(η(5)-C5Me4CH2OsBu)Ru(CO)2Cl | 160758-92-9

• 英文名称: (η(5)-C5Me4CH2OsBu)Ru(CO)2Cl
• CAS: 160758-92-9
• 化学式: C₁₆H₂₃ClO₃Ru
• 分子量: 399.88
• InChiKey: YHWJECFIQFFFKP-UHFFFAOYSA-M

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

• 作为产物：
  描述：

  (η(5)-C5Me4CH2Cl)Ru(CO)2Cl 、 仲丁醇 以 neat (no solvent) 为溶剂， 以91%的产率得到(η(5)-C5Me4CH2OsBu)Ru(CO)2Cl
  参考文献：
  名称：

  五甲基环戊二烯基络合物中的环甲基活化。4. [（C5Me4CH2Cl）RuCl（CO）2]及其相关化合物的合成，结构和反应：[（C5Me4CH2Cl）RuCl（CO）2]和[（C5Me4CH2Clt）Ru（PPh3）（CO）的X射线结构2]（OTf）

  摘要：

  The dicarbonyl chloro complex [(C(5)Me(4)CH(2)Cl)RuCl(CO)(2)] (4) is formed by carbonylation (1 atm, 20 degrees C, 5 min) of the dimeric tetramethylfulvene complex [{(C(5)Me(4)CH(2))RUCl(2)}(2)] (3), which is in turn made by oxygenation (1 atm, 20 degrees C, 30 min) of [{(C(5)Me(5))RUCl(2)}(2)] (1); since both reactions proceed in high yield, 4 is a readily accessible starting material for a range of Cp*-substituted ruthenium complexes. The C-Cl in 4 is readily substituted by nucleophiles to give [(C(5)Me(4)CH(2)X)Ru(CO)(2)Cl] (X = OH, OMe, OEt, O-i-Pr, OPh, OCH(2)Ph, NEt(2), H), and by PPh(3) (in the presence of NH4PF6) to give [(C(5)Me(4)CH(2)PPh(3))Ru(CO)(2)Cl]PF6. The Ru-Cl in the alkoxy complexes [(C(5)Me(4)CH(2)OR)Ru(CO)(2)Cl] is replaced by reaction with KX to give [(C(5)Me(4)CH(2)OR)Ru(CO)(2)X] (R = Me, X = Br, I, CN, SCN; R = Et, X = Br, I) and by PPh(3) in the presence of Ag+ to give [(C(5)Me(4)CH(2)OEt)Ru(CO)(2)(PPh(3))](+). Reaction of 4 with KCN or KSCN in MeOH gave a mixture of [(C(5)Me(4)CH(2)OMe)Ru(CO)(2)X], [(C(5)Me(5))Ru(CO)(2)X], and [(C(5)Me(4)CH(2)X)Ru(CO)(2)X] (X = CN, SCN). The amines are quaternized; e.g., [(C(5)Me(4)CH(2)NEt(2))Ru(CO)(2)Cl] reacted with MeI to give [(C(5)Me(4)CH(2)NEt(2)Me)Ru(CO)(2)I]I. X-ray crystal structure determinations were carried out for [(C(5)Me(4)CH(2)Cl)Ru(CO)(2)Cl] (orthorhombic, a = 18.291(3) Angstrom, b = 11.087(17) Angstrom, c = 6.877(12) Angstrom, V = 1394.6(4) Angstrom(3), Z = 4, D-c = 1.725 g cm(-3), space group Pnma (D-2h(16), NO. 62)) and [(C(5)Me(4)CH(2)OEt)Ru(CO)(2)(PPh(3))](+)(OTf)(-) (triclinic, a = 10.496(12) Angstrom, b = 12.509(9) Angstrom, c 12.738(7) Angstrom, alpha = 90.25(5)degrees, beta = 93.56(7)degrees, gamma = 93.85(7)degrees, V = 1666(2) Angstrom(3), Z = 2, D-c = 1.491 g cm(-3), space group P ($) over bar 1 (C-i(1) No. 2)).

  DOI：

  10.1021/om00002a015