Molybdenum Complexes of C,C-Bis(ethynyl)carboranes: Design, Synthesis, and Study of a Weakly Coupled Mixed-Valence Compound

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• 作者：Neil J. Brown ; Hannah N. Lancashire ; Mark A. Fox ; David Collison ; Ruth Edge ; Dmitry S. Yufit ; Judith A. K. Howard ; Mark W. Whiteley ; Paul J. Low
• 刊名：Organometallics
• 出版年：2011
• 出版时间：February 28, 2011
• 年：2011
• 卷：30
• 期：4
• 页码：884-894
• 全文大小：1047K
• 年卷期：v.30,no.4(February 28, 2011)
• ISSN：1520-6041

文摘

The design and study of organometallic mixed-valence complexes is complicated by the mixing of metal d and bridging ligand 蟺 orbitals, which often makes the assignment of metal oxidation states ambiguous. However, in the case of complexes based on the cycloheptatrienyl-ligated molybdenum fragment, Mo(dppe)(畏-C₇H₇), the strong ring to metal 蟺 bonding and metal to ring 未 back-bonding interactions stabilize four of the metal d orbitals, while the d_z² orbital is destabilized by filled鈭抐illed interactions with the a-type MO of the C₇H₇ ring. When the Mo(dppe)(畏-C₇H₇) auxiliary is used in conjunction with a 1,12-bis(ethynyl)-1,12-carbaborane-based bridging ligand, a weakly coupled (Robin and Day class II) mixed-valence system, [{Mo(dppe)(畏-C₇H₇)}₂{渭-1,12-(C鈮)₂-1,12-C₂B₁₀H₁₀}]⁺ ([2]⁺), with well-defined molybdenum oxidation states can be prepared. The near-IR region of [2]⁺ exhibits three intervalence charge transfer (IVCT) transitions and two lower intensity interconfigurational (or dd) transitions, which have been resolved through spectral deconvolution. The band shape of the lowest energy IVCT transition associated with [2]⁺, which arises from electron exchange between the d_z²-type orbitals at the two Mo centers, is in excellent agreement with the predictions of the Hush two-state model for weakly coupled mixed-valence complexes. The half-height bandwidths of the higher energy IVCT transitions, which arise from transitions between lower lying metal orbitals that have symmetry properties that permit more significant mixing with the bridging ligand, are in less good agreement with the Hush model, due to the breakdown of the two-state approximation through the greater involvement of the bridge-based orbitals in those transitions.