| 216434-55-8

• CAS: 216434-55-8
• 化学式: C₃₈H₄₀Co₂O₄P₂S₂
• 分子量: 804.799
• InChiKey: HXXYLZHNTGFTTQ-UHFFFAOYSA-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

• 作为产物：
  描述：

  S-butyldiphenylthiophosphinite 、 (acetylene)hexacarbonyldicobalt 以 甲苯 为溶剂， 以60%的产率得到
  参考文献：
  名称：

  Labile SR′C(O)CRCH-bridged dicobalt complexes;synthesis structures 13CO labelling studies

  摘要：

  Three alkyne-bridged dicobalt carbonyl complexes, [Co-2(mu-RCCH)(CO)(6)] (R=H la, Me Ib, CH,OH Ic) have been reacted with Ph2P(SPh) and with the new thiophosphine ligands, Ph2P(SR') (R' = Bu-n, Bu-t), to give, initially, both mono-substituted [Co-2(mu-RCCH)(CO)(5){PPh2(SR')}] [(R' = Ph; R = H 2a, Me 2b, CH2OH 2c), (R' = Bu-n; R= H 3a, Me 3b, CH2OH 3c), (R' = Bu-t; R= H 4a, Me 4b)] and bis-substituted [Co-2(mu-RCCH)(CO)(4){ PPh2(SPh)}(2)] [(R' = Ph; R = H 5a, Me 5b, CH2OH 5c), (R' = Bu-n; R = H 6a, Me 6b, CH2OH 6c), (R'=Bu-t; R=H 7a, Me 7b)] products. Thermolysis of complexes 2-4 gives [Co-2(mu-PPh2){mu-SR'C(O) CRCH}(CO)(4)] [(R' = Ph; R = H 8a, Me 8b, CH2OH Sc), (R' = Bu-n; R = H 9a, Me 9b), (R' = Bu-t; R= H 10a, R= Me 10b)] in which sulphur-phosphorus bond cleavage and sulphur-carbon bond formation at the dicobalt centre have occurred to generate SR'C(O)CRCH ligands incorporated into 5-membered ring metallacycles. The transformations are regiospecific with the bulky substituents (R = H) in all cases being located adjacent to the CO moiety of the metallacycle. Treatment of the complex [Co-2(mu-PPh2){mu-SPhC(O)CHCH}(CO)(4)] 8a with (CO)-C-13 and monitoring of the reaction via C-13-{H-1}-NMR spectroscopy reveals the formation of a selectively labelled species, [Co-2(mu-PPh2){mu-(SPhC)-C-13(O)CHCH}((CO)-C-13)(2)(CO)(2)], in which the ketonic bridging carbonyl signal has been enhanced, while only two of the four signals due to the terminal carbonyl groups have been similarly enhanced. The mechanistic implications of this labelling study are discussed and pathways postulated for the reversible fragmentation of the SR'C(O)CRCH-bridged dicobalt systems. Single crystal X-ray diffraction studies have been performed on [Co-2(mu-HCCH)(CO)(4){PPh2(SBun)}(2)] 6a, revealing axially substituted thiophosphine groups and on [Co-2(mu-PPh2){mu-sBu(n)C(O)CHCH}(CO)(4)] 9a, in which an almost planar Co-S-C-C=C metallacycle-coordinated to the other cobalt is observed. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0277-5387(98)00103-x