Pentamethylcyclopentadienyl-rhodium and -iridium halides. Part II. Reactions with mono-, di-, and tri-olefins
Pentamethylcyclopentadienyl-rhodium and -iridium halides. Part II. Reactions with mono-, di-, and tri-olefins
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五甲基环戊二烯基铑和五甲基环戊二烯基铱的卤化物。
DOI：
10.1039/j19700002875
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发表时间：
1970
期刊：
影响因子：
--
通讯作者：
P. Maitlis
中科院分区：
文献类型：
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作者：
K. Moseley;J. Kang;P. Maitlis
二聚体二氯甲基环戊二烯-Rh和-Ir的配合物[{M(C5Me5)Cl2}2]在碳酸钠的存在下与丁二烯、环庚三烯和6，6-二苯基富烯在乙醇中反应，得到了π-1-甲基烯丙基、π-环七-2，4-二烯和(1，1-二苯甲基)环戊二烯的五甲基环戊二烯-Rh(III)或-Ir(III)配合物。在与[{Rh(C5Me5)Cl2}2]相似的反应条件下，降冰片二烯和双环戊二烯生成五甲基环戊二烯-Rh(I)二烯配合物；乙烯生成双(乙烯)-Rh(I)和-Ir(I)配合物。在这些反应中含有氢化物中间体，并分离和表征了氢化物和重氢-氯(三苯基膦)五甲基环戊二烯的配合物。对于环戊二烯，[{Rh(C5Me5)Cl2}2]给出了阳离子和(cyclopentadienyl)-endo-H-pentamethylcyclopentadienerhodium(I).(Cyclopentadienyl)exo-H-pentamethylcyclopentadienerhodium(I)是用硼氢化钠还原[Rh(C5Me5)(C5H5)]+得到的，其活性远高于Endo-H-异构体。用卤代剂[Rh(C5Me5)(C5H5)]+生成[Rh(C5Me5)(C5H5)]+，而内-H-异构体裂解成[{Rh(C5Me5)X2}2]和[{Rh(C5H5)X2}2]。[{Ir(C5Me5)Cl2}2]与环戊二烯反应只生成[Ir(C5Me5)(C5H5)]+阳离子，还原时生成两种异构体的混合物exo-H-[Ir(C5Me5H)(C5H5)]和[Ir(C5Me5)(C5H6)]。记录了一些新的络合物和(C5Me5H)的质谱图。
The dimeric dichloropentamethylcyclopentadienyl-rhodium and -iridium complexes, [{M(C5Me5)Cl2}2], reacted in ethanol in the presence of sodium carbonate with butadiene, cycloheptatriene, and 6,6-diphenylfulvene, giving pentamethylcyclopentadienyl-rhodium(III) or -iridium(III) complexes of π-1-methylallyl, π-cyclohepta-2,4-dienyl, and (1,1-diphenylmethyl) cyclopentadienyl. Under similar conditions with [{Rh(C5Me5)Cl2}2], norbornadiene and dicyclopentadiene gave pentamethylcyclopentadienyl-rhodium(I) diene complexes; ethylene gave bis(ethylene)-rhodium(I) and -iridium(I) complexes. A hydrido-intermediate is implied in these reactions and both the hydrido- and deuterio-chloro(triphenyl phosphine) pentamethylcyclopentadienyliridium complexes were isolated and characterised. With cyclopentadiene, [{Rh(C5Me5)Cl2}2] gave the cation and (cyclopentadienyl)-endo-H-pentamethylcyclopentadienerhodium(I). (Cyclopentadienyl)exo-H-pentamethylcyclopentadienerhodium(I) was obtained by reduction of [Rh(C5Me5)(C5H5)]+ with sodium borohydride and was much more reactive than the endo-H-isomer. With halogenating agents [Rh(C5Me5)(C5H5)]+ was the product, whereas the endo-H-isomer underwent cleavage to [{Rh(C5Me5)X2}2] and [{Rh(C5H5)X2}2]. [{Ir(C5Me5)Cl2}2] reacted with cyclopentadiene to give only the [Ir(C5Me5)(C5H5)]+ cation, which on reduction, gave a mixture of two isomers, exo-H-[Ir(C5Me5H)(C5H5)] and [Ir(C5Me5)(C5H6)]. The mass spectra of some new complexes and of (C5Me5H) are recorded.