| 137332-99-1

• CAS: 137332-99-1
• 化学式: C₂₆H₁₄O₁₁Os₃S
• 分子量: 1105.06
• InChiKey: SBNDSSZJBUCMFP-YALODOGSSA-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：

  在 CO 作用下， 以 正庚烷 为溶剂， 以33%的产率得到
  参考文献：
  名称：

  Carbon-sulfur bond cleavage with a loss of stereochemistry in the ring opening of trans-2,4-diphenylthietane by Os3(CO)10(NCMe)2

  摘要：

  The reaction of Os3(CO)10(NCMe)2 with trans-2,4-diphenylthietane (2,4-DPT) at 25-degrees-C resulted in the formation of two isomers, cis- and trans-Os3(CO)10[mu-SC(H)PhCH2C(H)Ph] (1), in a combined yield of 76%. The cis product was characterized by single-crystal X-ray diffraction analysis and was found to contain a thiametalladiphenylcyclopentane ring formed by the opening of the thietane ring. The cis and trans isomers differ in the orientation of their phenyl substituents. The isomers are formed in approximately equal amounts in the early stages of the reaction, but the trans isomer subsequently slowly isomerizes to the cis isomer. The observed loss in stereochemistry at the carbon center is attributed to a stepwise ring-opening mechanism. When compound 1 was heated to 97-degrees-C under a CO atmosphere, five compounds were formed: Os3(CO)10[mu-SC(H)PhC(H) = C(H)Ph[(mu-H) (2) (22%), Os2(CO)7[mu-SC(H)(C6H4)CH2CH2Ph] (3) (11%), Os3(CO)11[mu-SC(H)PhCH2C(H)Ph] (4) (39%), H2Os6(CO)17(mu(3)-S)(mu(4)-S) (5) (a trace amount), and Os3(CO)12. Compounds 3 and 5 and the known compound Os3(CO)9(mu(3)-CO)(mu(3)-S) (6) were obtained in better yields by heating 2 to 125-degrees-C in octane solvent. Compounds 2-4 were characterized by IR, H-1 NMR, and single-crystal X-ray diffraction analyses. Compound 2 is an isomer of 1 and contains a diphenylpropenethiolate and hydride ligand formed by a ''beta-elimination'' transformation of the ring system in 1. The mechanism of this transformation was not established. Compound 3 contains only two metal atoms and an ortho-metalated phenyl ring. Compound 4 is a CO adduct of 1 formed by the cleavage of the sulfur-bridged metal-metal bond. Crystallographic data are as follows. cis-1: space group P2(1)/c, a = 8.674 (2) angstrom, b = 35.09 (1) angstrom, c = 9.449 (2) angstrom, beta = 106.41 (1)-degrees, Z = 4, 2053 reflections, R = 0.033. 2: space group C2/c, a = 13.845 (2) angstrom, b = 14.545 (4) angstrom, c = 28.907 (6) angstrom, beta = 98.88 (1)-degrees, Z = 8, 2519 reflections, R = 0.027. 3: space group P2(1)/c, a = 8.337 (1) angstrom, b = 17.311 (4) angstrom, c = 16.409 (3) angstrom, beta = 100.82 (1)-degrees, Z = 4, 2299 reflections, R = 0.036. 4: space group P1BAR, a = 14.319 (2) angstrom, b = 17.794 (5) angstrom, c = 12.257 (4) angstrom, alpha = 106.69 (2)-degrees, beta = 90.74 (2)-degrees, gamma = 82.56 (2)-degrees, Z = 4, 4020 reflections, R = 0.041.

  DOI：

  10.1021/om00037a024
• 作为产物：
  描述：

  在 CO 作用下， 以 正庚烷 为溶剂， 以22%的产率得到
  参考文献：
  名称：

  Carbon-sulfur bond cleavage with a loss of stereochemistry in the ring opening of trans-2,4-diphenylthietane by Os3(CO)10(NCMe)2

  摘要：

  The reaction of Os3(CO)10(NCMe)2 with trans-2,4-diphenylthietane (2,4-DPT) at 25-degrees-C resulted in the formation of two isomers, cis- and trans-Os3(CO)10[mu-SC(H)PhCH2C(H)Ph] (1), in a combined yield of 76%. The cis product was characterized by single-crystal X-ray diffraction analysis and was found to contain a thiametalladiphenylcyclopentane ring formed by the opening of the thietane ring. The cis and trans isomers differ in the orientation of their phenyl substituents. The isomers are formed in approximately equal amounts in the early stages of the reaction, but the trans isomer subsequently slowly isomerizes to the cis isomer. The observed loss in stereochemistry at the carbon center is attributed to a stepwise ring-opening mechanism. When compound 1 was heated to 97-degrees-C under a CO atmosphere, five compounds were formed: Os3(CO)10[mu-SC(H)PhC(H) = C(H)Ph[(mu-H) (2) (22%), Os2(CO)7[mu-SC(H)(C6H4)CH2CH2Ph] (3) (11%), Os3(CO)11[mu-SC(H)PhCH2C(H)Ph] (4) (39%), H2Os6(CO)17(mu(3)-S)(mu(4)-S) (5) (a trace amount), and Os3(CO)12. Compounds 3 and 5 and the known compound Os3(CO)9(mu(3)-CO)(mu(3)-S) (6) were obtained in better yields by heating 2 to 125-degrees-C in octane solvent. Compounds 2-4 were characterized by IR, H-1 NMR, and single-crystal X-ray diffraction analyses. Compound 2 is an isomer of 1 and contains a diphenylpropenethiolate and hydride ligand formed by a ''beta-elimination'' transformation of the ring system in 1. The mechanism of this transformation was not established. Compound 3 contains only two metal atoms and an ortho-metalated phenyl ring. Compound 4 is a CO adduct of 1 formed by the cleavage of the sulfur-bridged metal-metal bond. Crystallographic data are as follows. cis-1: space group P2(1)/c, a = 8.674 (2) angstrom, b = 35.09 (1) angstrom, c = 9.449 (2) angstrom, beta = 106.41 (1)-degrees, Z = 4, 2053 reflections, R = 0.033. 2: space group C2/c, a = 13.845 (2) angstrom, b = 14.545 (4) angstrom, c = 28.907 (6) angstrom, beta = 98.88 (1)-degrees, Z = 8, 2519 reflections, R = 0.027. 3: space group P2(1)/c, a = 8.337 (1) angstrom, b = 17.311 (4) angstrom, c = 16.409 (3) angstrom, beta = 100.82 (1)-degrees, Z = 4, 2299 reflections, R = 0.036. 4: space group P1BAR, a = 14.319 (2) angstrom, b = 17.794 (5) angstrom, c = 12.257 (4) angstrom, alpha = 106.69 (2)-degrees, beta = 90.74 (2)-degrees, gamma = 82.56 (2)-degrees, Z = 4, 4020 reflections, R = 0.041.

  DOI：

  10.1021/om00037a024