Reactions of zirconocene 2-vinylpyridine complexes with diisobutylaluminum hydride and fluoride

Reactions of zirconocene 2-vinylpyridine complexes with diisobutylaluminum hydride and fluoride
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DOI:
10.1021/om049589r
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发表时间:
2004-09-27
期刊:
影响因子:
2.8
通讯作者:
Weiss, T
Weiss, T
中科院分区:
化学2区
文献类型:
--
作者:
Arndt, P;Spannenberg, A;Weiss, T

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在茂锆2-乙烯基吡啶配合物Cp 2 Zr(2-vipy)(1)与(Bu 2AlH)-Bu-i和(Bu 2AlF)-Bu-i的反应中,形成了同构配合物[Cp 2 Zr(mu-eta(1):eta(2)-2-CH 2CH-C5 H4 N)(mu-H)][(Bu 2Al)-Bu-i](3)和[Cp 2 Zr(mu-eta(1):eta(2)-2-CH 2CH-C5 H4 N)(mu-H)][(Bu 2Al)-Bu-i](5)。这些络合物可以用作在外消旋-(ebthi)ZrF 2与(Bu 2AlH)-Bu 1反应形成二聚络合物[外消旋-(ebthi)ZrH(μ-H)](2)(6)中发现的氟从锆转移到铝(Zr-F与Al-H转移到Zr-H和Al-F)的模型。这些化合物对于理解(Bu 3Al)-Bu-i对二茂锆氟络合物的活化以及iBu 2AlH在烯烃催化聚合的活化过程中的作用是重要的。
In reactions of the zirconocene 2-vinylpyridine complex Cp2Zr(2-vipy) (1) with (Bu2AlH)-Bu-i and (Bu2AlF)-Bu-i the isostructural complexes [Cp2Zr(mu-eta(1):eta(2)-2-CH2CH-C5H4N)(mu-H)][(Bu2Al)-Bu-i] (3) and [Cp2Zr(mu-eta(1):eta(2)-2-CH2CH-C5H4N)(mu-H)][(Bu2Al)-Bu-i] (5) were formed. These complexes can serve as models for the transfer of fluorine from zirconium to aluminum (Zr-F with Al-H to Zr-H and Al-F) found in the reaction of rac-(ebthi)ZrF2 with (Bu2AlH)-Bu-i to form the dimeric complex [rac-(ebthi)ZrH(mu-H)](2) (6). The compounds are important in obtaining an understanding of the activation of zirconocene fluoro complexes by (Bu3Al)-Bu-i and of the role of iBu2AlH in activation processes for the catalytic polymerization of olefins.