[Mo2(CO)4(μ-I)(μ-η(7):η(7)-C14H12)][PF6] | 172370-17-1

• 英文名称: [Mo2(CO)4(μ-I)(μ-η(7):η(7)-C14H12)][PF6]
• CAS: 172370-17-1
• 化学式: C₁₈H₁₂IMo₂O₄*F₆P
• 分子量: 756.04
• InChiKey: LAZCUDQQORJUMW-UHFFFAOYSA-M

反应信息

• 作为产物：
  描述：

  [Mo2I(CO)5(μ-η(7):η(7)-C14H12)][PF6] 以 四氢呋喃 为溶剂， 以44%的产率得到[Mo2(CO)4(μ-I)(μ-η(7):η(7)-C14H12)][PF6]
  参考文献：
  名称：

  Synthesis, structure and reactivity of bicycloheptatrienyl-bridged dimolybdenum complexes: crystal structure of [Mo₂(CO)₄(µ-I)(µ-η⁷: η⁷-C₁₄H₁₂)][PF₆]

  摘要：

  Thermal rearrangement of bicycloheptatriene, C14H14, followed by reaction with 1 equivalent of [CPh(3)][PF6] at -26 degrees C afforded the cycloheptatriene-substituted cycloheptatrienyl cation, [C14H13][PF6] as a mixture of two isomers differing in the position of the CH2 group on the cycloheptatriene ring. Treatment of [C14H13][PF6] with a further equivalent of [CPh(3)][PF6] afforded the bicycloheptatrienyl dication [C14H12][PF6](2) which reacts with [Mo(CO)(3)(NCMe)(3)] to give the bicycloheptatrienyl bridged bimetallic [Mo-2(CO)(6)(mu-eta(7):eta(7)-C14H12)][PF6](2) 1. Reaction of [C14H13][PF6] with [Mo(CO)(3)(NCMe)(3)] leads to co-ordination at the cycloheptatrienyl ring and formation of [Mo(CO)(3)(eta(7)-C14H13)][PF6] 2 which is the precursor to [Mo-2(CO)(2)(eta(7)-C14H12)][PF6] 5 which contains an unco-ordinated, pendant cycloheptatrienyl ring. Complex 5 reacts with [Mo(CO)(2)(NCMe)(3)] to give doubly bridged [Mo-2(CO)(4)(mu-l)(mu-eta(7):eta(7)-(CH12)-H-14)][PF6] 7. X-Ray cyrstallographic characterisation of 7 reveals two crystallographically distinct cations both of which exhibit a twisted conformation of the bicycloheptatrienyl ligand. Reaction of 1 with Na[Mn(CO)(5)] results in conversion of the carbon-carbon bond which links the bridgehead carbons. from a single to a double bond and isolation of heptafulvalene-bridged [Mo-2(CO)(6)(mu-eta(6):eta(6)-C14H12)] 8. The acetonitrile derivative [Mo-2(CO)(4)(NCMe)(2)(mu-eta(7):eta(7)-C14H12)][BF4](2) 11, formed in a two-step synthesis from 1, is activated towards eta(7)-->eta(3) hapticity interconversion by comparison with [Mo(CO)(2)(NCMe)(eta(7)-C7H7)][BF4]. and when 11 is dissolved in acetonitrile at room temperature, the major product is [Mo-2(Co)(4)(NCMe)(6)(mu-eta(3):eta(3)-C14H12)][BF4](2) 13 Cyclic voltammetric investigations on [Mo-2(NCMe)(2) (Ph(2)PCH(2)CH(2)PPh(2))(2)(mu-eta(7):eta(7)-C14H12)][PF6](2) 15 reveal two discrete, reversible oxidations with Delta E degrees = 130 mV, indicating a limited degree of intermetallic electronic communication through the bicycloheptatrienyl ligand.

  DOI：

  10.1039/dt9950003231