“Constrained Geometry” Group 3 Metal Complexes of the Fluorenyl-Based Ligands [(3,6-tBu2Flu)SiR2NtBu]: Synthesis, Structural Characterization, and Polymerization Activity
“Constrained Geometry” Group 3 Metal Complexes of the Fluorenyl-Based Ligands [(3,6-tBu2Flu)SiR2NtBu]: Synthesis, Structural Characterization, and Polymerization Activity
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DOI：
10.1021/om0304210
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发表时间：
2003-10
期刊：
影响因子：
2.8
通讯作者：
E. Kirillov;L. Toupet;C. Lehmann;and Abbas Razavi;J. Carpentier
中科院分区：
文献类型：
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作者：
E. Kirillov;L. Toupet;C. Lehmann;and Abbas Razavi;J. Carpentier
Y（CH_2SiMe_3）_3（THF）_2与双质子配体[（3，6-tBu_2Cl_3 H_7）SiR_2NHtBu]（R = Me，1a; R = Ph，1b）发生烷烃消除反应，生成[η_3：η_1-（（3，6-tBu_2Cl_3 H_6）SiR_2NtBu）Y（CH_2SiMe_3）（THF）_2]（R = Me，2a; R = Ph，2b）。2a在甲苯溶液中是热稳定的，并且显示与THF解离相关的动态行为，而2b是热不稳定的。2a与H_2或PhSiH_3反应生成推定的配位络合物“[（3，6-tBu_2Flu）SiMe_2NtBu）YH（THF）]n”（3）。用1和2当量的nBuLi去质子化1a分别得到[（3，6-tBu 2C 13 H6）SiMe 2NHtBu]Li（5）和[（3，6-tBu 2C 13 H6）SiMe 2NtBu] Li 2（4），这两种化合物都进行了晶体学表征。LnCl_3（THF）_n前体之间的盐消除反应（Ln = Y，La，Nd）和1当量的4得到络合物的混合物，从该混合物中得到每个镧系中心含有两个螯合配体的离子络合物，[{η3：η1-η 4}。（3，6-tBu2C13H6）SiMe2NtBu}2Ln]-[Li（solvent）n]+（Ln = Y，solvent = THF，n = 4，6; Ln = La，solvent = THF，n = 4，7; Ln = La，solvent = Et2O，n = 2，8; Ln = Nd，solve.
Alkane elimination between Y(CH2SiMe3)3(THF)2 and the diprotio ligands [(3,6-tBu2C13H7)SiR2NHtBu] (R = Me, 1a; R = Ph, 1b) gave [η3:η1-((3,6-tBu2C13H6)SiR2NtBu)Y(CH2SiMe3)(THF)2] (R = Me, 2a; R = Ph, 2b). 2a is thermally stable in toluene solution and shows a dynamic behavior connected to THF dissociation, while 2b is thermally unstable. Reaction of 2a with H2 or PhSiH3 led to the putative hydrido complex “[(3,6-tBu2Flu)SiMe2NtBu)YH(THF)]n” (3). Deprotonation of 1a with 1 and 2 equiv of nBuLi gave [(3,6-tBu2C13H6)SiMe2NHtBu]Li (5) and [(3,6-tBu2C13H6)SiMe2NtBu]Li2 (4), respectively, both of which were characterized crystallographically. Salt elimination reactions between LnCl3(THF)n precursors (Ln = Y, La, Nd) and 1 equiv of 4 gave mixtures of complexes, from which ionic complexes that contain two chelated ligands per lanthanide center, [{η3:η1-(3,6-tBu2C13H6)SiMe2NtBu}2Ln]-[Li(solvent)n]+ (Ln = Y, solvent = THF, n = 4, 6; Ln = La, solvent = THF, n = 4, 7; Ln = La, solvent = Et2O, n = 2, 8; Ln = Nd, solve...