The potential of a cyclo-As5 ligand complex in coordination chemistry
The potential of a cyclo-As5 ligand complex in coordination chemistry
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DOI：
10.1039/c0sc00254b
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发表时间：
2010-09-01
期刊：
影响因子：
8.4
通讯作者：
Scheer, Manfred
中科院分区：
文献类型：
--
作者：
Krauss, Hannes;Balazs, Gabor;Scheer, Manfred
的反应(Cp *菲(η(5)5)](1)与Cu-I卤化物导致1 d-polymeric化合物的形成[{铜(μX)} (3) (CH3CN) {Cp *菲(η(5):η(2):埃塔(2):埃塔(2)5)}](n) (X = Cl (2), Br(3)),[{铜(μ(3)- i)} (2) {Cp *菲(η(5):η(2):埃塔(2)5)}](n)(4)和({铜(μi)}(3){崔}{Cp *菲(η(5):η(2):埃塔(2):埃塔(1):埃塔(1)和5)}{Cp *菲(η(5):η(5):埃塔(2)5)}](n)(5)。聚合物是通过环As-5环与（CuX）(n)基团的pi配位形成离散单元，并通过弱分子间As中心点中心点中心点Cu的sigma相互作用连接而成。只有聚合物4是一个例外，它显示了一个（CuI）(n)阶梯，由1分子交替配位。在聚合物5的侧臂中，在环as -5环下方发现了一种新的eta(5)配位，显示出一种前所未有的杂电性三层夹层配合物，中间层是多砷。所有产品均通过单晶x射线结构分析表征。为了定义1和它的磷类似物[Cp*Fe(eta(5)-P-5)] （1a）的配位行为的差异，描述了DFT计算。
The reaction of [Cp*Fe(eta(5)-As-5)] (1) with Cu-I halides leads to the formation of the 1D-polymeric compounds [{Cu(mu-X)}(3)(CH3CN){Cp*Fe(eta(5):eta(2):eta(2):eta(2)-As-5)}](n) (X = Cl (2), Br (3)), [{Cu(mu(3)-I)}(2){Cp*Fe(eta(5):eta(2):eta(2)-As-5)}](n) (4) and [{Cu(mu-I)}(3){CuI}{Cp*Fe(eta(5):eta(2):eta(2):eta(1):eta(1)-As-5)}{Cp*Fe(eta(5):eta(5):eta(2)-As-5)}](n) (5). The polymers are built up by the pi-coordination of the cyclo-As-5 ring to (CuX)(n) moieties forming discrete units, which are additionally linked by weak intermolecular As center dot center dot center dot Cu sigma-interactions. Only polymer 4 is an exception revealing a (CuI)(n) ladder which is alternately coordinated by molecules of 1. In a side arm of polymer 5 a novel eta(5)-coordination of a Cu atom below the cyclo-As-5 ring is found, showing an unprecedented heteroleptic triple-decker sandwich complex with a polyarsenic middle-deck. All products are characterised by single crystal X-ray structure analysis. To define the differences in the coordination behaviour of 1 and its phosphorus analogue [Cp*Fe(eta(5)-P-5)] (1a), DFT calculations are described.