高等学校化学学报 ›› 2004, Vol. 25 ›› Issue (11): 2019-2023.

• 研究论文 • 上一篇    下一篇

顺二羰基(三齿N-配体)铑(Ⅰ)配合物的分子内取代反应

张抒峰, 钱庆利, 陈义, 袁国卿   

  1. 中国科学院化学研究所, 北京100080
  • 收稿日期:2003-12-09 出版日期:2004-11-24 发布日期:2004-11-24
  • 基金资助:

    国家自然科学基金(批准号:20244001)资助

Intramolecular Substitution Reaction of cis-Dicarbonyl Rhodium(Ⅰ) Complexes Containing Tridentate N-Donor Ligand

ZHANG Shu-Feng, QIAN Qing-Li, CHEN Yi, YUAN Guo-Qing   

  1. Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China
  • Received:2003-12-09 Online:2004-11-24 Published:2004-11-24

摘要: 报道了3种不同结构的三齿N-配体以及与铑形成的顺二羰基配合物.研究表明,正方平面顺二羰基铑配合物在遇热条件下,其配体中未参与配位的授体N原子可取代它的一个端羰基而形成新的三齿配位结构.而在CO气氛下,三齿配位结构回到二齿配位状态.正方平面铑配合物的这一特殊分子内取代可逆反应过程,对于研究这类配合物结构、性能及催化作用均有重要的意义.非正方平面顺二羰基铑配合物则不发生上述分子内取代反应.利用IR和XPS对上述反应进行了表征.

关键词: 分子内取代, 铑配合物, 正方平面

Abstract: Square planar tetracoordinated Rh(Ⅰ) complex is a typical organometallic complex. In catalytic reactions its four-coordinated structure is the precursor of an active compound. The study on its structure is very important for investigating the catalytic procedure. In this paper, the intramolecular substitution reaction of a novel kind of square planar cis-dicarbonyl rhodium cationic complexes containing different N-coordinated tridentate ligands were studied. \%N,N\%-Bis(2-pyridylethyl)-aniline(DPBA), 1,2,3-tri(2-pyridyl) propane(TPP), tri(2-methylenepyridine) methane(TPM) were resolved in methanol respectively, into which an appropriate amount of [Rh(CO)2Cl]2 methanol solution was added under stirring at 0 ℃ and atmosphere of CO to get yellowish carbonyl rhodium complexes respectively. The changes of carbonyl rhodium complexes structures were analyzed by IR and XPS. It is shown that the uncoordinated electron donating nitrogen of the ligand, when heated, may replace the terminal carbonyl to form a new type of tridentate complexes, the weak N—Rh bond can replace the strong Rh—CO σ-π bond. The intramolecular substitution reaction is reversible. The formal cis-dicarbonyl bidentate N-coordinated complex recovers if the newly formed complex is put under the atmosphere of CO. So the rhodium complexes will not decompose for the drop of the terminal carbonyls and their stability is enhanced. There is no such reversible intramolecular substitution reaction in non square-planar cis-dicarbonyl rhodium complexes.

Key words: Intramolecular substitution, Rhodium complexes, Square planar

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