Dinuclear Ruthenium Nitrido Complexes Supported by an Oxygen Tripodal Ligand
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- 作者：Xiao-Yi Yi ; Ho-Yuen Ng ; Wai-Man Cheung ; Herman H. Y. Sung ; Ian D. Williams ; Wa-Hung Leung
- 刊名：Inorganic Chemistry
- 出版年：2012
- 出版时间：October 15, 2012
- 年：2012
- 卷：51
- 期：20
- 页码：10529-10535
- 全文大小：423K
- 年卷期：v.51,no.20(October 15, 2012)
- ISSN：1520-510X
文摘
Dinuclear ruthenium nitrido complexes supported by the Kl盲ui鈥檚 tripodal ligand [CpCo{P(O)(OEt)2}3]鈭?/sup> (LOEt鈥?/sup>) have been synthesized starting from the ruthenium(VI) nitrido precursor [LOEtRuVI(N)Cl2] (1). Heating a solution of 1 in CCl4 at reflux, followed by recrystallization from hexane under nitrogen, afforded the mixed-valence ruthenium(V)鈥搑uthenium(IV) 渭-nitrido complex [LOEtCl2RuV(渭-N)RuIVCl2LOEt] (2). The cyclic voltammogram of 2 exhibited reversible couples at 0.19 and 1.13 V versus Cp2Fe+/0, which are assigned as the RuV鈥揜uIV/RuIV鈥揜uIV and RuV鈥揜uV/RuV鈥揜uIV couples, respectively. Recrystallization of 2 from Et2O/heptane in air yielded the diamagnetic RuIV鈥揜uIV complex [H13O6][{LOEtRuIVCl2}2(渭-N)] ([H13O6][2]), which underwent cation exchange with n-Bu4NOH to give [n-Bu4N][2]. X-ray diffraction revealed that the complex anions in [H13O6][2] and [n-Bu4N][2] contain linear, symmetric Ru鈥揘鈥揜u bridges. Treatment of 1 with [(畏6-p-cymene)RuIICl2]2 in benzene afforded the tetranuclear ruthenium(IV) complex [LOEtCl2RuIV(渭-N)RuIV(H2O)Cl2]2 (3) containing symmetric RuIV鈥揘鈥揜uIV bridges. The reaction of 1 with [RuII(H)(Cl)(CO)(PCy3)2] (Cy = cyclohexyl) gave the ruthenium(VI)鈥搑uthenium(II) nitrido complex [LOEtCl2RuVI(渭-N)RuII(H)Cl(CO)(PCy3)2] (4). The observed short RuII鈥揘 bond distance [1.915(5) 脜] and high C鈥揙 stretching frequency (1985 cm鈥?) in 4 are suggestive of 蟺 interaction between RuII and the nitride.