₃C₆H₂ 18) were synthesized by metathesis reactions of the corresponding lithium salts and Zr(畏⁵-C₅H₅)₂Cl₂. Complexes 16-18 exhibit dynamic behavior in solution and this was studied by variable-temperature NMR experiments. The molecular structures of 4 and 10 were determined by single-crystal X-ray diffraction.