Benzothiazolin-2-ylidene Complexes of Iridium(I)
Benzothiazolin-2-ylidene Complexes of Iridium(I)
复制标题
铱(I) 苯并噻唑啉-2-亚基配合物
DOI：
10.1021/om060006i
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发表时间：
2006
期刊：
影响因子：
2.8
通讯作者：
F. Hahn
中科院分区：
文献类型：
--
作者：
H. Huynh;Nicole Meier;T. Pape;F. Hahn
烯丙基溴与苯并噻唑在整齐条件下反应，得到高产率的3-（2-丙烯基）苯并噻唑溴（H-1）Br。试图通过(H-1)+去质子合成相应的碳二聚体，分离出重排产物2,3-二（2-丙烯）-2 ',3 ' -二氢-2,2 ' -双苯并噻唑(2)。[Ir(μ-OMe)(cod)]2与盐（H-1）Br反应得到[IrBr(cod)（苯并噻唑）](3)（cod = 1,5-环二烯），其中含有n -配位的未取代苯并噻唑配体。通过(H-1)+的烯丙基取代基与[Ir(cod)(MeCN)2]BF4的预配位，并在(H-1)+的C2位置加碱去质子，IrI与苯并噻唑啉-2-基配体形成羰基配合物。使用NaH作为外碱得到了带有n -丙基取代的羰基配体的方形平面IrI配合物4，而与KOtBu脱质子得到了五配位IrI配合物[IrBr(cod)(η - 2-1)], 5。位移…
The reaction of allyl bromide with benzothiazole under neat conditions furnished 3-(2-propenyl)benzothiazolium bromide, (H-1)Br, in high yield. Attempts to synthesize the corresponding carbene dimer by deprotonation of (H-1)+ led to the isolation of the rearrangement product 2,3-di(2-propenyl)-2‘,3‘-dihydro-2,2‘-bisbenzothiazole (2). The reaction of [Ir(μ-OMe)(cod)]2 with the salt (H-1)Br unexpectedly afforded [IrBr(cod)(benzothiazole)] (3) (cod = 1,5-cyclooctadiene), which contained an N-coordinated unsubstituted benzothiazole ligand. The formation of carbene complexes of IrI with the benzothiazolin-2-ylidene ligand could be achieved via precoordination of the allyl substituent of (H-1)+ to [Ir(cod)(MeCN)2]BF4 and subsequent deprotonation at the C2 position of (H-1)+ by addition of base. The use of NaH as external base yielded the square planar IrI complex 4 with an N-propyl-substituted carbene ligand, while deprotonation with KOtBu gave the five-coordinated IrI complex [IrBr(cod)(η2-1)], 5. Displacement...