[Mo(C=CH2)(Ph2PCH2CH2PPh2)(η-C7H7)][PF6] | 171415-72-8

• 英文名称: [Mo(C=CH2)(Ph2PCH2CH2PPh2)(η-C7H7)][PF6]
• 英文别名: [Mo(C=CH2)(Ph2PC2H4PPh2)(η-C7H7)]PF6
• CAS: 171415-72-8
• 化学式: C₃₅H₃₃MoP₂*F₆P
• 分子量: 756.499
• InChiKey: FAVLVKGYKBYMQK-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

• 作为反应物：
  描述：

  [Mo(C=CH2)(Ph2PCH2CH2PPh2)(η-C7H7)][PF6] 在 t-BuOK 作用下， 以 四氢呋喃 为溶剂， 以78%的产率得到[Mo(CΞCH)(dppe)(η-C7H7)]
  参考文献：
  名称：

  Orbital Symmetry Control of Electronic Coupling in a Symmetrical, All-Carbon-Bridged “Mixed Valence” Compound: Synthesis, Spectroscopy, and Electronic Structure of [{Mo(dppe)(η-C₇H₇)}₂(μ-C₄)]ⁿ⁺(n= 0, 1, or 2)

  摘要：

  The cycloheptatrienyl molybdenum alkynyl complex [Mo(C CH)(dppe)(eta-C7H7)], 1 (dppe = Ph2PCH2CH2PPh2), undergoes oxidative dimerization on reaction with [FeCp2]PF6 in thf at -78 degrees C to give the bis(vinylidene) [{Mo(dppe)(eta-C7H7)}(2)(mu-C=CH-CH=C)][PF6](2), [2][PF6](2). Deprotonation of [2][PF6](2) with KOBut yields butadiyndiyibridged [{Mo(dppe)(eta-C7H7)}(2)(mu-C C-C C)], 3, which undergoes in situ aerial oxidation to give [{Mo(dppe)(q-C7H7)}2(p-C4)][PF6], [3]PF6, as the major product. The cyclic voltammogram of [3]PF6 exhibits a series of four redox processes indicative of sequential formation of [{Mo(dppe)(eta-C7H7)}(2)(mu-C-4)](n+) (n = 0, 1, 2, 3, 4) with the comproportionation constant, K-C, for [3]PF6 of 1.9 x 10(7). Spectroscopic investigations on [3]PF6 by IR, Raman, NIP., and EPR spectroscopy reveal properties characteristic of a d(5)/d(6) mixed valence complex with a localized electronic structure and an estimated intramolecular electron transfer rate in the range 10(8)-10(10) s(-1). The experimental NIR spectrum of [3]PF6 is consistent with the predicted spectral characteristics of a three-state model for bridge-mediated, electron transfer in a weakly coupled, symmetrical mixed valence system. The dication [3][PF6]2 was isolated by chemical oxidation and structurally characterized; magnetic susceptibility measurements on [3][PF6]2 in the temperature range 2-300 K reveal strong antiferromagnetic coupling with the exchange coupling constant Jab (defined according to the Hamiltonian (H) over cap (spin) = -J(ab)center dot(S) over cap (a)center dot(S) over cap (b)) determined as -406 (+/-3) cm(-1).

  DOI：

  10.1021/om200712m
• 作为产物：
  描述：

  (η-toluene)(η-cycloheptatrienyl)molybdenum hexafluorophosphate 、 三甲基乙炔基硅 在 Ph₂PCH₂CH₂PPh₂ 、 acetone 作用下， 以 丙酮 为溶剂， 以73%的产率得到[Mo(C=CH2)(Ph2PCH2CH2PPh2)(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