The neutral and one-electron oxidized group 10 metal, Ni(II), Pd(II) and Pt(II), six-membered chelate Salpn (Salpn = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,3-propanediamine) complexes have been investigated and compared to the five-membered chelate Salen (N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-ethanediamine) and Salcn (N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) complexes. Reaction of the Salpn complexes with 1 equivalent of AgSbF(6) affords the oxidized complexes which exist as ligand radical species in solution and in the solid state. The solid state structures of the oxidized complexes have been determined by X-ray crystal structure analysis. While the Ni and Pt analogues exhibit an essentially symmetric coordination sphere contraction upon oxidation, the oxidized Pd derivative exhibits an asymmetric metal binding environment demonstrating at least partial ligand radical localization. In comparison to the oxidized Salen and Salcn complexes, the propyl backbone of the Salpn complexes leads to a larger deviation from a planar geometry in the solid state. The electronic structure of the oxidized Salpn complexes was further probed by UV-vis-NIR measurements, electrochemistry, EPR spectroscopy, and theoretical calculations. The intense NIR band for the one-electron oxidized Salpn complexes shifts to lower energy in comparison to the 5-membered chelate analogues, which is attributed to lower metal d(xz) character in the β-LUMO for the Salpn series. The reactivity of the one-electron oxidized Salpn complexes with exogenous ligands was also studied. In the presence of pyridine, the oxidized Ni analogue exhibits a shift in the locus of oxidation to a Ni(III) species. The oxidized PtSalpn complex rapidly decomposes in the presence of pyridine, even at low temperature. Interestingly, electronic and EPR spectroscopy suggests that the addition of pyridine to the oxidized Pd analogue results in initial dissociation of the phenoxyl radical ligand, likely due to the increased flexibility of the propyl backbone.
Recent advances in surface organometallic chemistry have enabled the detailed characterization of the surface species in single‐site heterogeneous catalysts. However, the selective formation of bis‐grafted surface species remains challenging because of the heterogeneity of the supporting surface. Herein, we introduce a metal complex bearing bidentate disilicate ligands, −OSi(OtBu)2OSi(OtBu)2O−, as a molecular precursor, which has a silicate framework adjacent to the metal (Pt) center. The grafting of the precursors on silica supports (MCM‐41 and CARiACT Q10) proceeded through a substitution reaction on the silicon atoms of the disilicate ligand, which was verified by the detection of isobutene and tBuOH as the elimination products, to selectively yield bis‐grafted surface species. The chemical structure of the surface species was characterized by solid‐state NMR, and the chemical shift values of the ancillary ligands and 195Pt nuclei suggested that the bidentate coordination sphere was maintained following grafting.
The Smc5-Smc6 complex contains a heterodimeric core of two SMC proteins and non-Smc elements (Nse1-6), and plays an important role in DNA repair. We investigated the functional roles of Nse4 and Nse1 in Dictyostelium discoideum. Nse4 and Nse3 expressed as Flag-tagged fusion proteins were highly enriched in nuclei, while Nse1 was localized in whole cells. Using yeast two-hybrid assays, only the interaction between Nse3 and Nse1 was detected among the combinations. However, all of the interactions among these three proteins were recognized by co-immunoprecipitation assay using cell lysates prepared from the cells expressing green fluorescent protein (GFP)-or Flag-tagged fusion proteins. GFP-tagged Nse1, which localized in whole cells, was translocated to nuclei when co-expressed with Flag-tagged Nse3 or Nse4. RNAi-mediated Nse1 and Nse4 knockdown cells (Nse1 KD and Nse4 KD cells) were generated and found to be more sensitive to UV-induced cell death than control cells. Upon starvation, Nse1 and Nse4 KD cells had increases in the number of smaller fruiting bodies that formed on non-nutrient agar plates or aggregates that formed under submerged culture. We found a reduction in the mRNA level of pdsA, in vegetative and 8 h-starved Nse4 KD cells, and pdsA knockdown cells displayed effects similar to Nse4 KD cells. Our results suggest that Nse4 and Nse1 are involved in not only the cellular DNA damage response but also cellular development in D. discoideum.
Grafting of a platinum precursor bearing a disilicate ligand, −OSi(OtBu)2OSi(OtBu)2O−, achieved the selective formation of bis‐grafted surface species on silica supports. The chemical‐shift values of the ancillary ligands were almost identical before and after the grafting, thus suggesting that the coordination sphere around platinum of the grafted species was nearly independent of the type of silica support and the degree of substitution on the disilicate ligand. More information can be found in the Full Paper by J.‐C. Choi et al. (DOI: 10.1002/chem.202101927).
A single dose of a first-generation 5-HTRA and dexamethasone had a favorable suppressive effect on nausea and vomiting in weekly CBDCA+PTX therapy for NSCLC.
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