η(1)-(2-tert-butyl-1H-1,3-benzazaphosphole-P)pentacarbonyltungsten | 442692-44-6

• 英文名称: η(1)-(2-tert-butyl-1H-1,3-benzazaphosphole-P)pentacarbonyltungsten
• CAS: 442692-44-6
• 化学式: C₁₆H₁₄NO₅PW
• 分子量: 515.115
• InChiKey: RKJOJCSYTLUSQM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
  None
• sp3杂化的碳原子比例：
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• 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：

  η(1)-(2-tert-butyl-1H-1,3-benzazaphosphole-P)pentacarbonyltungsten 、 叔丁基锂 、 碘甲烷 以 not given 为溶剂， 生成 η(1)(P)-(2-t-butyl-3-methyl-1,3-benzazaphosphol)-pentacarbonyl-tungsten
  参考文献：
  名称：

  摘要：

  1H-1,3-Benzazaphospholes react with M(CO)(5)(THF) (M = Cr, Mo, W) to give thermally and relatively air stable eta(1)-(1H-1,3-Benzazaphosphole-P)M(CO)(5) complexes. The H-1- and C-13-NMR-data are in accordance with the preservation of the phosphaaromatic pi-system of the ligand. The strong upfield P-31 coordination shift, particularly of the Mo and W complexes, forms a contrast to the downfield-shifts of phosphine-M(CO)(5) complexes and classifies benzazaphospholes as weak donor but efficient acceptor ligands. Nickelocene reacts as organometallic species with metalation of the NH-function. The resulting ambident 1,3-benzazaphospholide anions prefer a mu(2)-coordination of the eta(5)-CpNi-fragment at phosphorus to coordination at nitrogen or a eta(3)-heteroallyl-eta(5)-CpNi-semisandwich structure. This is shown by characteristic NMR data and the crystal structure analysis of a eta(5)-CpNi-benzazaphospholide. The latter is a P-bridging dimer with a planar Ni2P2 ring and trans-configuration of the two planar heterocyclic phosphido ligands arranged perpendicular to the four-membered ring.

  DOI：

  10.1002/1521-3749(200213)628:13<2869::aid-zaac2869>3.0.co;2-3
• 作为产物：
  描述：

  四氢呋喃 、 六羰基钨 、 2-(tert-butyl)-1H-1,3-benzazaphosphole 以 四氢呋喃 为溶剂， 以63%的产率得到η(1)-(2-tert-butyl-1H-1,3-benzazaphosphole-P)pentacarbonyltungsten
  参考文献：
  名称：

  摘要：

  1H-1,3-Benzazaphospholes react with M(CO)(5)(THF) (M = Cr, Mo, W) to give thermally and relatively air stable eta(1)-(1H-1,3-Benzazaphosphole-P)M(CO)(5) complexes. The H-1- and C-13-NMR-data are in accordance with the preservation of the phosphaaromatic pi-system of the ligand. The strong upfield P-31 coordination shift, particularly of the Mo and W complexes, forms a contrast to the downfield-shifts of phosphine-M(CO)(5) complexes and classifies benzazaphospholes as weak donor but efficient acceptor ligands. Nickelocene reacts as organometallic species with metalation of the NH-function. The resulting ambident 1,3-benzazaphospholide anions prefer a mu(2)-coordination of the eta(5)-CpNi-fragment at phosphorus to coordination at nitrogen or a eta(3)-heteroallyl-eta(5)-CpNi-semisandwich structure. This is shown by characteristic NMR data and the crystal structure analysis of a eta(5)-CpNi-benzazaphospholide. The latter is a P-bridging dimer with a planar Ni2P2 ring and trans-configuration of the two planar heterocyclic phosphido ligands arranged perpendicular to the four-membered ring.

  DOI：

  10.1002/1521-3749(200213)628:13<2869::aid-zaac2869>3.0.co;2-3

文献信息

• Metalated 1,3-azaphospholes: synthesis of lithium-1,3-benzazaphospholides and reactivity towards organoelement and organometal halides
  作者：Anushka Surana、Shreeyukta Singh、Raj Kumar Bansal、Normen Peulecke、Anke Spannenberg、Joachim Heinicke

  DOI：10.1016/s0022-328x(01)01035-x

  日期：2002.3

  Metalation of benzazaphospholes 1a–e with t-BuLi provided the ambident anions 1a–eLi in high selectivity. A crystal structure analysis of 1bLi·3THF reveals monomers and coordination of lithium at nitrogen. The tungsten pentacarbonyl complexes also react preferably at nitrogen as shown by the reaction of 2a and 2d with t-BuLi. Addition at the PC bond is a minor process in the case of 2a. Compounds

  苯并氮杂磷1a - e与t -BuLi的金属化提供了高选择性的阴离子1a - e Li。1b Li ·3THF的晶体结构分析显示，单体和锂在氮原子上的配位。如2a和2d与t- BuLi的反应所示，五羰基钨络合物还优选在氮下反应。在2a的情况下，在PC键处加成是一个较小的过程。化合物1a，c Li和2d Li与卤代烷在磷处反应，得到3-烷基-1,3-苯并氮杂唑3a和3d或相应的W（CO）5络合物4d。甚至乙酰基和新戊酰氯也能攻击磷的1e Li，从而得到P-酰基衍生物5e和6e。甲硅烷基化可以在氮或磷发生，得到7和/或8根据由取代基在位置2 2-的不同效果施加空间和电子效应吨丁基是由图示在上N和P中的空间位阻基团1d的分子几何通过晶体结构分析确定。软有机金属卤化物，诸如Me 3的SnCl，CPFe的量（CO）2 I和CPW（CO）3 Cl可反应1李优选在磷得到的甲锡烷基或单体有机-过渡金属衍生物9