Mono- and di-cyclopentadienyl zirconium derivatives containing the dimethylsilylcyclopentadienyl ligand. Agostic linear Si–H–Zr interaction in the molecular structure of [Zr{η5-C5H4(SiMe2H)}Cl3]2
Mono- and di-cyclopentadienyl zirconium derivatives containing the dimethylsilylcyclopentadienyl ligand. Agostic linear Si–H–Zr interaction in the molecular structure of [Zr{η5-C5H4(SiMe2H)}Cl3]2
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[Zr{η5-C5H4(SiMe2H)}Cl3]2 分子结构中含有二甲基甲硅烷基环戊二烯基配体的单环戊二烯基锆衍生物。
DOI：
10.1039/b010221k
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发表时间：
2001
期刊：
影响因子：
--
通讯作者：
Avelino Martín
中科院分区：
文献类型：
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作者：
Gemma Ciruelo;T. Cuenca;R. Gómez;P. Gómez;Avelino Martín
合成了二甲基硅基取代的单、双取代氯化锆，研究了它们与氨基、烷基试剂的反应。甲硅烷基环戊二烯C5 H5（SiMe 2 H）1、C5 H4（SiMe 2 H）22和C5 H4（SiMe 3）（SiMe 2 H）3可以通过Na（C5 H5）与适当的氯硅烷试剂反应来制备。锂盐Li[C5 H4（SiMe 2 H）]与ZrCl 4或[Zr（C5 H5）Cl 3]反应生成茂金属配合物[Zr（C5 H4 R）{C5 H4（SiMe 2 H）} Cl 2]（R = SiMe 2 H4或H5），而二甲硅烷基环戊二烯C5 H4（SiMe 2 H）2与ZrCl 4反应生成单环茂金属配合物[Zr{C5 H4（SiMe 2 H）} Cl 3] 6，它交换了Si-H和Zr-Cl键。6与氨基锂的反应产生不同的产物，这取决于氮原子的碱性和其氨基取代基的空间需求。与LiN（SiMe 3）2和LiNH（2，6-Me 2C 6 H3）反应得到相应的氨基锆配合物[Zr{C5 H4（SiMe 2 H）}（NRR′）Cl 2]（R = R′ = SiMe 37; R = H，R′ = 2，6-Me 2C 6 H38），但在与LiNHtBu反应的情况下，形成已知的环戊二烯基甲硅烷基氨基衍生物[Zr（η5，η1-C5 H4 SiMe 2NtBu）Cl 2]。通过4和5与适当的氨基或甲基试剂反应，合成了单氨基、二氨基和二烷基二环己基配合物[Zr（C5 H4 R）{C5 H4（SiMe 2 H）}X（Y）]（R = SiMe 2 H9或H10，X = Cl，Y = NHtBu; R = SiMe 2 H11或H12，X = Y = NHtBu; R = SiMe 2 H13或H14，X = Y = Me）.化合物9与化学计量的水反应，Zr-酰胺键选择性水解，得到相应的μ-氧代双核配合物[{Zr[C5 H4（SiMe 2 H）]2Cl}2（μ-O）] 15。[Zr{C5 H4（SiMe 2 H）} Cl 3] 6的分子结构由X射线晶体学确定。化合物6是固态的二聚体，其中二聚化通过Zr-H-Si agostic相互作用和两个氯桥发生。
Dimethylsilyl substituted mono- and di-cyclopentadienyl zirconium chlorides have been prepared and their reactions with amido and alkyl reagents studied. The silylcyclopentadienes C5H5(SiMe2H) 1, C5H4(SiMe2H)22 and C5H4(SiMe3)(SiMe2H) 3 can be prepared by reaction of Na(C5H5) with the appropriate chlorosilane reagent. The lithium salt Li[C5H4(SiMe2H)] reacts with ZrCl4 or [Zr(C5H5)Cl3] to give the metallocene complexes [Zr(C5H4R){C5H4(SiMe2H)}Cl2] (R = SiMe2H 4 or H 5) whereas the reaction of the disilylcyclopentadiene C5H4(SiMe2H)2 with ZrCl4 afforded the monocyclopentadienyl complex [Zr{C5H4(SiMe2H)}Cl3] 6, which exchanges the Si–H and Zr–Cl bonds. The reaction of 6 with lithium amides produces different products depending on the basicity of the nitrogen atom and the steric demands of its amido substituents. The reaction with LiN(SiMe3)2 and LiNH(2,6-Me2C6H3) afforded the corresponding amido zirconium complexes [Zr{C5H4(SiMe2H)}(NRR′)Cl2] (R = R′ = SiMe37; R = H, R′ = 2,6-Me2C6H38), but in the case of the reaction with LiNHtBu the known cyclopentadienylsilylamido derivative [Zr(η5,η1-C5H4SiMe2NtBu)Cl2] was formed. The monoamido, diamido and dialkyl dicyclopentadienyl complexes [Zr(C5H4R){C5H4(SiMe2H)}X(Y)] (R = SiMe2H 9 or H 10, X = Cl, Y = NHtBu; R = SiMe2H 11 or H 12, X = Y = NHtBu; R = SiMe2H 13 or H 14, X = Y = Me) have been synthesized by reaction of 4 and 5 with the appropriate amido or methyl reagent. Compound 9 reacts with a stoichiometric amount of water with selective hydrolysis of the Zr–amido bond to give the corresponding μ-oxo dinuclear complex [{Zr[C5H4(SiMe2H)]2Cl}2(μ-O)] 15. The molecular structure of [Zr{C5H4(SiMe2H)}Cl3] 6 was established by X-ray crystallography. Compound 6 is a dimer, in the solid state, in which dimerization occurs through Zr–H–Si agostic interactions and two chloride bridges.