Cobalt complexes with pyrazole ligands as catalyst precursors for the peroxidative oxidation of cyclohexane: Z-ray absorption spectroscopy studies and biological applications

[CoCl(-Cl)(Hpz(Ph))(3)](2) (1) and [CoCl2(Hpz(Ph))(4)] (2) were obtained by reaction of CoCl2 with HC(pz(Ph))(3) and Hpz(Ph), respectively (Hpz(Ph)=3-phenylpyrazole). The compounds were isolated as air-stable solids and fully characterized by IR and far-IR spectroscopy, MS(ESI+/-), elemental analysis, cyclic voltammetry (CV), controlled potential electrolysis, and single-crystal X-ray diffraction. Electrochemical studies showed that 1 and 2 undergo single-electron irreversible (CoCoIII)-Co-II oxidations and (CoCoI)-Co-II reductions at potentials measured by CV, which also allowed, in the case of dinuclear complex 1, the detection of electronic communication between the Co centers through the chloride bridging ligands. The electrochemical behavior of models of 1 and 2 were also investigated by density functional theory (DFT) methods, which indicated that the vertical oxidation of 1 and 2 (that before structural relaxation) affects mostly the chloride and pyrazolyl ligands, whereas adiabatic oxidation (that after the geometry relaxation) and reduction are mostly metal centered. Compounds 1 and 2 and, for comparative purposes, other related scorpionate and pyrazole cobalt complexes, exhibit catalytic activity for the peroxidative oxidation of cyclohexane to cyclohexanol and cyclohexanone under mild conditions (room temperature, aqueous H2O2). Insitu X-ray absorption spectroscopy studies indicated that the species derived from complexes 1 and 2 during the oxidation of cyclohexane (i.e., Ox-1 and Ox-2, respectively) are analogous and contain a Co-III site. Complex 2 showed low invitro cytotoxicity toward the HCT116 colorectal carcinoma and MCF7 breast adenocarcinoma cell lines.

Reappraisal of the wrong-sign HBB¯ coupling and the study of h→Zγ

It has been pointed out recently that current experiments still allow for a two Higgs doublet model where the hbb¯ coupling (kDmb/v) is negative; a sign opposite to that of the Standard Model. Due to the importance of delayed decoupling in the hH+H− coupling, h→γγ improved measurements will have a strong impact on this issue. For the same reason, measurements or even bounds on h→Zγ are potentially interesting. In this article, we revisit this problem, highlighting the crucial importance of h→VV, which can be understood with simple arguments. We show that the impacts on kD<0 models of both h→bb¯ and h→τ+τ− are very sensitive to input values for the gluon fusion production mechanism; in contrast, h→γγ and h→Zγ are not. We also inquire if the search for h→Zγ and its interplay with h→γγ will impact the sign of the hbb¯ coupling. Finally, we study these issues in the context of the flipped two Higgs doublet model.