W(O)Cl2(PMePh2)2(ethylene) | 102307-86-8

• 英文名称: W(O)Cl2(PMePh2)2(ethylene)
• CAS: 102307-86-8
• 化学式: C₂₈H₃₀Cl₂OP₂W
• 分子量: 699.249
• InChiKey: IYIKIBHQUOTYPU-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
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• 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：

  二苯基甲氧基膦 、 W(O)Cl2(PMePh2)2(ethylene) 以 not given 为溶剂， 生成 [WCl2O(PMePh2)3]
  参考文献：
  名称：

  具有强π供体和π受体配体的钨配合物：W（E）Cl2（L）（PR3）2（E = O，NR，S和L = CO，CNR，CH2CHR和OCHMe）

  摘要：

  摘要一系列钨配合物W（E）Cl2（L）（PR3）2的合成与表征，该配合物既包含π供体基团（E =氧代，亚氨基或硫代），又包含π受体配体（L =报告了CO，CNtBu，CH2 = CHR，O = CHMe（PR3 = PMe3，PMePh2）。这些化合物是通过用L取代W（E）Cl2（PR3）3中的膦配体，以及通过向WCl2（PMePh2）4氧化杂杂烯酮EL，环氧化物或环硫化物而制备的。根据光谱数据和氧代羰基（4），氧代乙烯（7）和亚氨基羰基（25）的光谱数据和X射线晶体结构，所有化合物均具有带有π供体和π受体顺式的八面体结构。 ）复合体。乙烯配体的取向垂直于钨-氧，-氮或-硫的多键，并且通过NMR是非通量的。这些几何特征是d2金属中心的电子结构的直接结果。乙醛的二价配位显示了钨（IV）-氧代中心的基本π碱度。CO拉伸频率表明供体能力的顺序为：氧代

  DOI：

  10.1016/s0277-5387(00)86523-7
• 作为产物：
  描述：

  [WCl2O(PMePh2)3] 在 ethylene 作用下， 以 苯 为溶剂， 以74%的产率得到W(O)Cl2(PMePh2)2(ethylene)
  参考文献：
  名称：

  具有强π供体和π受体配体的钨配合物：W（E）Cl2（L）（PR3）2（E = O，NR，S和L = CO，CNR，CH2CHR和OCHMe）

  摘要：

  摘要一系列钨配合物W（E）Cl2（L）（PR3）2的合成与表征，该配合物既包含π供体基团（E =氧代，亚氨基或硫代），又包含π受体配体（L =报告了CO，CNtBu，CH2 = CHR，O = CHMe（PR3 = PMe3，PMePh2）。这些化合物是通过用L取代W（E）Cl2（PR3）3中的膦配体，以及通过向WCl2（PMePh2）4氧化杂杂烯酮EL，环氧化物或环硫化物而制备的。根据光谱数据和氧代羰基（4），氧代乙烯（7）和亚氨基羰基（25）的光谱数据和X射线晶体结构，所有化合物均具有带有π供体和π受体顺式的八面体结构。 ）复合体。乙烯配体的取向垂直于钨-氧，-氮或-硫的多键，并且通过NMR是非通量的。这些几何特征是d2金属中心的电子结构的直接结果。乙醛的二价配位显示了钨（IV）-氧代中心的基本π碱度。CO拉伸频率表明供体能力的顺序为：氧代

  DOI：

  10.1016/s0277-5387(00)86523-7

文献信息

• Hall, Keith A.; Mayer, James M., Journal of the American Chemical Society, 1992, vol. 114, # 26, p. 10402 - 10411
  作者：Hall, Keith A.、Mayer, James M.

  DOI：——

  日期：——
• Deoxygenative coupling of ketones and alkenes by tungsten(II) compounds
  作者：Jeffrey C. Bryan、Jeffrey B. Arterburn、Gerald K. Cook、James M. Mayer

  DOI：10.1021/om00060a010

  日期：1992.12

  Tungsten(II) compounds such as WCl2(PMePh2)4 (1) react with acetone and ethylene tro give a good yield of the tungsten(IV)-oxo complexes W(O)(CH2=CH2)Cl2(PMePh2)2 (4) and a moderate amount of 3-methyl-1-butene. Cyclopentanone and ethylene plus 1 yield 4 and vinylcyclopentane; methyl vinyl ketone and ethylene give 4 and 3-methyl- 1,4-pentadiene. The react ion of cyclopentanone and propylene with 1 yields a small amount of 2-cyclopentylpropene. Intramolecular deoxygenative coupling occurs with 6- and 7-en-2-ones to form 1-methyl-2-methylene-substituted cyclopentyl and cyclohexyl ring systems, respectively. The net result of these reactions is transfer of the ketone oxygen atom to tungsten, accompanied with its replacement by a hydrogen and a vinyl group. The suggested mechanism for this deoxygenative coupling (Scheme I) is coordination of both the ketone and ethylene to tungsten, coupling to form a 2-oxametal-lacyclopentane, beta-hydrogen elimination to an allyloxy hydride species, C-0 bond cleavage to an oxo allyl hydride complex, and reductive elimination of alkene. Consistent with the suggestion of an oxametallacycle, hydrolysis of the reaction mixture of 1 and 6-hepten-2-one provides stereospecifically trans-1,2-di-methylcyclopentanol. The enones methyl vinyl ketone and 5-hexen-2-one react with 1 to form stable complexes in which the enone is bound in an eta4 fashion, similar to the proposed mixed alkene ketone intermediates in the coupling reactions. A related tungsten(II) butadiene complex, WCl2(CH2=CHCH=CH2)(PMePhl)2, has also been isolated.
• On the mechanism of oxygen-atom or nitrene-group transfer in reactions of epoxides and aziridines with tungsten(II) compounds
  作者：Lauren M. Atagi、Diana E. Over、Donald R. McAlister、James M. Mayer

  DOI：10.1021/ja00003a021

  日期：1991.1

  The tungsten(II) complexes WCl2(PMePh2)4 (1) and WCl2(CH2=CH2)2(PMePh2)2 (2) react with epoxides and aziridines to form tungsten(IV)-oxo and -imido complexes. The relative reactivities of epoxides with 2 have been determined from competition experiments. More substituted epoxides are harder to deoxygenate: the reactivities of ethylene, isobutylene, and tetramethylethylene oxides fall in the geometric progression 100:10:1. cis-2-Butene oxide is deoxygenated faster than its trans isomer. Reaction occurs with predominant (greater-than-or-equal-to 85%) retention of configuration (e.g. cis epoxides to cis olefins). The reaction of 2 with ethylene-d4 oxide yields W(O)Cl2(CH2=CH2)(PMePh2)2 (4) and uncoordinated CD2=CD2. The data suggest that de-epoxidation occurs via oxygen atom abstraction, and not via an oxametallacyclobutane which rearranges to an oxo-ethylene complex. Similarly, the tungsten center is suggested to attack the nitrogen atom of the aziridines, rather than react by initial oxidative addition of a C-N bond. This is indicated by the observation of an N-bound complex of aziridine and by the much slower rates of reaction for aziridines with bulky substituents on the nitrogen. The reactivities of para-substituted styrene epoxides are not strongly affected by the nature of the substituent (a-rho+-value of -0.5 is calculated with Hammett sigma+ parameters) indicating that the transition state is not very polar, although there appears to be some conjugation between the phenyl ring' and the epoxide. In sum, the data are most consistent with either concerted oxygen or nitrene transfer to tungsten or a mechanism involving a short-lived radical intermediate.
• Oxidative addition of carbon dioxide, epoxides, and related molecules to WCl2(PMePh2)4 yielding tungsten(IV) oxo, imido, and sulfido complexes. Crystal and molecular structure of W(O)Cl2(CO)(PMePh2)2
  作者：Jeffrey C. Bryan、Steven J. Geib、Arnold L. Rheingold、James M. Mayer

  DOI：10.1021/ja00243a047

  日期：1987.4
• Synthesis and characterization of high-valent oxo olefin and oxo carbonyl complexes. Crystal and molecular structure of W(O)Cl2(CH2:CH2)(PMePh2)2
  作者：Fu Min. Su、Clive. Cooper、Steven J. Geib、Arnold L. Rheingold、James M. Mayer

  DOI：10.1021/ja00272a081

  日期：1986.6