Reactivity of co-ordinated ligands. Part XX. Preparation and reactions of cyclo-octadiene complexes of iron, ruthenium, and osmium
Reactivity of co-ordinated ligands. Part XX. Preparation and reactions of cyclo-octadiene complexes of iron, ruthenium, and osmium
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配位配体的反应性。
DOI：
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发表时间：
1974
期刊：
影响因子：
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通讯作者：
Jack Lewis
中科院分区：
文献类型：
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作者：
A. Deeming;S. Ullah;Antonio J. P. Domingos;B. Johnson;Jack Lewis
合成了三羰基（η-环辛-1，5-二烯）钌（Ⅰ）和三羰基（η-环辛-1，3-二烯）锇（Ⅱ）配合物，研究了它们的反应活性，并与相应的铁配合物进行了比较。与Ph_3CBF_4反应，发生脱离子反应，得到环辛二烯鎓配合物[（C_8H_（11）M（CO）_3]~+。它们与阴离子亲核试剂反应生成中性配合物，其中一些含有η-烯丙基和金属-碳σ-键。研究了环辛-1，5-二烯的催化异构化反应以及二烯配合物的催化异构化反应，在一种情况下观察到一种新的缩环反应。对于铁和钌的η-烯丙基络合物，已经观察到羰基配体被PPh 3取代，并且还描述了羰基化反应以得到双环[4.2.1]壬-2-烯-9-酮。
The complexes tricarbonyl(η-cyclo-octa-1,5-diene)ruthenium, (I), and tricarbonyl(η-cyclo-octa-1,3-diene)osmium, (II), have been prepared and their reactivities examined and compared to those of the corresponding iron complexes. On reaction with Ph3CBF4 hydride-ion abstraction occurs to give cyclo-octadienylium complexes [(C8H11)M(CO)3]+. These react with anionic nucleophiles to give neutral complexes, some of which contain η-allyl groups and metal–carbon σ-bonds. Catalytic isomerisations of cyclo-octa-1,5-diene have been studied as well as those of the diene complexes, a novel ring contraction being observed in one case. Substitution of a carbonyl ligand by PPh3 has been observed for the η-allyl complexes of iron and ruthenium, and a carbonylation reaction to give bicyclo[4.2.1] non-2-en-9-one is also described.