| 138897-23-1

• CAS: 138897-23-1
• 化学式: C₃₅H₃₄MoO₄P₂Si
• 分子量: 704.626
• InChiKey: GZTBXXHWLZHKSY-PTPCTUKCSA-N

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：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  三甲基氯硅烷 、 、 lithium hexamethyldisilazane 以 四氢呋喃 为溶剂， 以27%的产率得到
  参考文献：
  名称：

  Synthesis and reactions of complexes of 1,3-bis(diphenyl-phosphino)-2-methylallyl with molybdenum or tungsten tetracarbonyls

  摘要：

  Treatment of molybdenum or tungsten hexacarbonyls with the diphosphine CH2 = C(CH2PPh2)2 gives complexes [M{(Ph2PCH2)2C = CH2}(CO)4] (M = Mo, 3a; or W, 3b). Either of these complexes with sodium ethoxide in boiling ethanol exhibits prototropic rearrangement to give [M{Ph2PCH = CMeCH2PPh2}(CO)4] (M = Mo, 4a; or W, 4b). Treatment of either complexes 3 or 4 with strong bases such as methyllithium, lithium 2,2,6,6-tetramethylpiperidide or lithium bis(trimethylsilyl)amide gave bright orange solutions of the symmetrical 1,3-bis(diphenylphosphino)-2-methylallylmetal tetracarbonyl anions [M{Ph2PCHC(Me)CHPPh2}(CO)4]- 5. The molybdenum complex 5a, when treated with D2O, gave [Mo(Ph2PCH = CMeCHDPPh2)(CO)4] 6, which was shown to be a monodeuterio-complex by H-2, H-1 and C-13 NMR spectroscopy. Both the P-31-{H-1} and the C-13-{H-1} NMR spectra of this compound showed secondary isotope effects and the C-13-{H-1} spectrum showed that there was no plane of symmetry, whereas with the corresponding perhydro complex 4a, there is such a plane (going through the Mo and the two P). The carbanions 5 react with electrophiles such as Mel, SiMe3Cl, Etl, allyl bromide, PhCH2Br or PPh2Cl to give substitution products [M(Ph2PCH = CMeCHR'PPh2)(CO)4] (R' = Me, 7; SiMe3, 8; Et, 9; CH2 = CHCH2, 10; CH2Ph, 11, or PPh2, 13); these complexes were fully characterised. Treatment of 7a (M = Mo) with LiMe and then an equivalent amount of methanol, followed by more LiMe and methanol, gave the isomerised product [Mo(Ph2PCMe = CMeCH2PPh2)(CO)4] 12. When a solution of complex 13a M = M) was heated in toluene the tricarbonyl [Mo{(Ph2P)2CHCMe = CHPPh2}(CO)3] 14a, in which all three phosphoruses are co-ordinated, was formed; similarly the corresponding tungsten complex 13b, when heated in decane, gave [W{(Ph2P)2CHCMe = CHPPh2}(CO)3] 14b. Proton, H-2, C-13 and P-31 NMR data, infrared [nu(C = O)] and some mass spectral data are given and discussed.

  DOI：

  10.1039/dt9910003303