(η(6)-MeC6H4CHMe2)Ru(2,3-Et2C2B4H4) | 121141-52-4

• 英文名称: (η(6)-MeC6H4CHMe2)Ru(2,3-Et2C2B4H4)
• 英文别名: (p-isopropyltoluene)Ru(Et2C2B4H4)
• CAS: 121141-52-4
• 化学式: C₁₆H₂₈B₄Ru
• 分子量: 364.712
• InChiKey: KZOKZQSGADOPAK-PFFKWKOBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (η(6)-MeC6H4CHMe2)Ru(2,3-Et2C2B4H4) 在 H₂O 作用下， 以 further solvent(s) 为溶剂， 以88%的产率得到(p-isopropyltoluene)Ru(Et2C2B3H5)
  参考文献：
  名称：

  有机过渡金属金属碳硼烷。12. 芳烃-金属-碳硼烷三层三明治。设计合成钴、铁、钌和锇的同质和异质双金属配合物

  摘要：

  本文描述了包含形式环 Et{sub 2}C{sub 2}B{sub 3}H{sub 3}{sup 4{minus}} 桥连配体的三层夹心复合物新家族的系统制备和表征，包括此类的第一个物种，包含第二或第三行过渡金属。通式 (L)M(Et{sub 2}C{sub 2}B{sub 3}H{sub 3})M{prime}(L) (M = Ru, Os; M{prime} = Co ，Ru；L = 伞花烃（对异丙基甲苯）、Cp 或 C{sub 5}Me{sub 5}）通过 (1) Closo-(L)M(Et{sub 2}C) 的合成逐步获得{sub 2}B{sub 4}H{sub 4}) 金属碳硼烷，(2) 这些配合物的斩首（去除顶点 BH）得到 nido-(L)M(Et{sub 2}C{sub 2}B{ sub 3}H{sub 5}), (3) 桥去质子化形成相应的单阴离子或双阴离子，(4)阴离子

  DOI：

  10.1021/ja00195a034
• 作为产物：
  描述：

  (p-cymene)ruthenium(II) chloride 、 Na(1+)Li(1+){nido-2,3-Et2C2B4H4}(2-) 以 四氢呋喃 为溶剂， 以58%的产率得到(η(6)-MeC6H4CHMe2)Ru(2,3-Et2C2B4H4)
  参考文献：
  名称：

  有机过渡金属金属碳硼烷。12. 芳烃-金属-碳硼烷三层三明治。设计合成钴、铁、钌和锇的同质和异质双金属配合物

  摘要：

  本文描述了包含形式环 Et{sub 2}C{sub 2}B{sub 3}H{sub 3}{sup 4{minus}} 桥连配体的三层夹心复合物新家族的系统制备和表征，包括此类的第一个物种，包含第二或第三行过渡金属。通式 (L)M(Et{sub 2}C{sub 2}B{sub 3}H{sub 3})M{prime}(L) (M = Ru, Os; M{prime} = Co ，Ru；L = 伞花烃（对异丙基甲苯）、Cp 或 C{sub 5}Me{sub 5}）通过 (1) Closo-(L)M(Et{sub 2}C) 的合成逐步获得{sub 2}B{sub 4}H{sub 4}) 金属碳硼烷，(2) 这些配合物的斩首（去除顶点 BH）得到 nido-(L)M(Et{sub 2}C{sub 2}B{ sub 3}H{sub 5}), (3) 桥去质子化形成相应的单阴离子或双阴离子，(4)阴离子

  DOI：

  10.1021/ja00195a034

文献信息

• Organotransition-Metal Metallacarboranes. 40. Regiospecific Halogenation of Transition-Metal Small Carborane Complexes
  作者：Kenneth E. Stockman、Dawn L. Garrett、Russell N. Grimes

  DOI：10.1021/om00010a033

  日期：1995.10

  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.
• Organotransition-Metal Metallacarboranes. 39. Arene-Capped Ruthenium-Carborane Tetradecker Sandwich Complexes
  作者：Peter Greiwe、Michal Sabat、Russell N. Grimes

  DOI：10.1021/om00008a015

  日期：1995.8

  A new family of C2B3-bridged tetradecker sandwich complexes, having cymene rather than cyclopentadienyl end rings, has been synthesized via reactions of metal ions with nido-(p-CHMe(2)C(6)H(4)Me)Ru(Et(2)C(2)B(3)H(3)-5-Y)(-) anions that are iso electronic analogues of the nido-(eta(5)-C(5)Me(5))Co(Et(2)C(2)B(3)H(3)-5-Y)(-)synthons employed in earlier work. Bridge-deprotonation of CyRu(Et(2)C(2)B(3)H(4)-5-Y) (Cy = p-isopropyltoluene; 3, Y = Me; 6, Y = Cl), followed by treatment with CoCl2 in THF and separation of the products on silica in air, afforded the tetradecker sandwiches [CyRu(2,3-Et(2)C(2)B(3)H(2)-5-Y)]Co-2 (8a, Y = Me; 8b, Y = Cl) as the major products, isolated as air-stable paramagnetic green crystals in 40% and 55% yield, respectively. In addition, the minor products CyRu(Et(2)C(2)B(3)H(2)-5-Me)Co(Et(2)C(2)B(3)H(2)-5-Et)RuCy (8c) and CyRu-(Et(2)C(2)B(3)H(2)-5-Cl)Co(Et(2)C(2)B2B(3)H(3))RuCY (8d) were obtained. The formation of 8b proceeds via a cobalt-protonated diamagnetic complex [CyRu(2,3-Et(2)C(2)B(3)H(2)-5-Cl)]2CoH (7b) which was isolated and characterized; 8a is assumed to form via an analogous intermediate 7a although this species was not isolated. A similar reaction of 3(-) with NiCl2 gave moderately air-stable, diamagnetic [CyRu(2,3-Et(2)C(2)B(3)H(2)-5-Me)]Ni-2 (9). Reactions of the anion of the B(4,5,6)-trimethyl complex CYRu(Et(2)C(2)B(3)Me(3)H(2)) with CoCl2 and NiCl2 generated the corresponding tetradecker products [CyRu(2,3-Et(2)C(2)B(3)Me(3))]Co-2 (10) and [CyRu(2,3-Et(2)C(2)B(3)Me(3))]Ni-2 (11) in low yields. The new compounds were characterized via H-1 and/or C-13 NMR, IR, UV-visible, and mass spectra, supported by X-ray crystal structure determinations on 8a, 8c, and 9, which established the tetradecker sandwich geometry. The proton NMR spectrum of paramagnetic 8a was completely assigned via the technique of correlated spectroscopy, involving generation of the diamagnetic anion 8a(-) via stepwise reduction of the neutral compound. Crystal data for 8a: Ru2CoClC34.5B6H59, space group (triclinic); a = 13.631(5) Angstrom, b = 16.447(5) Angstrom, c = 9.008(3) alpha = 100.07(3)degrees, beta = 108.12(3)degrees, gamma 94.03(3)degrees; Z = 2; R = 0.038 for 5527 independent reflections. Crystal data for 8c: Ru2Co2C35B6H60, space group P2(1)/n (monoclinic); a = 12.781(3) Angstrom, b = 11.120(4) Angstrom, c = 26.214(4) Angstrom, beta = 96.71 degrees; Z = 4; R = 0.031 for 3052 observed reflections. Crystal data for 9: Ru2NiC34B6H58, space group (triclinic); a = 12.577(7) Angstrom, b = 14.330(6) Angstrom, c = 11.671(7) Angstrom, alpha = 113.24(4)degrees, beta = 111.71(4)degrees, gamma = 83.24(4)degrees; Z = 2; R = 0.028 for 4073 independent reflections.