Reactions of Os3(CO)10(μ-H)2 with 1,8-Bis(ferrocenyl)octatetrayne Yield Products Involving Cyclizations and Trans-Hydrogenation of Alkyne Groups
Reactions of Os3(CO)10(μ-H)2 with 1,8-Bis(ferrocenyl)octatetrayne Yield Products Involving Cyclizations and Trans-Hydrogenation of Alkyne Groups
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Os3(CO)10(μ-H)2 与 1,8-双(二茂铁基)辛四炔的反应产生涉及炔基环化和反式氢化的产物
DOI：
10.1021/om020447b
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发表时间：
2002
期刊：
影响因子：
2.8
通讯作者：
Mark D. Smith
中科院分区：
文献类型：
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作者：
R. D. Adams;and Bo Qu;Mark D. Smith
1，8-二(二茂铁基)八氢呋喃(1)与Os_3(CO)_10(μ-H)_2(2)反应，合成了三个新的含两个电活性二茂铁基的Os簇合物： OS_3(CO)_9(μ_3，η_3-FcCCHC4COC_⋮)(μ-H)(3)，OS_3(CO)_10(μ_3，η_2-E-FcCHCHC2−C⋮C−C_⋮_ffc)(4)和Os_6(CO)_20(μ_3，μ_3-η_2-η_2-E，E-FcCCHC2−_C2CHCHFc)(5)。用红外光谱、核磁共振氢谱和单晶X-射线衍射法对三个化合物进行了结构表征。在化合物3中，四炔链偶联到CO配体上，并环化形成一个八元杂双环，其中包含两个五元环，这些环连接了三个Os原子的闭合簇合物。化合物4含有一个三角形的三铯簇合物。化合物5含有两个三角形的三铯簇合物。在4和5中，两个氢化物配体都从簇团转移到了炔基上，形成了具有E-立体化学的烯基。提出了双金属位上反式加氢的反应机理。循环伏安和差示脉冲伏安测试表明，该电极有两个可逆单电极。
The reaction of 1,8-bis(ferrocenyl)octatetrayne (1) with Os3(CO)10(μ-H)2 (2) yielded three new osmium cluster complexes containing two electroactive ferrocenyl groups: Os3(CO)9(μ3,η3-FcCCHC4COC⋮CFc)(μ-H) (3); Os3(CO)10(μ3,η2-E-FcCHCHC2−C⋮C−C⋮CFc) (4); and Os6(CO)20(μ3,μ3-η2-η2-E,E-FcCHCHC2−C2CHCHFc) (5). All three compounds were characterized by IR, 1H NMR, and single-crystal X-ray diffraction analyses. In compound 3, the tetrayne chain was coupled to a CO ligand and cyclized to form an eight-membered heterobicycle containing two five-membered rings that bridges a closed cluster of three osmium atoms. Compound 4 contains one triangular triosmium cluster. Compound 5 contains two triangular triosmium clusters. In both 4 and 5, both the hydride ligands were transferred from the cluster to an alkyne group to form an olefinic group with E-stereochemistry. A mechanism for trans-hydrogenation at a bimetallic site is proposed. Cyclic and differential pulse voltammetric measurements show two reversible one-electr...