Investigation of monomeric versus dimeric fac-rhenium(I) tricarbonyl systems containing the noninnocent 8-oxyquinolate ligand

Helen C. Zhao, Barbara Mello, Bi Li Fu, Hara Chowdhury, David J. Szalda, Ming-Kang Tsai, David C. Grills, Jonathan Rochford

研究成果: 雜誌貢獻期刊論文同行評審

21 引文 斯高帕斯(Scopus)

摘要

Synthesis and characterization of the dimeric [fac-Re(R-OQN)(CO) 3]2 and monomeric fac-Re(R-OQN)(CO)3(CH 3CN) complexes are reported where R = unsubstituted, 2-methyl, 5,7-dimethyl, or 5-fluoro and OQN = 8-oxyquinolate. Facile solvolysis of the dimeric systems is observed in coordinating media quantitatively yielding the monomer complexes in situ. Due to poor synthetic yields of the dimeric precursors, a direct synthetic strategy for isolation of the acetonitrile monomer complexes with an improved yield was developed. The fac-Re(CH 3CN)2(CO)3Cl complex was easily generated in situ as a convenient intermediate to give the desired products in quantitative yield via reaction with the appropriately substituted 8-hydroxyquinoline and tetramethylammonium hydroxide base. Key to the success of this reaction is the precipitation of the product with triflic acid, whose conjugate triflate base is here noncoordinating. Furthermore, isolation of the solvated single crystal [fac-Re(FOQN)(CO)3](μ-Cl)[fac-Re(FHOQN)(CO)3] ·CH3C6H5 has allowed a unique opportunity to access a possible reaction intermediate, giving insight into the formation of the [fac-Re(R-OQN)(CO)3]2 dimeric systems. Spectroscopic features (UV-vis, FTIR, and 1H NMR) of both monomeric and dimeric structures are discussed in terms of the π-electron-donating ability of the oxyquinolate ligand. Interpretation of these electronic effects and the associated steric properties is aided by single-crystal X-ray diffraction, electrochemical, and DFT/TD-DFT computational studies.

原文英語
頁(從 - 到)1832-1841
頁數10
期刊Organometallics
32
發行號6
DOIs
出版狀態已發佈 - 2013 三月 25

ASJC Scopus subject areas

  • 物理與理論化學
  • 有機化學
  • 無機化學

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