Tris(triazolyl)borate (Ttz) ligands offer unique advantages for enzyme modeling since the distal nitrogens can bind H+ to change the donor properties. Recently, we reported [TtztBu,MeCu(I)NO2]- (1  ) as a structural and functional model for copper nitrite reductase (Dixon et al. Inorg Chem. 2012  , 51, 7004.). Increasing the amount of acid added to (1  ) increased NO(g) generated, suggesting that H+ promoted the ability of (1  ) to reduce nitrite. Therefore TtzR1,R2CuCO (2  ) was studied under acidic conditions, where vCO shifted gradually as a function of [H+] (shifted up 30 cm-1 by IR and Resonance Raman). Deconvolution of the IR spectra as a function of H+ concentration led to the assignment of bands that represent at least three distinct protonated species. Additionally, DFT provides information regarding the nature of these species. Thus Ttz's donor ability is reduced as a function of increasing [H+]. This can enhance electrophilic catalysis with Ttz-complexes.

Spectroscopy of tris(triazolyl)borate copper carbonyl complexes: Dramatic tuning of donor properties with concentration of H<sup>+</sup>

245th National Meeting (2013)

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Spectroscopy of tris(triazolyl)borate copper carbonyl complexes: Dramatic tuning of donor properties with concentration of H+

Spectroscopy of tris(triazolyl)borate copper carbonyl complexes: Dramatic tuning of donor properties with concentration of H⁺