期刊文献+
任意字段
题名或关键词
题名
关键词
文摘
作者
第一作者
机构
刊名
分类号
参考文献
作者简介
基金资助
栏目信息

氢氧根钌配合物的合成及其对乙腈的催化水化研究 被引量：1

Study on Synthesis of Ruthenium Hydroxo Complex and Its Catalytic Hydration for Acetonitrile
下载PDF
导出
摘要 利用三乙胺对配合物[TpRu(PPh3)2(H2O)]BF4脱质子化合成了氢氧根钌配合物TpRu(PPh3)2(OH),并研究了TpRu(PPh3)2(OH)催化水化乙腈的反应。机理研究表明,催化循环的关键中间体为氧配位的酰亚胺配合物TpRu(PPh3)(CH3CN)(OCMe=NH),经过生成TpRu(PPh3)(κ2-N,O-NH=CMeN=CMeO)、水亲核进攻开环生成TpRu(PPh3)(NH=C(OH)Me)(OCMe=NH)、乙腈取代其NH=C(OH)Me配体产生乙酰胺、同时生成TpRu(PPh3)(CHCN)(OCMe=NH)完成催化循环。 Ruthenium hydroxo complex TpRu（PPh3）2 （OH） has been synthesized by deprotonation of [-Tp- Ru（PPh3）2 （H20）-]BF4 in the presence of triethyl amine. The catalytic hydration of acetonitrile by TpRu （PPh3）2 （OH） is studied. The catalytic mechanism is proposed that O-bonded imido complex TpRu（PPb3） （CH3CN）（OCMe=NH） is the key intermediate, which then undergoes nucleophilic attack at the carbon atom of nitrile ligand to form TpRu（PPh3）（k^2 -N ,O-NH=CMeN=CMeO）. Ring-opening necleophilic attack of TpRu（PPh3 ） （k^2 -N ,O-NH = CMeN= CMeO） by water pruduces TpRu（PPh3 ） （NH = C（OH） Me） （OCMe= NH）. The displacement of NH = C（OH）Me ligand in the latter complex by acetonitrile forms acetamide, and regenerates TpRu（PPh3）（CH3CN）（OCMe=NH） to fulfill the catalytic cycle.
作者 尹传奇 杜小秋 柏正武
机构地区 武汉工程大学化工与制药学院绿色化工过程省部共建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
出处 《化学与生物工程》 CAS 2009年第8期25-28,共4页 Chemistry & Bioengineering
基金 湖北省自然科学基金资助项目(2006ABA282) 湖北省教育厅基金资助项目(D200615005)
关键词 氢氧根钌配合物 乙腈 催化水化 机理 ruthenium hydroxo complex acetonitrile catalytic hydration mechanism
分类号 O626.11 [理学—有机化学] TQ032.41 [化学工程]
  • 相关文献

参考文献17

  • 1Jung H K, James B, Jik C. Kinetics and mechanism of a cobalt (Ⅲ) complex catalyzed hydration of nitriles[J]. J Am Chem Soc, 1993, 115(9): 3618-3622.
  • 2Breno K L, Pluth M D, Tyler D R. Organometallic chemistry in aqueous solution. Hydration of nitriles to amides catalyzed by a water-soluble molybdocene, (MeCp)2 Mo(OH) ( H3O) + [J]. Organometallics, 2003, 22(6): 1203-1211.
  • 3Kaminskaia N V,Kostic N M. Nitrile hydration catalyzed by palladium(Ⅱ) complexes[J]. J Chem Soc, Dalton Trans, 1996, (18) :3677-3686.
  • 4Feng Y, Lail M, Barakat K A, et al. Evidence for the net addition of arene C-H bonds across a Ru(Ⅱ)-hydroxide bond [J]. J Am Chem Soc, 2005, 127(41): 14174-14175.
  • 5Feng Y, Lail M, Foley N A, et al. Hydrogen-deuterium exchange between TpRu (PMe3) (L) X ( Tp = hydridotris (pyrazolyl) borate; L=PMe3 and X=OH, OPh, Me, Ph, or NHPh; L= NCMe and X= Ph) and deuterated arene solvents: Evidence for metal-mediated processes [J]. J Am Chem Soc, 2006, 128(24): 7982-7994.
  • 6Masters C. Homogeneous Transition Metal Catalyst[M]. New York: Chapman & Hall, 1981: 70-82.
  • 7Bennett M A, Yoshida T. Synthesis and reactivity of zerovalent platinum complexes of short-lived cyclic alkynes. Formation of monomeric platinum(Ⅱ) hydroxo-, methoxo-, and sigma-carbonbonded complexes by oxidative addition reactions with water, methanol, and activated hydrocarbons and catalysis of nitrile to amide hydration[J]. J Am Chem Soc, 1978, 100(6): 1750-1759.
  • 8Bennett M A, Yoshida T. Homogeneously catalyzed hydration of nitriles to carboxamides[J]. J Am Chem Soc, 1973, 95(9): 3030-3031.
  • 9Jensen C M, Trogler W C. Kinetics and mechanism of nitrile hydration catalyzed by unhindered hydridobis(phosphine) platinum (Ⅱ) complexes. Regioselective hydration of acrylonitrile[J]. J Am Chem Soc, 1986, 108(4): 723-729.
  • 10Jensen C M, Trogler W C. Catalytic hydration of terminal alkenes to primary alcohols[J]. Science, 1986, 233(4768) : 1069- 1071.

二级参考文献18

  • 1Leither,W.Angew.Chem.,Int.Ed.Engl.1995,34,2207.
  • 2Leither,W.Coord.Chem.Rev.1996,153,257.
  • 3Yin,C.; Xu,Z.; Yang,S.Y.; Ng,S.M.; Wong,K.Y.; Lin,Z.; Lau,C.P.Organometallics 2001,20,1216.
  • 4Munshi,P.; Main,A.D.; Linehan,J.C.; Tai,C.C.; Jessop,P.G.J.Am.Chem.Soc.2002,124,7963.
  • 5Thomas,C.A.; Bonilla,R.J.; Huang,Y.; Jessop,P.G.Can.J.Chem.2001,79,719.
  • 6Ng,S.M.; Yin,C.; Yang,C.; Chan,T.; Lau,C.P.Eur.J.Inorg.Chem.2004,1788.
  • 7Chan,W.C.; Lau,C.P.; Chen,Y.Z.; Fang,Y.Q.; Ng,S.M.Organometallics 1997,16,34.
  • 8Perrin,D.R.; Armanego,W.L.Purification of Laboratory Chemicals,2nd ed.,Pergmon,Oxford,1980.
  • 9Kim,H.S.; Kim,J.J.; Lee,B.G.; Jung,O.S.; Jang,H.G.; Kang,S.O.Angew.Chem.,Int.Ed.2000,39,4096.
  • 10Tsuda,T.; Sanada,S.; Ueda,K.; Saegusa,T.Inorg.Chem.1976,15,2329.

共引文献4

同被引文献21

  • 1Masters, C. Homogeneous Transition Metal Catalyst, Chapman & Hall, New York, 1981.
  • 2Bennett, M. A.; Yoshida, T. J, Am. Chem. Soc. 1978, 100(6), 1750.
  • 3Bennett, M. A.; Yoshida, T.J. Am. Chem. Soc. 1973, 95(9), 3030.
  • 4Jensen, C. M.; Trogler, W. C. J. Am. Chem. Soc. 1986, 108, 723.
  • 5Jensen, C. M; Trogler, W. C. Science 1986, 233, 1069.
  • 6Yoshida, T.; Matsuda, T.; Okano, T.; Kitani, T.; Otsuka, S. J. Am. Chem. Soc. 1979, 101, 2027.
  • 7Kim, J. H.; Britten, J.; Chin, J. J. Am. Chem. Soc. 1993, 115(9), 3618.
  • 8Breno, K. L.; Pluth, M. D.; Tyler, D. R. Organometallics 2003, 22(6), 1203.
  • 9Kaminskaia, N. V.; Kosti6, N. M. J. Chem. Soc., Dalton Trans. 1996, 3677.
  • 10Feng, Y.; Lail, M.; Barakat, K. A.; Cundari, T. R.; Gunnoe, T. B.; Petersen, J. L. J. Am. Chem. Soc. 201}5, 127, 14174.

引证文献1

二级引证文献3

化学与生物工程
2009年 第8期

相关作者

内容加载中请稍等...

相关机构

内容加载中请稍等...

相关主题

内容加载中请稍等...

浏览历史

内容加载中请稍等...
;
使用帮助 返回顶部