Heterobimetallic N‑Heterocyclic Carbene Complexes: A Synthetic, Spectroscopic, and Theoretical Study

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Pell, T. P., Wilson, D. J., Skelton, B. W., Dutton, J. L., & Barnard, P. J. (2016). Heterobimetallic N‑Heterocyclic carbene complexes: A synthetic, spectroscopic, and theoretical study. Inorganic Chemistry, 55(14), 6882-6891. doi: 10.1021/acs.inorgchem.6b00222



030701 Quantum Chemistry

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A new synthetic methodology has been developed for the preparation of heterobimetallic group 11 and group 12 complexes of a symmetrical bis-NHC “pincer” ligand. The synthetic route involved the initial preparation of a mononuclear [Au(NHC)2]+ complex with pendent imidazole moieties on the NHC ligands. Subsequent alkylation of the imidazole groups with Et3OBF4 and metalation with a second metal ion (Ag(I) or Hg(II)) provided two heterobimetallic complexes. Four homobimetallic (Cu(I)2, Ag(I)2, Au(I)2, and Hg(II)2) complexes of the same bis-NHC “pincer” ligand were also prepared. The homobimetallic Cu(I)2, Au(I)2, and Hg(II)2 complexes and heterobimetallic Au(I)−Ag(I) and Au(I)−Hg(II) complexes and the synthetic intermediates for the heterobimetallic complexes were characterized by X-ray crystallography. These X-ray structures show that the bimetallic complexes adopt “twisted” conformations in the solid state, supporting short M···M interactions. Crystalline samples of the homobimetallic Ag(I)2 and Au(I)2 and heterobimetallic Au(I)−Ag(I) and Au(I)−Hg(II) complexes were emissive at room temperature and at 77 K. The geometries of the synthesized complexes were optimized at the M06-L/def2-SVP level of theory, and the electronic nature of the M···M interactions for all synthesized complexes was investigated using natural bond orbital (NBO) calculations.


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David Wilson is affiliated with Avondale College as a Conjoint Senior Lecturer.

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