{Et4N}{closo-1,8-Me2-11-(Et)-2-I-2,2,2-(carbonyl)3-2,1,8-tungstacarborane} | 138923-73-6

• 英文名称: {Et4N}{closo-1,8-Me2-11-(Et)-2-I-2,2,2-(carbonyl)3-2,1,8-tungstacarborane}
• CAS: 138923-73-6
• 化学式: C₈H₂₀N*C₉H₁₉B₉IO₃W
• 分子量: 713.555
• InChiKey: QSCWKRRPMZSJLV-UHFFFAOYSA-M

反应信息

• 作为反应物：
  描述：

  {Et4N}{closo-1,8-Me2-11-(Et)-2-I-2,2,2-(carbonyl)3-2,1,8-tungstacarborane} 在 CO 、 AgBF₄ 作用下， 以 二氯甲烷 为溶剂， 以92%的产率得到{closo-1,8-Me2-11-(Et)-2,2,2,2-tetracarbonyl-2,1,8-tungstacarborane}
  参考文献：
  名称：

  Brew, Stephen A.; Carr, Nicholas; Jeffery, John C., Journal of the American Chemical Society, 1992, vol. 114, # 6, p. 2203 - 2210

  摘要：

  DOI：
• 作为产物：
  描述：

  NEt4{W(CMe)(CO)2(η5-C2B9H9Me2) 在 HI 作用下， 以 二氯甲烷 、 水 为溶剂， 以40%的产率得到{Et4N}{closo-1,8-Me2-11-(Et)-2-I-2,2,2-(carbonyl)3-2,1,8-tungstacarborane}
  参考文献：
  名称：

  Brew, Stephen A.; Carr, Nicholas; Jeffery, John C., Journal of the American Chemical Society, 1992, vol. 114, # 6, p. 2203 - 2210

  摘要：

  DOI：

文献信息

• Alkylidyne(carbaborane) complexes of the Group 6 metals. Part 4. Formation of unsaturated dimetal species, including ‘reverse’ polytopal isomerisation, and reactions with trimethylphosphine
  作者：Stephen A. Brew、F. Gordon A. Stone

  DOI：10.1039/dt9920000867

  日期：——

  Treatment of a mixture of [NEt4][W( = CMe)(CO)2(eta(5)-7,8-C2B9H9-7,8-Me2)] and [W( = CMe)(CO)2(eta-C5H5)] with HBF4.Et2O in CH2Cl2 at -78-degrees-C affords the dimetal complex [W2(mu-CMe)(CO)3(eta-C5H5)eta(5)-7,8-C2B9H8-10-Et-7,8-Me2}], which with PMe3 gives [W2(mu-CMe)(CO)3(PMe3)(eta-C5H5)eta(5)-7,8-C2B9H8-10-Et-7,8-Me2}]. Mixtures of the salts [X][WI(CO)3eta(5)-2,8-C2B9H8-10-(CH2R)-2,8-Me2}] (X = NMe3Ph or AsPh4, R = C6H4Me-4) and the compounds [M( = CR)(CO)2(eta-C5H5)] (M = W or Mo) in CH2Cl2 react with AgBF4 to yield the dimetal complexes [MW(mu-CR)(CO)3(eta-C5H5)eta(5)-2,8-C2B9H8-10-(CH2C6H4Me-4)-2,8-Me2}] and [W2(mu-CC6H4Me-4)(CO)4(eta-C5H5)eta(5)-2,8-C2B9H8-10-(CH2C6H4Me-4)-2,8-Me2}]. The corresponding reaction between a mixture of [AsPh4][WI(CO)3eta(5)-2,8-C2B9H8-10-(CH2R)-2,8-Me2}] (R = C6H4Me-4) and [W( = CMe)(CO)2-(eta-C5H5)], in the presence of TIBF4, affords equal amounts of the two isomers [W2(mu-CMe)(CO)3-(eta-C5H5)eta(5)-2,8-C2B9H8-10-(CH2R)-2,8-Me2}] and [W2(mu-CMe)(CO)3(eta-C5H5)eta(5)-7,8-C2B9H8-10-(CH2R)-7,8-Me2}]. The latter product is the result of a polytopal rearrangement of the cage CMe groups in the precursor. This isomerisation also occurs in the formation of the complexes [W2-(mu-CMe)(CO)3(eta-C5H5)eta(5)-7,8-C2B9H8-10-(CH2R)-7,8-Me2}] (R = Me or C6H4Me-4) from reactions of AgBF4 with mixtures of [X][WI(CO)3eta(5)-2,8-C2B9H8-10-(CH2R)-2,8-Me2}] and [W( = CMe)(CO)2-(eta-C5H5)]. Some reactions of the dimetal compounds containing eta(5)-C2B9H8-10-(CH2R)-Me2 groups with PMe3 have been studied, and the crystal structure of [W2(mu-CC6H4Me-4)(CO)3(PMe3)(eta-C5H5)-eta(5)-2,8-C2B9H8-10-(CH2C6H4Me-4)-2,8-Me2}] has been determined by X-ray crystallography. The W-W bond [2.798(1) angstrom] is spanned essentially symmetrically by the p-tolymethylidyne group [mu-C-W (average) 2.03 angstrom]. One W atom carries the C5H5 ring, a CO group and the PMe3 ligand [W-P 2.478(3) angstrom]. The other W atom is co-ordinated by two CO groups and a nido-2,8-C2B9H8-10-(CH2C6H4Me-4)-2,8-Me2 icosahedral fragment. The NMR data (H-1, C-13-H-1}, B-11-H-1}, B-11, and P-31-H-1}) for the new compounds are reported and discussed.