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 Grills, Jonathan Rochford

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)1832-1841
Number of pages10
JournalOrganometallics
Volume32
Issue number6
DOIs
Publication statusPublished - Mar 25 2013

Fingerprint

Rhenium
rhenium
Carbon Monoxide
Ligands
ligands
isolation
monomers
methylidyne
solvolysis
reaction intermediates
single crystals
products
Discrete Fourier transforms
hydroxides
acetonitrile
Monomers
Single crystals
Oxyquinoline
Reaction intermediates
nuclear magnetic resonance

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Zhao, H. C., Mello, B., Fu, B. L., Chowdhury, H., Szalda, D. J., Tsai, M. K., ... Rochford, J. (2013). Investigation of monomeric versus dimeric fac-rhenium(I) tricarbonyl systems containing the noninnocent 8-oxyquinolate ligand. Organometallics, 32(6), 1832-1841. https://doi.org/10.1021/om301250v

Investigation of monomeric versus dimeric fac-rhenium(I) tricarbonyl systems containing the noninnocent 8-oxyquinolate ligand. / Zhao, Helen C.; Mello, Barbara; Fu, Bi Li; Chowdhury, Hara; Szalda, David J.; Tsai, Ming Kang; Grills, David; Rochford, Jonathan.

In: Organometallics, Vol. 32, No. 6, 25.03.2013, p. 1832-1841.

Research output: Contribution to journalArticle

Zhao, Helen C. ; Mello, Barbara ; Fu, Bi Li ; Chowdhury, Hara ; Szalda, David J. ; Tsai, Ming Kang ; Grills, David ; Rochford, Jonathan. / Investigation of monomeric versus dimeric fac-rhenium(I) tricarbonyl systems containing the noninnocent 8-oxyquinolate ligand. In: Organometallics. 2013 ; Vol. 32, No. 6. pp. 1832-1841.
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AB - 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.

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