[2-bis(trimethylsilyl)methyl-3-(2-thienyl)-2H-1,4,2-diazaphosphole-κP]pentacarbonyltungsten(0) | 1260237-14-6

• 英文名称: [2-bis(trimethylsilyl)methyl-3-(2-thienyl)-2H-1,4,2-diazaphosphole-κP]pentacarbonyltungsten(0)
• 英文别名: [2-bis(trimethylsilyl)methyl-3-(2-thienyl)-2H-1,4,2-diazaphosphole-κN1]pentacarbonyltungsten(0)
• CAS: 1260237-14-6；1260237-13-5
• 化学式: C₁₈H₂₃N₂O₅PSSi₂W
• 分子量: 650.452
• InChiKey: CJUWGTSMHLEEAL-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

• 作为反应物：
  描述：

  [2-bis(trimethylsilyl)methyl-3-(2-thienyl)-2H-1,4,2-diazaphosphole-κP]pentacarbonyltungsten(0) 、 [2-bis(trimethylsilyl)methyl-3-(2-thienyl)-2H-1,4,2-diazaphosphole-κP]pentacarbonyltungsten(0) 在 (n-Bu)4NF 、 [Et₃NH][O₃SCF₃ 作用下， 以 四氢呋喃 为溶剂， 以68%的产率得到[2-methyl-3-(2-thienyl)-2H-1,4,2-diazaphosphole-κP]pentacarbonyltungsten(0)
  参考文献：
  名称：

  When Sterics Overcome Electronics: An Unusual Haptotropic P→N Pentacarbonyltungsten Shift

  摘要：

  Acid-induced ring expansion of 2H-azaphosphirene complexes 1a-c with HCN is described. These reactions yielded 2H-1,4,2-diazaphosphole complexes 2a-c as a mixture with their kappa N-coordination isomers 3a-c in different ratios, depending upon the steric demand of the C-3-substituent on the diazaphosphole ring. DFT calculations revealed that the isomerization can proceed in one step via a haptotropic P -> N W(CO)(5) shift. When a mixture of 2b and 3b was heated in acetonitrile, complete decomplexation with formation of 2H-1,4,2-diazaphosphole 5 was observed. Reaction of 2b and 3b with tetra-n-butylammonium fluoride in the presence of [Et3NH][OTf] led to complete desilylation of the P-CH(SiMe3)(2) substituent and formation of complex 6, showing only kappa P-coordination. In addition to NMR, IR, and UV/vis spectra, the single-crystal X-ray diffraction structures of 2a,b and 6 are discussed.

  DOI：

  10.1021/om1007709
• 作为产物：
  描述：

  氢氰酸 、 [2-bis(trimethylsilyl)methyl-3-(2-thienyl)-2H-azaphosphirene-κP]pentacarbonyltungsten(0) 在 CF₃SO₃H 、 pyridine 作用下， 以 二氯甲烷 为溶剂， 生成 [2-bis(trimethylsilyl)methyl-3-(2-thienyl)-2H-1,4,2-diazaphosphole-κP]pentacarbonyltungsten(0) 、 [2-bis(trimethylsilyl)methyl-3-(2-thienyl)-2H-1,4,2-diazaphosphole-κP]pentacarbonyltungsten(0)
  参考文献：
  名称：

  When Sterics Overcome Electronics: An Unusual Haptotropic P→N Pentacarbonyltungsten Shift

  摘要：

  Acid-induced ring expansion of 2H-azaphosphirene complexes 1a-c with HCN is described. These reactions yielded 2H-1,4,2-diazaphosphole complexes 2a-c as a mixture with their kappa N-coordination isomers 3a-c in different ratios, depending upon the steric demand of the C-3-substituent on the diazaphosphole ring. DFT calculations revealed that the isomerization can proceed in one step via a haptotropic P -> N W(CO)(5) shift. When a mixture of 2b and 3b was heated in acetonitrile, complete decomplexation with formation of 2H-1,4,2-diazaphosphole 5 was observed. Reaction of 2b and 3b with tetra-n-butylammonium fluoride in the presence of [Et3NH][OTf] led to complete desilylation of the P-CH(SiMe3)(2) substituent and formation of complex 6, showing only kappa P-coordination. In addition to NMR, IR, and UV/vis spectra, the single-crystal X-ray diffraction structures of 2a,b and 6 are discussed.

  DOI：

  10.1021/om1007709