Facile 畏5鈥撐?sup>1 Ring Slippage of the Cycloolefin Ligands in Osmocene and Bis(畏5-indenyl)ruthenium(II)
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- 作者：Wai-Man Cheung ; Enrique Kwan Huang ; Jun Zhu ; Xiao-Yi Yi ; Herman H. Y. Sung ; Ian D. Williams ; Wa-Hung Leung
- 刊名：Inorganic Chemistry
- 出版年：2013
- 出版时间：September 16, 2013
- 年：2013
- 卷：52
- 期：18
- 页码：10449-10455
- 全文大小：556K
- 年卷期：v.52,no.18(September 16, 2013)
- ISSN：1520-510X
文摘
畏5鈥撐?sup>1 ring slippage of [OsCp2] (Cp = 畏5-C5H5) and [Ru(畏5-ind)2] (ind = indenyl) resulting from reaction with the ruthenium(VI) nitride [Ru(LOEt)(N)Cl2] (1; LOEt鈥?/sup> = [CoCp{P(O)(OEt)2}3]鈭?/sup>) is reported. The treatment of [OsCp2] or [Ru(畏5-ind)2] with 1 resulted in 畏5-畏1 ring slippage of the cycloolefin ligands and formation of the trinuclear nitrido complexes [Cp(畏1-C5H5)Os(NRuLOEtCl2)2] (2) or [(畏5-ind)(畏1-ind)Ru(NRuLOEtCl2)2] (3). No reactions were found between [OsCp2] and amines, such as pyridine and 2,2鈥?bipyridyl, or other metal nitrides, such as [Os(LOEt)(N)Cl2], indicating that the electrophilic property of 1 is essential for ring slippage. The crystal structures of 2 and 3 have been determined. The short Os鈥揘 distances in 2 [1.833(5) and 1.817(5) 脜] and the (ind)Ru鈥揘 distances in 3 [1.827(5) and 1.852(5) 脜] are indicative of multiple bond character, consistent with density functional theory (DFT) calculations. Therefore, 2 and 3 may be described by two resonance forms: RuVI鈥揗II鈥揜uVI and RuIV鈥揗VI鈥揜uIV (M = Os, Ru). Also, DFT calculations indicate that for the reaction of 1 with [OsCp2] or [Ru(畏5-ind)2], 畏5鈥撐?sup>1 ring slippage is energetically more favorable than the 畏5鈥撐?sup>3 counterpart. The driving force for 畏5鈥撐?sup>1 ring slippage is believed to be the formation of the strong M鈥揘 (M = Os, Ru) (multiple) bonds. By contrast, the same reaction with acetonitrile is energetically uphill, and thus no ring slippage occurs.