[Mo(CΞCH)(dppe)(η-C7H7)] | 1262296-21-8

• 英文名称: [Mo(CΞCH)(dppe)(η-C7H7)]
• 英文别名: [Mo(CΞCH)(dppe)(η-C₇H₇)]；[Mo(CCH)(dppe)(η-cycloheptatrienyl)]；[Mo(CCH)(Ph2PC2H4PPh2)(η-C7H7)]
• CAS: 1262296-21-8
• 化学式: C₃₅H₃₂MoP₂
• 分子量: 610.527
• InChiKey: QQDUBYCONJSGLF-UHFFFAOYSA-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：

  氘代溴苯 、 [Mo(CΞCH)(dppe)(η-C7H7)] 在 [PdCl₂(P(C₆H₅)3)2] 、 CuI 作用下， 以 further solvent(s) 为溶剂， 以16%的产率得到[Mo(CCC6D5)(dppe)(η-cycloheptatrienyl)]
  参考文献：
  名称：

  Experimental observation of spin delocalisation onto the aryl-alkynyl ligand in the complexes [Mo(CCAr)(Ph2PCH2CH2PPh2)(η-C7H7)]+ (Ar = C6H5, C6H4-4-F; C7H7 = cycloheptatrienyl): an EPR and ENDOR investigation

  摘要：

  该顺磁性芳基-炔基复合物[Mo(CCAr)(dppe)(η-C7H7)]+（dppe = Ph2PCH2CH2PPh2；Ar = C6H5，[1]+；C6D5，[2]+；C6H4-4-F，[3]+；C6H4-4-Me，[5]+）和[Mo(CCBut)(dppe)(η-C7H7)]+ [4]+已在结合EPR和ENDOR研究中进行了探讨。获得了关于未配对自旋密度在芳基-炔基配体框架上离域的直接实验证据。4-氟衍生物[3]+的X波段溶液EPR谱展示了芳基远端对位的超精细耦合分裂[aiso(19F) = 4.5 MHz，(1.6 G)]，此外还存在与95/97Mo、31P和C7H7环的1H耦合。1H ENDOR谱的全面分析受到系统低g各向异性的限制，这妨碍了定向选择的使用。然而，通过对[1]+、[2]+、[4]+和[5]+的1H cw-ENDOR冷冻溶液谱进行互相比较，并结合基于DFT研究得到的计算值进行谱模拟，促进了对[1]+中实验性aiso(1H)超精细耦合的估计，包括芳基-炔基配体的C6H5取代基的邻位±3.7 MHz（±1.3 G）和对位±3.9 MHz（±1.4 G）位点。

  DOI：

  10.1039/c0dt00642d
• 作为产物：
  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