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NO Reactions Inside Crystals

Von Wiley-VCH zur Verfügung gestellt

Solid-state dicobalt complexes chemisorb the toxic greenhouse gas nitric oxide (NO) and facilitate its selective transformation in a solvent-free reaction. In-crystal dimetallic cooperativity is proposed. Depending on the counter anion present in the solid, a nitrite-bridged dicobalt(II,III) or dicobalt(III,III) complex is synthesized in this gas-solid reaction.


Reactions of chemisorbed reagents inside the crystalline molecular solid state are rare but offer unexploited methods for selective solvent-free chemical synthesis. Here we show that the greenhouse gas precursor, nitric oxide (NO) is chemisorbed by crystals of the hexafluorophosphate salts of complexes containing dicobalt sites. On NO sorption a cascade of reactions results in the in-crystal synthesis of nitrite and other gaseous NOx. Recrystallization enabled structural elucidation of the mixed valent {[(bpbp)Co2(μ-(η1-O : η1-N)-ONO)]2(bdc)}4+ (bpbp=2,6-bis(N,N-bis(2-pyridylmethyl)aminomethyl)-4-tert-butylphenolato, bdc=1,4-benzenedicarboxylato) cation. Overlapping signals in the solid-state EPR spectra confirm the CoIICoIII oxidation state and the presence of NO2 trapped inside the unrecrystallised solid products (br. g=4, triplet g=2 (340 mT), A(N)=73 MHz), despite three cycles of vacuum and N2 flushing. Consistently, νN−O bands appear in the Raman and IR spectra that are due to the coordinated nitrate and the trapped NO2 that were synthesized in-crystal. The latter is expelled by heating the solid to 160 °C or by recrystallization. Dimetallic cooperativity is proposed for the NO transformations in these rare examples of selective, chemisorptive substrate reactions in the solid-state.

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