A new catalytic system for the dehydrogenative oxidation of alcohols using a water-soluble Cp*Ir complex bearing a bipyridine-based functional ligand as catalyst has been developed. With this catalytic system, a variety of primary and secondary alcohols have been efficiently converted to aldehydes and ketones, respectively, in aqueous media without using any oxidant. Reuse of the catalyst by a very simple procedure has been also accomplished.

The first homogeneous catalytic system for the efficient reversible dehydrogenation-hydrogenation reactions of nitrogen heterocycles in one flask has been developed using the pyridonate Cp*Ir complex as the single catalyst at relatively low temperature. The reversible catalytic reactions proceed with the reversible interconversion of catalytic species and can be nearly quantitatively repeated five times with almost no loss of efficiency. The remarkable feature of the present homogeneous catalytic system is that the reversible dehydrogenation-hydrogenation reactions proceed with the reversible interconversion of the catalytic species, depending on the absence or presence of hydrogen.

Abstract. While climate change mitigation targets necessarily concern maximum mean state changes, understanding impacts and developing adaptation strategies will be largely contingent on how climate variability responds to increasing anthropogenic perturbations. Thus far Earth system modeling efforts have primarily focused on projected mean state changes and the sensitivity of specific modes of climate variability, such as the El Niño–Southern Oscillation. However, our knowledge of forced changes in the overall spectrum of climate variability and higher-order statistics is relatively limited. Here we present a new 100-member large ensemble of climate change projections conducted with the Community Earth System Model version 2 over 1850–2100 to examine the sensitivity of internal climate fluctuations to greenhouse warming. Our unprecedented simulations reveal that changes in variability, considered broadly in terms of probability distribution, amplitude, frequency, phasing, and patterns, are ubiquitous and span a wide range of physical and ecosystem variables across many spatial and temporal scales. Greenhouse warming in the model alters variance spectra of Earth system variables that are characterized by non-Gaussian probability distributions, such as rainfall, primary production, or fire occurrence. Our modeling results have important implications for climate adaptation efforts, resource management, seasonal predictions, and assessing potential stressors for terrestrial and marine ecosystems.

[reaction: see text] An efficient catalytic system for oxidant-free oxidation of alcohols has been developed. A new Cp*Ir catalyst bearing a 2-hydroxypyridine ligand has been designed on the concept of "ligand-promoted dehydrogenation". Various secondary alcohols can be dehydrogenatively oxidized to ketones under neutral conditions with high turnover numbers by using the new Cp*Ir catalyst.