In Wacker oxidation and inspired Pd(ii)/Cu(ii)-catalyzed C-H activations, copper(ii) is believed to serve in re-oxidizing of Pd(0) in the catalytic cycle. Herein we report that non-redox metal ions like Sc(iii) can promote Wacker-type oxidations even better than Cu(ii); both Sc(iii) and Cu(ii) can greatly promote Pd(ii)-catalyzed olefin isomerization in which the redox properties of Cu(ii) are not essential, indicating that the Lewis acid properties of Cu(ii) can play a significant role in Pd(ii)-catalyzed C-H activations in addition to its redox properties. Characterization of catalysts using UV-Vis and NMR indicated that adding Sc(OTf)3 to the acetonitrile solution of Pd(OAc)2 generates a new Pd(ii)/Sc(iii) bimetallic complex having a diacetate bridge which serves as the key active species for Wacker-type oxidation and olefin isomerization. Linkage of trivalent Sc(iii) to the Pd(ii) species makes it more electron-deficient, thus facilitating the coordination of olefin to the Pd(ii) cation. Due to the improved electron transfer from olefin to the Pd(ii) cation, it benefits the nucleophilic attack of water on the olefinic double bond, leading to efficient olefin oxidation. The presence of excess Sc(iii) prevents the palladium(0) black formation, which has been rationalized by the formation of the Sc(iii)H-Pd(ii) intermediate. This intermediate inhibits the reductive elimination of the H-Pd(ii) bond, and facilitates the oxygen insertion to form the HOO-Pd(ii) intermediate, and thus avoids the formation of the inactive palladium(0) black. The Lewis acid promoted Wacker-type oxidation and olefin isomerization demonstrated here may open up a new opportunity in catalyst design for versatile C-H activations.

Redox-inactive metal ions have been recognized to be able to participate in redox metal-ion-mediated biological and chemical oxidative events; however, their roles are still elusive. This work presents how the redox-inactive metal ions affect the oxidative reactivity of a well-investigated manganese(II) with its corresponding manganese(IV) complexes having cross-bridged cyclam ligand. In dry acetone, the presence of these metal ions can greatly accelerate stoichiometric oxidations of triphenylphosphine and sulfides by the manganese(IV) complexes through electron transfer or catalytic sulfoxidations by the corresponding manganese(II) complexes with PhIO. Significantly, the rate enhancements are highly Lewis-acid strength dependent on added metal ions. These metal ions like Al(3+) can also promote the thermodynamic driving force of the Mn(IV)-OH moiety to facilitate its hydrogen abstraction from ethylbenzene having a BDE(CH) value of 85 kcal/mol, while it is experimentally limited to 80 kcal/mol for Mn(IV)-OH alone. Adding Al(3+) may also improve the manganese(II)-catalyzed olefin epoxidation with PhIO. However, compared with those in electron transfer, improvements in hydrogen abstraction and electron transfer are minor. The existence of the interaction between Lewis acid and the manganese(IV) species was evidenced by the blue shift of the characteristic absorbance of the manganese(IV) species from 554 to 537 nm and by converting its EPR signal at g = 2.01 into a hyperfine 6-line signal upon adding Al(3+) (I = 5/2). Cyclic voltammograms of the manganese(IV) complexes reveal that adding Lewis acid would substantially shift its potential to the positive direction, thus enhancing its oxidizing capability.

Physical damage is one of the main factors that cause seedling mortality in many ecosystems. However, the impact of physical damage due to rainfall erosion on seedling mortality is seldom investigated. In this study, we ask the following question: how does rainfall erosion influence seedling damage and establishment in the Loess Plateau region of China? Seedling damage and establishment experiments under different patterns of simulated rainfall were conducted. The seedling damage rate, damage type and growth status were investigated. The seedling damage rate was influenced by rainfall intensity and duration and by the runoff volume. The mean damage rate of all three studied species did not exceed 15 per cent, and the highest damage rate of individual species under special rainfall events was approximately 30 per cent. The type of damage suffered by the seedlings of Sophora viciifolia (which produces large seeds) mainly took the form of striking down, whereas seedlings of Artemisia scoparia (which produces small seeds) suffered the highest rates of washing away among the three studied species. In the seedling establishment experiment, after 120 days with six rainfall events, S. viciifolia had the highest seedling establishment rate (80·1 ± 2·5 per cent), followed by Bothriochloa ischaemun (67·2 ± 2·2 per cent), and A. scoparia (28·1 ± 2·5 per cent). The seedling damage rate, damage type and establishment rate were also related to seed size. Whether physical damage to seedlings is a major factor limiting vegetation restoration in eroded environments requires further research. Copyright © 2012 John Wiley & Sons, Ltd.

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