[Mo(C=C(H)Bu(t))(Me2PCH2CH2PMe2)(η-C7H7)][PF6] | 171415-76-2

• 英文名称: [Mo(C=C(H)Bu(t))(Me2PCH2CH2PMe2)(η-C7H7)][PF6]
• CAS: 171415-76-2
• 化学式: C₁₉H₃₃MoP₂*F₆P
• 分子量: 564.323
• InChiKey: OZLZSMPLUDVETK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 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：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  (η-toluene)(η-cycloheptatrienyl)molybdenum hexafluorophosphate 、 1,2-双(二甲基瞵)乙烷 在 acetone 作用下， 以 丙酮 为溶剂， 以1.3%的产率得到[Mo(C=C(H)Bu(t))(Me2PCH2CH2PMe2)(η-C7H7)][PF6]
  参考文献：
  名称：

  Vinylidene complexes of the molybdenum auxiliary Mo(Ph2PCH2CH2PPh2)(C7H7). Structural and spectroscopic investigations on vinylidene ligand orientation

  摘要：

  The new vinylidene complexes [Mo{C=C(H)R}(L-L)(eta-C7H7)](+)[L-L=Ph(2)PCH(2)CH(2)PPh(2)(dppe), R = Bu(t), Bu(n) or H; L-L = Ph(2)PCH(2)PPh(2) (dppm), R = Bu(t); L-L = Me(2)PCH(2)CH(2)PMe(2) (dmpe). R = Bu(t)] have been synthesised by reaction of an excess: of alk-1-yne, RC=CH, either with [Mo(Me(2)CO)(L-L)(eta-C7H7)](+)(L-L=dppe or dmpe) {formed in situ from [Mo(eta(6)-C(6)H(5)Me)(eta-C7H7)](+) and dppe or dmpe in acetone) or with [MoCl(L-L)(eta-C7H7)](L-L = dppe or dppm) in methanol in the presence of [NH4][PF6]. The formation of [Mo{C=C(H)Bu(t)}(dmpe)(eta-C7H7)](+) is accompanied by conversion of the excess of alkyne into polymeric (BUC)-C-t=CH with respective M(n) and M(w) values of 29 x 10(3) and 63 x 10(3) as determined by gel permeation chromatography. Deprotonation of [Mo{C=C(H)Bu(n)}(dppe)(eta-C7H7)](+) with KOBu(t) yields the alkynyl [Mo(C=CBu(n))(dppe)(eta-C7H7)]. The disubstituted vinylidenes [Mo(C=C(Me)R)(dppe)(eta-C7H7)](+) (R = Bu(t) or Bu(n)) were obtained by C-beta methylation of [Mo(C=CR)(dppe)(eta-C7H7)] with Mel. One-electron oxidation of the alkynyls [Mo(C=CR)(dppe)(eta-C7H7)](R = Bu(n) or Ph) with [Fe(eta-C5H5)(2)](+) yields the 17-electron radicals [Mo(C=CR)(dppe)(eta-C7H7)](+) (R = Bu(n) or Ph) which undergo coupling at C-beta to yield dimeric, divinylidene-bridged [Mo-2(dppe)(2)(eta-C7H7)(2)(mu-C(4)R(2))](2+) (R = Bu(n) or Ph). The crystal structures of [Mo(C=C(H)Ph}(dppe)(eta-C7H7)][BF4] and [Mo-2(dppe)(2)(eta-C7H7)(2)(mu C(4)Ph(2))][PF6](2), have been determined. In the former the vinylidene substituents lie approximately in the pseudo-mirror plane of the Mo(dppe)(eta-C7H7) moiety (a vertical orientation) with the phenyl substituent directed 'up' towards the cycloheptatrienyl ring. In the latter centrosymmetric dimer the vinylidene ligand is rotated by 19.1 degrees away from an exact vertical orientation and the phenyl substituents are located 'down' into a pocket enclosed by two phenyl groups of the dppe ligand. Variable-temperature H-1 NMR investigations on [Mo(C=CH2)(dppe) (eta-C7H7)](+) are consistent with a preferred vertical orientation of the vinylidene ligand in solution at low temperature and the barrier to vinylidene rotation has been estimated as 51.9 +/- kJ mol(-1). The H-1 and P-31 NMR solution spectra of [Mo{C=C(R')Bu(n)}(dppe)(eta-C7H7)](+) (R' = H or Me) are also consistent;with a vertically orientated vinylidene ligand and reveal the existence of two isomeric forms of each complex which differ in the location of the n-butyl substituent in the 'up' or 'down' position.

  DOI：

  10.1039/dt9950002873