| 138896-93-2

• CAS: 138896-93-2
• 化学式: C₃₂H₂₆MoO₄P₂
• 分子量: 632.444
• InChiKey: DBBMTAPCUVZKMP-SQSDHZSQSA-N

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：

  、 2,2,6,6-tetramethylpiperidinyl-lithium 在 碘甲烷 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以82%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
• 作为产物：
  描述：

  cis{1,1'-bis(diphenylphosphinomethyl)ethene-P,P'}tetracarbonylmolybdenum(0) 在 potassium tert-butylate 作用下， 以 not given 为溶剂， 生成
  参考文献：
  名称：

  Rearrangements of the unsaturated ligand 1,1-bis(diphenylphosphinomethyl)ethene and its chalcogenides and group VI metal carbonyl complexes

  摘要：

  In contrast to the behaviour of other unsaturated organophosphines, treatment of the new ligand (Ph2PCH2)2C = CH2 with Ph2PH in the presence of KOBu(t) does not result in addition to the double bond; instead, an allylic rearrangement occurs to give cis and trans Ph2PCH = C(CH3)CH2PPh2 in a 3:7 ratio. In the case of (Ph2P(E)CH2)2C = CH2 [E = S, Se] only the trans isomer is obtained from this reaction, while under similar conditions (CO)4M(Ph2PCH2)2C = CH2 [M = Cr, Mo, W] yields only a cis product in which the two phosphorus atoms remain chelated. The products of these and related reactions are characterized by elemental analysis and C-13 and P-31 NMR spectroscopy.

  DOI：

  10.1016/s0277-5387(00)86199-9

文献信息

• Transition-metal complexes of di- and tri-phosphines derived from 1,1-bis(diphenylphosphinomethyl)ethene
  作者：Jonathan L. Bookham、William Clegg、William McFarlane、Eric S. Raper

  DOI：10.1039/dt9930003567

  日期：——

  Base-catalysed rearrangements of and/or additions of PPh2H to [M(CO)4(Ph2PCH2)2C=CH2}] (M = Cr la, Mo lb or W lc) lead to cis-[M(CO)4cis-Ph2PCH=C(Me)CH2PPh2}] 2a-2c and to fac-[M(CO)3(Ph2PCH2)2C(Me)PPh2}] 3b, 3c. The structures of lb, 2b and 3b have been determined by single-crystal X-ray diffraction. Marked differences are seen in the chelate-ring conformations of 1 b with an exocyclic C=C bond, 2b with an endocyclic C=C bond, and cis-[Mo(CO)4Ph2P(CH2)3PPh2}] with no C=C bond. Proton, C-13 and P-31 NMR data for 3b and 3c were obtained and a two-dimensional rotating frame nuclear Overhauser experiment was used to identify anisochronous methylene resonances in the proton NMR spectrum of 3b thus confirming a dependence of 3J(PH) on dihedral angle in these rigid polycyclic systems.