The quaternary carbon at 184 29 ppm (C8) displays cross-peaks wit

The quaternary carbon at 184.29 ppm (C8) displays cross-peaks with H4 and H6, whereas the signal at 58.55 ppm (C9) couples with H5 and H7 as can be seen in the 13C,1H HMBC plot (Supporting Information, Fig. S4). The 1H NMR spectra of the coordinated to osmium(IV) 1H-indazole and

its 2H-tautomer differ significantly. In particular the chemical shift of H3 differs for 1 and 2 by ca. 10 ppm. In addition, the position of NH signal differs by 38.8 ppm (δ 124.7 ppm for [OsIVCl5(1H-ind)]− and 85.9 ppm for [OsIVCl5(2H-ind)]−). A significant downfield SB203580 order shift of C3 resonance in 1 by 99.04 ppm compared to that in [OsIVCl5(1H-ind)]− at 200.66 ppm is also of note. The shifts of other carbon signals are in the range from 1.55 to 17.51 ppm (in [OsIVCl5(1H-ind)]− the carbon resonances are at 75.94 (C9), 81.88 (C7), 106.16 (C5), 139.58 (C4), 163.74 (C6) and 173.67 (C8) ppm) [39]. The cyclic voltammograms (CV) of 1 and 2 in DMSO (0.2 M (n-Bu4N)[BF4]/DMSO) at a carbon disk working electrode,

recorded with a scan rate of 0.2 V/s, display a reversible one-electron reduction wave attributed to the OsIV → OsIII process with a potential value of 0.03 and 0.13 V for 1 and 2 respectively. Irreversible single electron reduction wave (Ired) attributed to the OsIII → OsII process is observed at − 1.43 ( Fig. 2) and − 1.33 V for 1 and 2, correspondingly. Epacadostat The redox waves OsIV/OsIII for 1 and 2 are characterized by a peak-to-peak separation (ΔEp) of 74 and 95 mV respectively, and an anodic peak current (ipa) that is almost equal to the cathodic peak current (ipc) in both cases, as expected for a reversible electron transfer process. The one-electron nature of the electron transfer process was verified by comparing the peak current height (ip) with that of the standard ferrocene/ferrocenium couple under the same experimental conditions.

The application of Lever’s equation  [58] (Eq.  (1)) [EL(Cl) = − 0.24 [59], SM(OsIII/OsII) = 1.01 [59], and IM(OsIII/OsII) = − 0.40 [59]] equation(1) E=SM∑EL+IMfor OsIII → OsII process has allowed the estimate Idoxuridine of the yet unknown EL ligand parameter for 2H-ind tautomer (1, EL = 0.18 V), whereas EL ligand parameter for 1H-ind tautomer in 2, according to Eq.  (1), is 0.28 V. Reported EL value for 1H-ind tautomer is 0.26 V [20]. This finding demonstrates the increase of the net electron-donor character (decrease of EL) of 2H-ind tautomer compared to 1H-ind tautomer, which results in decreased reduction potential of 1. The aqueous solubility of 1 is 1.2 mM at 298 K, compared to 1.3 mM for 2. The aqueous solution behavior of 1 and 2 with respect to hydrolysis was studied by optical spectroscopy at 294 K over 24 h (Fig. 3). Both complexes are stable in aqueous solution. Immediate hydrolysis was excluded since the peak at m/z 485 assigned to [OsIVCl5(Hind)]− was observed in the negative ion ESI mass spectrum of the aqueous solution of both 1 and 2 after 24 h. The UV–vis spectra of 1 and 2 are compared in Fig. 4.

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