Newly developed oxo-tethered Ru amido complexes (R,R)-1 and their HCl adducts (R,R)-2 exhibited excellent catalytic performance for both asymmetric transfer hydrogenation and the hydrogenation of ketonic substrates under neutral conditions without any cocatalysts to give chiral secondary alcohols with high levels of enantioselectivity.

Abstract. We examined potential interferences from water vapor and atmospheric background gases (N 2 , O 2 , and Ar), and biases by isotopologues of target species, on accurate measurement of atmospheric CO 2 and CH 4 by means of wavelength-scanned cavity ring-down spectroscopy (WS-CRDS). Changes of the background gas mole fractions in the sample air substantially impacted the CO 2 and CH 4 measurements: variation of CO 2 and CH 4 due to relative increase of each background gas increased as Ar < O 2 < N 2 , suggesting similar relation for the pressure-broadening effects (PBEs) among the background gas. The pressure-broadening coefficients due to variations in O 2 and Ar for CO 2 and CH 4 are empirically determined from these experimental results. Calculated PBEs using the pressure-broadening coefficients are linearly correlated with the differences between the mole fractions of O 2 and Ar and their ambient abundances. Although the PBEs calculation showed that impact of natural variation of O 2 is negligible on the CO 2 and CH 4 measurements, significant bias was inferred for the measurement of synthetic standard gases. For gas standards balanced with purified air, the PBEs were estimated to be marginal (up to 0.05 ppm for CO 2 and 0.01 ppb for CH 4 ) although the PBEs were substantial (up to 0.87 ppm for CO 2 and 1.4 ppb for CH 4 ) for standards balanced with synthetic air. For isotopic biases on CO 2 measurements, we compared experimental results and theoretical calculations, which showed excellent agreement within their uncertainty. We derived instrument-specific water correction functions empirically for three WS-CRDS instruments (Picarro EnviroSense 3000i, G-1301, and G-2301), and evaluated the transferability of the water correction function from G-1301 among these instruments. Although the transferability was not proven, no significant difference was found in the water vapor correction function for the investigated WS-CRDS instruments as well as the instruments reported in the past studies within the typical analytical precision at sufficiently low water concentrations (< 0.7 % for CO 2 and < 0.6 % for CH 4 ). For accurate measurements of CO 2 and CH 4 in ambient air, we concluded that WS-CRDS measurements should be performed under complete dehumidification of air samples, or moderate dehumidification followed by application of a water vapor correction function, along with calibration by natural airbased standard gases or purified air-balanced synthetic standard gases with the isotopic correction.

A concise asymmetric transfer hydrogenation of diaryl ketones, promoted by bifunctional Ru complexes with an etherial linkage between 1,2-diphenylethylenediamine (DPEN) and η(6)-arene ligands, was successfully developed. Because of the effective discrimination of substituents at the ortho position on the aryl group, unsymmetrical benzophenones were smoothly reduced in a 5:2 mixture of formic acid and triethylamine with an unprecedented level of excellent enantioselectivity. For the non-ortho-substituted benzophenones, the oxo-tethered catalyst electronically discerned biased substrates, resulting in attractive performance yielding chiral diarylmethanols with >99% ee.

A family of bifunctional Ir, Rh, and Ru complexes bearing chiral monosulfonylated diamine ligands has been evaluated for asymmetric hydrogenation of acyclic imines (1) to the corresponding amines (2). A chiral Ir complex, [Cp*IrCl{(S,S)-Tscydn}] (3a), combined with silver salts caused a marked improvement in the catalyst performance in terms of the activity and selectivity. The use of an excess amount of the silver salt, AgSbF 6 , increased enantioselectivity up to 72% ee in the asymmetric hydrogenation of N-(1-phenylethylidene)benzylamine (1a). A stoichiometric reaction of 3a with AgSbF 6 in acetonitrile afforded an isolable cationic complex, [Cp*Ir(Tscydn)(CH 3 CN)] + SbF 6 -(4) which was fully characterized by NMR spectroscopy and X-ray crystallography. The resulting cationic complex 4 readily reacted with H 2 under ambient conditions in the presence of triethylamine to give a hydridoiridium complex, [Cp*IrH{(S,S)-Tscydn}] (5) and showed comparable catalytic behavior to that for the catalyst system generated in situ from 3a and AgSbF 6 . On the basis of the additive effect on the outcome of the hydrogenation as well as the 13 C{ 1 H} NMR spectrum of a reaction mixture of imine 1a and AgSbF 6 , the mechanism of the imine hydrogenation including heterolytic bond cleavage of H 2 on a cationic complex to generate a hydrido intermediate and the following Htransfer to the imine substrates activated by the silver cation was proposed.