Carbon monoxide;ethynylbenzene;tungsten | 131896-57-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Carbon monoxide;ethynylbenzene;tungsten
• CAS: 131896-57-6；131759-51-8；131896-58-7
• 化学式: C₂₅H₁₈OW
• 分子量: 518.267
• InChiKey: LHPWOXLGESLPDJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.96
• 重原子数：
  27
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Carbon monoxide;ethynylbenzene;tungsten 、 三苯基膦 以 正庚烷 为溶剂， 以45%的产率得到
  参考文献：
  名称：

  钨的中性和阴离子炔烃配合物中的立体因子（0）

  摘要：

  The labile W(0) source [W(CO)3(NCC2H5)3] (2) reacts with the bulky alkyne bis(trimethylsilyl)acetylene (BTMSA) under reduced pressure to give the tris(alkyne) complex [W(Me3SiC = CSiMe3)3(CO)] (3), which has a low barrier to alkyne rotation. The terminal alkyne PhC = CH reacts similarly with 2 to give the tris(alkyne) complex [W(PhC = CH)3(CO)] (4), isolated as an oil and derivatized by substitution with PPh3 to give [W(PhC = CH)3(PPh3)] (6). Complex 6 is monoisomeric, with all three alkynes oriented with the acetylenic hydrogens proximal to the phosphine, while 4 exists as a mixture of isomers. C-13 NMR spectroscopy indicates that 4 exists in C6D5CD3 as a mixture of 4(3) (4%), 4(2) (64%), and 4(1) (32%), with three, two, and one acetylenic hydrogen, respectively, proximal to the carbonyl. Phosphine substitution is also feasible with the more sterically crowded tris(alkyne) substrate [W(PhC = CPh)3(CO)] (7), which reacts with PMe2Ph to give [W(PhC = CPh)3(PMe2Ph)] (8), in which DELTA-G-double-dagger for alkyne rotation is 13.2 (3) kcal mol-1. The importance of steric factors in determining bonding interactions and alkyne rotation barriers in [W(RC = CR)3(L)] complexes was evaluated by comparison of the NMR characteristics of [W(PhC = CPh)3(SnPh3)]- (9-) with those of [W(PhC = CPh)3(SnMe3)]- (10-), prepared by naphthalenide reduction of 7 and addition of Me3SnCl. The alkyne rotation barrier in 10- (DELTA-G-double-dagger = 12.7 (2) kcal mol-1) is similar to that in 9- (DELTA-G-double-dagger = 13.1 kcal mol-1), implying that steric factors are not dominant. NMR parameters involving Sn-119 suggest that 9- and 10- are best thought of as complexes of ''[W(PhC = CPh)3]'' with R3Sn-anions.

  DOI：

  10.1021/om00048a028
• 作为产物：
  描述：

  tris(propionitrile)tungsten tricarbonyl 、 苯乙炔 以 neat (no solvent) 为溶剂， 以64%的产率得到Carbon monoxide;ethynylbenzene;tungsten
  参考文献：
  名称：

  钨的中性和阴离子炔烃配合物中的立体因子（0）

  摘要：

  The labile W(0) source [W(CO)3(NCC2H5)3] (2) reacts with the bulky alkyne bis(trimethylsilyl)acetylene (BTMSA) under reduced pressure to give the tris(alkyne) complex [W(Me3SiC = CSiMe3)3(CO)] (3), which has a low barrier to alkyne rotation. The terminal alkyne PhC = CH reacts similarly with 2 to give the tris(alkyne) complex [W(PhC = CH)3(CO)] (4), isolated as an oil and derivatized by substitution with PPh3 to give [W(PhC = CH)3(PPh3)] (6). Complex 6 is monoisomeric, with all three alkynes oriented with the acetylenic hydrogens proximal to the phosphine, while 4 exists as a mixture of isomers. C-13 NMR spectroscopy indicates that 4 exists in C6D5CD3 as a mixture of 4(3) (4%), 4(2) (64%), and 4(1) (32%), with three, two, and one acetylenic hydrogen, respectively, proximal to the carbonyl. Phosphine substitution is also feasible with the more sterically crowded tris(alkyne) substrate [W(PhC = CPh)3(CO)] (7), which reacts with PMe2Ph to give [W(PhC = CPh)3(PMe2Ph)] (8), in which DELTA-G-double-dagger for alkyne rotation is 13.2 (3) kcal mol-1. The importance of steric factors in determining bonding interactions and alkyne rotation barriers in [W(RC = CR)3(L)] complexes was evaluated by comparison of the NMR characteristics of [W(PhC = CPh)3(SnPh3)]- (9-) with those of [W(PhC = CPh)3(SnMe3)]- (10-), prepared by naphthalenide reduction of 7 and addition of Me3SnCl. The alkyne rotation barrier in 10- (DELTA-G-double-dagger = 12.7 (2) kcal mol-1) is similar to that in 9- (DELTA-G-double-dagger = 13.1 kcal mol-1), implying that steric factors are not dominant. NMR parameters involving Sn-119 suggest that 9- and 10- are best thought of as complexes of ''[W(PhC = CPh)3]'' with R3Sn-anions.

  DOI：

  10.1021/om00048a028