[W(CO)(acetylacetonate)2(η2-MeN=CMe)]O3SCF3 | 1014698-21-5

• 英文名称: [W(CO)(acetylacetonate)2(η2-MeN=CMe)]O3SCF3
• 英文别名: [W(CO)(η2-MeN=CMe)(acetylacetonato)2][OTf]；[W(CO)(η2-MeN=CMe)(acac)2][OTf]
• CAS: 1014698-21-5
• 化学式: CF₃O₃S*C₁₄H₂₀NO₅W
• 分子量: 615.237
• InChiKey: RDQBRFNOCFSXGM-UHFFFAOYSA-M

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：

  [W(CO)(acetylacetonate)2(η2-MeN=CMe)]O3SCF3 、 sodium trimethoxyborohydride 以 四氢呋喃 为溶剂， 以75%的产率得到[W(CO)(acetylacetonate)2(η2-MeN=CHMe)]
  参考文献：
  名称：

  Reduction of π-Bound Nitriles to π-Bound Imines in a Tungsten(II) Bis(acetylacetonate) Coordination Sphere

  摘要：

  Addition of MeOTf (OTf = CF3SO3) to complexes of the type W(CO)(acac)(2)(eta(2)-N=CR) (acac = acetylacetonate) [R = Ph (1a), Me (1b)] yields cationic iminoacyl triflate salts of the type [W(CO)(acac)2(17 mu(2)-MeN=CR)][OTf]. Complexes 2a and 2b undergo nucleophilic attack at the iminoacyl carbon with Na[HB(OMe)(3)] or MeMgBr to form neutral 772-imine complexes of the type W(CO)(acac)(2)[eta(2)- MeN=C(Nuc)R] [Nuc = H (3a, 3b), Me (4)]. Hydride addition to 2b results in W(CO)(acac)(2)(eta(2)- MeN=CHMe), 3b, a complex that exhibits interconversion of diastereomers at ambient temperature on the NMR time scale. X-ray structures of cationic iminoacyl complex 2a and neutral imine complex 4 confirm eta(2)-C=N bonding of both the iminoacyl and imine ligands.

  DOI：

  10.1021/om7009039
• 作为产物：
  描述：

  [W(CO)(acetylacetonate)2(η2-NCMe)] 、 三氟甲烷磺酸甲酯 以 二氯甲烷 为溶剂， 以75%的产率得到[W(CO)(acetylacetonate)2(η2-MeN=CMe)]O3SCF3
  参考文献：
  名称：

  Reduction of π-Bound Nitriles to π-Bound Imines in a Tungsten(II) Bis(acetylacetonate) Coordination Sphere

  摘要：

  Addition of MeOTf (OTf = CF3SO3) to complexes of the type W(CO)(acac)(2)(eta(2)-N=CR) (acac = acetylacetonate) [R = Ph (1a), Me (1b)] yields cationic iminoacyl triflate salts of the type [W(CO)(acac)2(17 mu(2)-MeN=CR)][OTf]. Complexes 2a and 2b undergo nucleophilic attack at the iminoacyl carbon with Na[HB(OMe)(3)] or MeMgBr to form neutral 772-imine complexes of the type W(CO)(acac)(2)[eta(2)- MeN=C(Nuc)R] [Nuc = H (3a, 3b), Me (4)]. Hydride addition to 2b results in W(CO)(acac)(2)(eta(2)- MeN=CHMe), 3b, a complex that exhibits interconversion of diastereomers at ambient temperature on the NMR time scale. X-ray structures of cationic iminoacyl complex 2a and neutral imine complex 4 confirm eta(2)-C=N bonding of both the iminoacyl and imine ligands.

  DOI：

  10.1021/om7009039

文献信息

• Reduction of an η²-Iminoacyl Ligand to η²-Iminium Enabled by Adjacent Carbon Monoxide Ligand Replacement with a Variable Electron Donor Alkyne Ligand in a Cationic Tungsten(II) Bis(acetylacetonate) Complex
  作者：Andrew B. Jackson、Chetna Khosla、Peter S. White、Joseph L. Templeton

  DOI：10.1021/ic800738a

  日期：2008.10.6

  complex 3b[BAr' 4 ], and phenylacetylene complex 5a[BAr' 4 ] confirm replacement of CO by these ligands in the [W(L)(eta (2)-MeNCR)(acac) 2] (+) products. X-ray structures of alkyne-imine complexes 6[BAr' 4 ] and 8 show products resulting from nucleophilic addition at the iminoacyl carbon, and the X-ray structure of 9[BAr' 4 ] reflects methylation at the imine nitrogen to form a rare eta (2)-iminium ligand

  [W（CO）（eta（2）-MeNCR）（acac）2]（+）类型的阳离子亚氨基酰基-羰基钨络合物容易受热用两个电子供体取代CO以产生[W（L）（eta（2）-MeNCR）（acac）2]（+）（L =叔丁基异腈[R = Ph（2a），Me（2b）] ，2,6-二甲基苯基异腈[R = Me（2c）]，三苯基膦[R = Ph（3a），Me（3c）]和三环己基膦[R = Ph（3b）]）。三环己基膦配合物3b在NMR时间范围内，在室温下显示快速，可逆的膦配体交换。有效地用苯乙炔或2-丁炔进行光解替换一氧化碳，以形成[W（eta（2）-炔）（eta（2）-MeNCR）（acac）2]（+）络合物（5a-d）可变电子供体eta（2）-炔烃与W（II）配位域中的eta（2）-亚氨基酰基配体配对。PMe 3加到1a或5b上，通过亲核形成[W（L）（eta（2）-MeNC（PMe 3）Ph）（acac）2]（+）[L