W(CO)5(di(1-cyclohepta-2,4,6-trienyl)sulfane) | 847202-52-2

• 英文名称: W(CO)5(di(1-cyclohepta-2,4,6-trienyl)sulfane)
• CAS: 847202-52-2
• 化学式: C₁₉H₁₄O₅SW
• 分子量: 538.233
• InChiKey: DYJGQXOHJYRETQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  None

反应信息

• 作为反应物：
  描述：

  W(CO)5(di(1-cyclohepta-2,4,6-trienyl)sulfane) 以 四氢呋喃 为溶剂， 以52.8%的产率得到W(CO)5((1-cyclohepta-2,4,6-trienyl)benzyl-sulfane
  参考文献：
  名称：

  Reactions of Di(1-cyclohepta-2, 4, 6-trienyl)sulfane, S(C7H7)2, with Derivatives of the Hexacarbonyls, M(CO)6 (M = Cr, Mo, W)

  摘要：

  AbstractMononuclear carbonylmetal complexes of chromium, molybdenum and tungsten containing the sulfane S(C7H7)2 (1) have been obtained starting from precursors such as the THF‐stabilized pentacarbonylmetal fragments, [M(CO)5](thf), the acetonitrile intermediates M(CO)6‐x(CH3CN)x (x = 1, 2, 3) (M = Cr, Mo, W) or the η4‐norbornadiene complexes M(CO)4(C7H8) (M = Cr, Mo). In addition to the pentacarbonyls, M(CO)5[S(C7H7)2] (M = Cr (2a), Mo (2b), W (2c)) which contain 1 unchanged as a two‐electron sulfane ligand with two pending cyclohepta‐2, 4, 6‐trienyl substituents, isomeric complexes M(CO)5[S(CH2Ph)(C7H7)] (M = Cr (3a), W (3c)) were obtained at higher temperatures (40‐50 °C) in which one of the two organic groups has been transformed into a benzyl substituent. In the tetracarbonyls, cis‐M(CO)4[S(C7H7)(η2‐C7H7)] (M = Mo (4b), W (4c)), the ligand 1 serves as an olefinic sulfane four‐electron chelate ligand. The reaction of either Mo(CO)6 or (mesitylene)Mo(CO)3 with S(C7H7)2 (1) in boiling THF leads to the sulfur‐free ditropyl complex Mo(CO)3[(η6‐C7H7)‐C7H7] (5b, two isomers). The 1H and 13C NMR spectra of the new complexes 2‐4 reveal various dynamic processes including pyramidal inversion of the sulfur atom and [1, 7]‐sigmatropic shifts at the C7H7 ring. The molecular structures of 2c, 3a, 4b and 4c have been determined by X‐ray crystallography.

  DOI：

  10.1002/zaac.200400196
• 作为产物：
  描述：

  四氢呋喃 、 六羰基钨 、 di(1-cyclohepta-2,4-6-trienyl)sulfane 以 四氢呋喃 为溶剂， 以57.6%的产率得到W(CO)5(di(1-cyclohepta-2,4,6-trienyl)sulfane)
  参考文献：
  名称：

  Reactions of Di(1-cyclohepta-2, 4, 6-trienyl)sulfane, S(C7H7)2, with Derivatives of the Hexacarbonyls, M(CO)6 (M = Cr, Mo, W)

  摘要：

  AbstractMononuclear carbonylmetal complexes of chromium, molybdenum and tungsten containing the sulfane S(C7H7)2 (1) have been obtained starting from precursors such as the THF‐stabilized pentacarbonylmetal fragments, [M(CO)5](thf), the acetonitrile intermediates M(CO)6‐x(CH3CN)x (x = 1, 2, 3) (M = Cr, Mo, W) or the η4‐norbornadiene complexes M(CO)4(C7H8) (M = Cr, Mo). In addition to the pentacarbonyls, M(CO)5[S(C7H7)2] (M = Cr (2a), Mo (2b), W (2c)) which contain 1 unchanged as a two‐electron sulfane ligand with two pending cyclohepta‐2, 4, 6‐trienyl substituents, isomeric complexes M(CO)5[S(CH2Ph)(C7H7)] (M = Cr (3a), W (3c)) were obtained at higher temperatures (40‐50 °C) in which one of the two organic groups has been transformed into a benzyl substituent. In the tetracarbonyls, cis‐M(CO)4[S(C7H7)(η2‐C7H7)] (M = Mo (4b), W (4c)), the ligand 1 serves as an olefinic sulfane four‐electron chelate ligand. The reaction of either Mo(CO)6 or (mesitylene)Mo(CO)3 with S(C7H7)2 (1) in boiling THF leads to the sulfur‐free ditropyl complex Mo(CO)3[(η6‐C7H7)‐C7H7] (5b, two isomers). The 1H and 13C NMR spectra of the new complexes 2‐4 reveal various dynamic processes including pyramidal inversion of the sulfur atom and [1, 7]‐sigmatropic shifts at the C7H7 ring. The molecular structures of 2c, 3a, 4b and 4c have been determined by X‐ray crystallography.

  DOI：

  10.1002/zaac.200400196