(η(5)-C5Me5)Co(2,3-Et2C2B4H3-5-Cl) | 169780-49-8

• 英文名称: (η(5)-C5Me5)Co(2,3-Et2C2B4H3-5-Cl)
• CAS: 169780-49-8
• 化学式: C₁₆H₂₈B₄ClCo
• 分子量: 358.089
• InChiKey: MHDAPASEWZUJGK-XWPLVQGESA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  (η(5)-C5Me5)Co(2,3-Et2C2B4H3-5-Cl) 在 n-butyllithium 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以56%的产率得到
  参考文献：
  名称：

  有机过渡金属金属碳硼烷。41. BB和Cp * -Cp *连接的钴碳硼烷簇的合成和结构

  摘要：

  In an application of Wurtz-type coupling reactions to metallacarborane chemistry, treatment of the B(5)-halogenated close complexes Cp*Co(2,3-Et(2)C(2)B(4)H(3)-5-X) (X = Cl, Br, I; Cp* = eta(5)-C(5)Me(5)) with sodium metal in THF gave a single red-orange, air-stable product in 20-34% isolated yield. This species was characterized via NMR, UV-visible and mass spectroscopy and X-ray crystallography as a B-B-linked dimer, 5,5'-[Cp*CO(Et(2)C(2)B(4)H(3))](2) (2). Reactions of the same halogenated monomers, as well. as the parent complex (X = H), with alkyllithium reagents in THF generated in 28-56% yield the orange, air-stable dimeric products [(-CH(2)C(5)Me(4))Co(Et(2)C(2)B(4)H(3)-5-X)](2) (3a-d; X = H, Cl, Br, I), which are linked via Cp*-Cp* connections. This geometry, apparently novel to metallacarborane chemistry, was established by an X-ray diffraction study on 3c and supported by spectroscopic data for the four species. Decapitation of these dimers in wet TMEDA gave in high yield the corresponding nido complexes [(-CH(2)C(5)Me(4))Co(Et(2)C(2)B(3)H(4)-5-X)]2 (4a-d; X = H, Cl, Br, I) as air-stable yellow solids. In contrast, 2 was unaffected by similar treatment. The reaction of nido-Cp*Co(Et(2)C(2)B(3)H(4)-5-Cl) with sodium in THF gave the yellow air-stable dimeric species [Cp*Co(Et(2)C(2)B(3)H(4))]2 (8) together with the unsubstituted monomer Cp*Co(Et(2)C(2)B(3)H(5)), a previously characterized complex. An X-ray crystal structure determination on 8 disclosed that the two CoC2B3 units are connected via a B-B-B three-center bond such that the two C2B3 rings are almost mutually perpendicular.

  DOI：

  10.1021/om00010a034
• 作为产物：
  描述：

  (η5-C5Me5)Co(Et2C2B4H4) 、 氯 以 二氯甲烷 为溶剂， 以97%的产率得到(η(5)-C5Me5)Co(2,3-Et2C2B4H3-5-Cl)
  参考文献：
  名称：

  Organotransition-Metal Metallacarboranes. 40. Regiospecific Halogenation of Transition-Metal Small Carborane Complexes

  摘要：

  Methods for efficient, controlled direct halogenation of C2B3 and C2B4 carborane ligands in neutral nido- and closo-metallacarborane sandwich complexes are described. In an extension of our earlier work in this area, reactions of nido-Cp'Co(2,3-Et(2)C(2)B(3)H(5)) (CP' = Cp*, Cp; Cp* = eta(5)-C(5)Me(5)) With N-halosuccinimides placed Cl, Br, or I substituents on B(4) and/or B(6) but not on the middle boron (B(5)). In contrast, similar treatment of closo-LM-(2,3-Et(2)C(2)B(4)H(4)) species in which LM is Cp'Co, Cp*FeH, (eta(6)-C8H10)Fe, or (eta(6)-MeC(6)H(4)CHMe(2))-Ru gave only B(5)-monohalogen products. However, the triple-decker sandwich complex CpCo(2,3-Et(2)C(2)B(3)H(5))CoCp was readily tribrominated by N-bromosuccinimide. Reactions of Cp'CO(Et(2)C(2)B(4)H(4)) with Cl-2 rapidly formed the respective B(5)-Cl derivatives, which in turn were converted to the B(4,5,6)-Cl-3 species; analogous reactions with Br-2 and I-2 were much slower and gave essentially only B(5)-monosubstituted products. The Cp'Co(Et(2)C(2)B(4)H(3)-5-X) derivatives (X = Cl, Br, I) were decapitated with TMEDA to give the corresponding nido-Cp'Co(Et(2)C(2)B(3)H(4)-5-X) products. The reaction of Cp*(FeH)-H-II(Et(2)C(2)B(4)H(4)) with TMEDA was found to both deprotonate and decapitate the complex, affording respectively Cp*Fe-III-(Et(2)C(2)B(4)H(4)) and the previously unknown nido-Cp*Fe-III-(Et(2)C(2)B(3)H(5)) complex. The new compounds were isolated via column chromatography and obtained in most cases as air-stable colored crystalline solids, characterized via multinuclear NMR, FTIR and mass spectroscopy.

  DOI：

  10.1021/om00010a033