Unexpected Differences in the Coordination Behaviour of 1,2,4-Triphosphaferrocenes towards CuI Chloride
Unexpected Differences in the Coordination Behaviour of 1,2,4-Triphosphaferrocenes towards CuI Chloride
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DOI：
10.1002/ejic.200800852
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发表时间：
2008-11-01
影响因子：
2.3
通讯作者：
Scheer, Manfred
中科院分区：
文献类型：
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作者：
Deng, Shining;Schwarzmaier, Christoph;Scheer, Manfred
1，2，4-三磷二茂铁[FeCpR(ETA(5)-P(3)C(2)Tbu(2))][Cp-R=Cp(1)，Cp‘(2)]对氯化铜的配位行为受铁上环戊二烯取代方式的影响。二聚铜配合物[{FeCp(eta(5)：eta(1)：eta(1)-p(3)tBu(2)C(2))}{Mu-CuCl-(MeCN)}(2)(3)和[{FeCp‘(eta(5)：eta(1)：eta(1)-P(3)tBu(2)C(2))}(mu-CuCl)](2)(4)，其中两个1，2，41-三磷二茂铁通过两个CuCL中心连接形成二聚体络合物，按1：1化学计量比反应得到。而在3中发现了一个四配位的铜原子，而4由于更大的Cp‘’的空间效应而具有一个三配位的铜原子。莱兰德。然而，如果在CP衍生物1的1：2化学计量比中以过量的CuCL进行反应，则得到相同的产物3，而在三叔丁基取代的CP‘’配体配合物2的情况下，在温和的条件下，三磷醇环在铁三层夹心配合物[{FeCp‘](2)(u，Eta(4)：eta(4)：eta(1)：eta(1)-P-4)}(mu-CuCl(MeCN)}](infinity)(5)包埋在CuCl2聚合物基质中。(C)Wiley-VCH Verlag GmbH&Co.KGaA，69451，德国温海姆)
The coordination behaviour of 1,2,4-triphosphaferrocenes [FeCpR(eta(5)-P(3)C(2)tBu(2))] [Cp-R = Cp (1), Cp''' (2)] towards Cu-I chloride is significantly influenced by the substitution pattern of the cyclopentadienyl ring attached to iron. The dimeric copper complexes [{FeCP(eta(5):eta(1):eta(1)-p(3)tBu(2)C(2))} {mu-CuCl-(MeCN)}(2) (3) and [{FeCp''' (eta(5):eta(1):eta(1)-P(3)tBu(2)C(2))}(mu-CuCl)](2) (4), in which two 1,2,41-triphosphaferrocenes are linked by two CuCl centres to form dimeric complexes were obtained in reactions using a 1:1 stoichiometry. Whereas in 3 a tetracoordinated Cu atom is revealed, 4 possesses a threefold-coordinated Cu atom due to the steric influence of the bulkier Cp'''. ligand. However, if the reaction is carried out with an excess of CuCl in a 1:2 stoichiometry for the Cp derivative 1 the same product 3 is obtained, whereas in the case of a tri-tert-butyl-substituted Cp''' ligand complex 2 the triphospholyl ring is fragmented tinder mild conditions to a tetrdphosphabutadiene moiety within an iron triple-decker sandwich complex [{FeCp''')(2) (mu,eta(4):eta(4):eta(1):eta(1)-P-4)}(mu-CuCl(MeCN)}](infinity) (5) embedded in a CuCl polymer matrix. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)