Long-range electronic coupling of MM quadruple bonds (M = Mo or W) via a 2,6-azulenedicarboxylate bridge

Mikhail V. Barybin, Malcolm H. Chisholm, Naresh S. Dalal, Thomas H. Holovics, Nathan J. Patmore, Randall E. Robinson, David J. Zipse

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47 Citations (Scopus)


The preparation of 2,6-azulenedicarboxylic acid (I) from its diester, 2-CO2tBu-B-CO2-C10H6 (II), is reported together with the crystal and molecular structure of the ester, II. From the reactions between the dicarboxylic acid I and the MM quadruply bonded complexes M2(O2CtBu) 4, where M = Mo or W, the azulenedicarboxylate bridged complexes {M2(O2CtBu)3}2(μ-2,6- (CO2)2-C10H6) have been isolated, III (M = Mo) and IV (M = W). The latter compounds provide examples of electronically coupled M2 centers via a polar bridge. The compounds show intense electronic absorptions due to metal-to-bridge charge transfer. This occurs in the visible region of the spectrum for III (M = Mo) but in the near-IR for IV (M = W). One electron oxidation with Ag+PF 6- in THF generates the radical cations III+ and IV+. By both UV-vis-NIR and EPR spectroscopy the molybdenum ion III+ is shown to be valence trapped or Class II on the Robin and Day classification scheme. Electrochemical, UV-vis-NIR, and EPR spectroscopic data indicate that, in the tungsten complex ion IV+, the single electron is delocalized over the two W2 centers that are separated by a distance of ca. 13.6 Å. Furthermore, from the hyperfine coupling to 183W (I = 1/2), the singly occupied highest molecular orbital is seen to be polarized toward one W2 center in relationship to the other. Electronic structure calculations employing density functional theory indicate that the HOMO in compounds III and IV is an admixture of the two M2 δ orbitals that is largely centered on the M2 unit having proximity to the C5 ring of the azulenedicarboxylate bridge. The energy of the highest occupied orbital of the bridge lies very close in energy to the M2 δ orbitals. However, this orbital does not participate in electronic coupling by a hole transfer superexchange mechanism, and the electronic coupling in the radical cations of III and IV occurs by electron transfer through the bridge π* system.

Original languageEnglish
Pages (from-to)15182-15190
Number of pages9
JournalJournal of the American Chemical Society
Issue number43
Early online date8 Oct 2005
Publication statusPublished - 1 Nov 2005
Externally publishedYes


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