{NiH(t-BuSCH2CH2)3N}BPh4 | 127997-87-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: {NiH(t-BuSCH2CH2)3N}BPh4
• CAS: 127997-87-9
• 化学式: C₁₈H₄₀NNiS₃*C₂₄H₂₀B
• 分子量: 744.644
• InChiKey: HWEJAUIFHCQGSV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.66
• 重原子数：
  48.0
• 可旋转键数：
  4.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  {NiH(t-BuSCH2CH2)3N}BPh4 在 carbon monoxide 作用下， 以 四氢呋喃 为溶剂， 以60%的产率得到{NiCO(t-BuSCH2CH2)3N}BPh4
  参考文献：
  名称：

  Reaction sequence related to that of carbon monoxide dehydrogenase (acetyl coenzyme A synthase): thioester formation mediated at structurally defined nickel centers

  摘要：

  DOI：

  10.1021/ja00169a076
• 作为产物：
  描述：

  {NiCl(t-BuSCH2CH2)3N}BPh4 、 sodium tetrahydroborate 以 四氢呋喃 为溶剂， 以40%的产率得到{NiH(t-BuSCH2CH2)3N}BPh4
  参考文献：
  名称：

  Reaction sequence related to that of carbon monoxide dehydrogenase (acetyl coenzyme A synthase): thioester formation mediated at structurally defined nickel centers

  摘要：

  DOI：

  10.1021/ja00169a076

文献信息

• Structural and reaction chemistry of nickel complexes in relation to carbon monoxide dehydrogenase: a reaction system simulating acetyl-coenzyme A synthase activity
  作者：Pericles Stavropoulos、Mark C. Muetterties、Michel Carrie、R. H. Holm

  DOI：10.1021/ja00022a041

  日期：1991.10

  A series of nickel complexes [Ni(NS3R)L]+ derived from the tripodal ligand NS3R = N(CH2CH2SR)3 (R = i-Pr, t-Bu) has been prepared in order to investigate the stabilities and reactions of certain species potentially relevant to the nickel sites in carbon monoxide dehydrogenase (CODH). Reaction of [Ni(NS3R)Cl]+ with MeMgCl affords [Ni(NS3R)Me]+, which with CO yields [Ni(NS3R)COMe]+. Reaction of [Ni(NS3tBu)Cl]+ with NaBH4 gives [Ni(NS3tBu)H]+ and the Ni(I) species [Ni(NS3tBu)]+. The hydride complex was obtained with minimal Ni(I) contamination by removal of ethylene from the equilibrium system [Ni(NS3tBu)Et]+/[Ni(NS3tBu)H]+/C2H4. Reaction of [Ni(NS3tBu)]+ with CO affords [Ni(NS3tBu)CO]+, whereas [Ni(NS3tBu)H]+ under the same conditions gives Ni(CO)4 and protonated ligand. All reactions were performed in THF, and all complexes were isolated as BPh4-salts. This series includes rare examples of the stabilization of Ni-methyl, -acyl, -hydride, and -carbonyl ligands in the absence of nonphysiological (C/P/As) coligands. Trigonal-bipyramidal stereochemistry has been demonstrated for five complexes with L = Cl, Me, COMe, H, and CO by X-ray crystallography. The methyl/acyl transformations with carbon monoxide and the formation in high yield of the thioesters R'SCOMe (R' = Et, CH2Ph, Ph) upon reaction of [Ni(NS3R)COMe]+ with thiols in THF are two previously undocumented processes mediated at Ni(II) sites lacking non-physiological (C/P/As) ligation. These are relevant to current views of the catalytic reaction cycle of Clostridium thermoaceticum CODH, which is presented. The Ni(II)-H and Ni(I)-CO species may be pertinent to the CO/CO2 activity of CODH. Full details of all preparations, other reactions, and structures are presented. This work is an initial attempt to place the reaction chemistry of CODH on a rational basis, and provides some viability for the present reaction cycle of the enzyme.