No abstract

By changing template cation but introducing trivalent iron ions in the known niccolite structural metal formate frameworks, three complexes formulated [NH 2 (CH 3 ) 2 ][Fe III M II (HCOO) 6 ] (M = Fe for 1, Mn for 2, and Co for 3) were synthesized and magnetically characterized. The variation in the compositions of the complexes leads to three different complexes: mixed-valent complex 1, heterometallic but with the same spin state complex 2, and heterometallic heterospin complex 3. The magnetic behaviors are closely related to the divalent metal ions used. Complex 1 exhibits negative magnetization assigned as N eel N-Type ferrimagnet, with an asymmetric magnetization reversal in the hysteresis loop, and complex 2 is an antiferromagnet with small spin canting (R canting ≈ 0.06°and T canting = 35 K), while complex 3 is a ferrimagnet with T N = 32 K.

No abstract

Wir stellen eine RhIII‐katalysierte C‐H‐Aktivierung/Abfangcyclisierung vor, an der eine nukleophile Addition einer C(sp3)‐Rh‐Spezies an polarisierte Doppelbindungen beteiligt ist. Dies ist die erste intermolekulare katalytische Methode zur direkten Synthese von 1‐Aminoindolinen mit großer Substratbreite und unter milden Reaktionsbedingungen.

A method to directly arylate toluene derivatives with aryl bromides to generate diarylmethanes, which are important building blocks in drug discovery, is described. In this method, KN(SiMe) in combination with a (NIXANTPHOS)Pd catalyst accomplished the deprotonative activation of toluene derivatives to permit cross-coupling with aryl bromides. Good to excellent yields are obtained with a range of electron-rich to neutral aryl bromides. Both electron-rich and electron-poor toluene derivatives are well tolerated, and even 2-chlorotoluene performs well, providing a platform for introduction of additional functionalization. This discovery hinges on the use of a main group metal to activate toluene for deprotonation by means of a cation-π interaction, which is secured by a bimetallic K(NIXANTPHOS)Pd assembly. Mechanistic and computational studies support acidification of toluene derivatives by the K-cation- π interaction, which may prove pertinent in the development of other, new reaction systems.

A highly efficient asymmetric cascade reaction between keto esters and alkynyl alcohols and amides is reported. The success of the reaction was attributed to the combination of chiral Lewis acid N,N'-dioxide nickel(II) catalysis with achiral π-acid gold(I) catalysis working as an asymmetric relay catalytic system. The corresponding spiroketals and spiroaminals were synthesized in up to 99 % yield, 19:1 d.r., and more than 99 % ee under mild reaction conditions. Control experiments suggest that the N,N'-dioxide ligand was essential for the formation of the spiro products.

The objective of this study was to investigate the effects of drought stress on the activity of antioxidant enzymes and osmotic adjustment substance content in the tillering period of drought-sensitive and drought-tolerant rice cultivars. The results showed that the superoxide dismutase (SOD), peroxidase (POD), catalase activity (CAT), hydrogen peroxide content, soluble protein content and soluble sugar content increased with the accumulation of time and intensity of drought stress. Compared with the drought-sensitive cultivar, drought-resistant cultivar had a smaller photosynthetic affected area, longer CAT enzyme activity duration, and lower H 2 O 2 accumulation. Unlike POD and CAT enzymes, which maintain the ability to scavenge hydrogen peroxide under long drought conditions, ascorbate peroxidase (APX) enzymes seem to be a rapid response mechanism to scavenge hydrogen peroxide under drought stress. Under a −10 kPa water potential, using soluble sugars on the osmotic adjustment ability of the drought-resistant cultivars was more efficient; under −40 kPa water potential, drought-resistant cultivars can maintain relative high levels of ascorbate (ASA) content in the short term. After the restoration of irrigation, the indices gradually returned to control levels. The ASA content showed faster accumulation ability in drought-resistant cultivars and faster recovery. The soluble protein content recovered more slowly in drought-sensitive cultivars under the −40 kPa treatment. Drought-resistant cultivars showed stronger resistance to drought in the −10 kPa treatment and obtained similar yield to the control, while the drought-sensitive cultivars were more obviously affected by the drought stress.

Three bidentate ruthenium­(II) complexes with a pyridonate fragment were prepared and fully characterized. These complexes are structurally similar, but differ in their pendant substituents. Complex 1 contains a phenyl unit, whereas complexes 2 and 3 have uncoordinated thienyl and thiazolyl groups, respectively. These complexes were tested as catalysts for β-alkylation of secondary alcohols with primary alcohols, and 3 shows the highest activity, suggesting the thiazolyl ring participates in the catalytic process. Furthermore, 3 is an excellent catalyst for α-alkylation of ketones with primary alcohols. Various α-alkylated ketones were synthesized in high yields, by using 0.05 mol % 3 and 0.25 equiv of t-BuOK within 30 min.