Dalton Transactions

doi: 10.1039/C9DT90083Gpmid: 30968081

doi: 10.1039/c9dt90083gpmid: 30964491

doi: 10.1039/c9dt90084epmid: 30968082

doi: 10.1039/C9DT90084Epmid: 30968082

doi: 10.1039/C9DT90085Cpmid: 30968083

doi: 10.1039/c9dt90085cpmid: 30968083

doi: 10.1039/c9dt90075fpmid: 30964483

Brazeau, Sarah E. N.; Doerrer, Linda H.

doi: 10.1039/c8dt05028gpmid: 30869674

Investigation of Cu–O2 oxidation reactivity is important in biological and anthropogenic chemistry. Zeolites are one of the most promising Cu/O based oxidation catalysts for development of industrial-scale CH4 to CH3OH conversion. Their oxidation mechanisms are not well understood, however, highlighting the importance of the investigation of molecular Cu(i)–O2 reactivity with O-donor complexes. Herein, we give an overview of the synthesis, structural properties, and O2 reactivity of three different series of O-donor fluorinated Cu(i) alkoxides: K[Cu(OR)2], [(Ph3P)Cu(μ-OR)2Cu(PPh3)], and K[(R3P)Cu(pinF)], in which OR = fluorinated monodentate alkoxide ligands and pinF = perfluoropinacolate. This breadth allowed for the exploration of the influence of the denticity of the ligand, coordination number, the presence of phosphine, and K⋯F/O interactions on their O2 reactivity. K⋯F/O interactions were required to activate O2 in the monodentate-ligand-only family, whereas these connections did not affect O2 activation in the bidentate complexes, potentially due to the presence of phosphine. Both families formed trisanionic, trinuclear cores of the form {Cu3(μ3-O)2}3−. Intramolecular and intermolecular substrate oxidation were also explored and found to be influenced by the fluorinated ligand. Namely, {Cu3(μ3-O)2}3− from K[Cu(OR)2] could perform both monooxygenase reactivity and oxidase catalysis, whereas those from K[(R3P)Cu(pinF)] could only perform oxidase catalysis.

Deol, Harnimarta; Singh, Gurpreet; Kumar, Manoj; Bhalla, Vandana

doi: 10.1039/c9dt00307jpmid: 30896692

In modern organic synthesis, the utilization of metal NPs for carrying out fundamental organic transformations is an area of great interest. This frontier article describes the exploitation of supramolecular assemblies of AIEE-active materials as nanoreactors, stabilizers and shape directing agents for the preparation of various types of metal NPs without using any additives, reducing agents, stabilizing agents, etc. This article further summarizes the utilization of the as-prepared supramolecular ensembles as reusable nanocatalysts for carrying out various organic transformations under mild conditions.

Miao, Hao; Li, Miao; Li, Hong-Qing; Shen, Fu-Xing; Zhang, Yi-Quan; Wang, Xin-Yi

doi: 10.1039/c9dt00207cpmid: 30874271

The first bis-tridentate nitronyl nitroxide mono-radical was synthesized. From this ligand and a bis-bidentate nitronyl nitroxide ligand, metal complexes of MnII and CoII ions were also synthesized and characterized. Field-induced slow magnetic relaxation was observed in the radical-bridged CoII complex.