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Acta Chimica Sinica ›› 2011, Vol. 69 ›› Issue (17): 2021-2025. Previous Articles     Next Articles

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一种水溶性氢氧根钌配合物的合成及其对乙腈的催化水化作用

尹传奇*,刘珺,柏正武   

  1. (武汉工程大学化工与制药学院 绿色化工过程教育部重点实验室 湖北省新型反应器与绿色化学工艺重点实验室 武汉 430074)
  • 投稿日期:2011-03-06 修回日期:2011-05-03 发布日期:2011-05-10
  • 通讯作者: 尹传奇 E-mail:zhyfyin@126.com
  • 基金资助:

    氢氧根钌配合物的合成及其对腈、末端炔烃的催化水化;过渡金属氢氧根配合物的合成及其对腈、末端炔烃的催化水化

Synthesis of a Water-Soluble Ruthenium Hydroxide Complex and Its Role in Catalytic Hydration of Acetonitrile

YIN Chuan-Qi, LIU Jun, BAI Zheng-Wu   

  1. (School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Key Laboratory for Green Chemical Process of Ministry of Education, Hubei Key Laboratory of Novel Reactor and Green Chemical Technology, Wuhan 430074)
  • Received:2011-03-06 Revised:2011-05-03 Published:2011-05-10
  • Contact: Chuan-Qi YIN E-mail:zhyfyin@126.com

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In the presence of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene), a novel water-soluble hydroxide ruthenium complex [(bipy)2Ru(H2O)(OH)](OTf) was synthesized by deprotonation of [(bipy)2Ru(H2O)2]- (OTf)2 (bipy＝2,2-bipyridine, Otf－＝triflate), which was prepared using RuCl3•3H2O as starting material. The hydration of acetonitrile to form acetamide catalyzed by [(bipy)2Ru(H2O)(OH)](OTf) was studied. O-bonded imido complex [(bipy)2Ru(N≡CCH3)(OCMe＝NH)]＋ is postulated to be the key intermediate, which then undergoes nucleophilic attack at the carbon atom of nitrile ligand to form [(bipy)2Ru(k2-N,O- NH＝CMeN＝CMeO)]＋. Ring-opening nucleophilic attack of [(bipy)2Ru(k2-N,O-NH＝CMeN＝CMeO)]＋by water produces {(bipy)2Ru[NH＝C(OH)Me](OCMe＝NH)}＋. The displacement of NH＝C(OH)Me ligand in the latter complex by acetonitrile forms acetamide, and regenerates [(bipy)2Ru(N≡CCH3)- (OCMe＝NH)]＋ to fulfill catalytic cycle.

Key words: water-soluble ruthenium hydroxide complex, acetonitrile, catalytic hydration, mechanism