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Angewandte Chemie (International Ed. in... Dec 2019The activation of white phosphorus (P ) by transition-metal complexes has been studied for several decades, but the functionalization and release of the resulting...
The activation of white phosphorus (P ) by transition-metal complexes has been studied for several decades, but the functionalization and release of the resulting (organo)phosphorus ligands has rarely been achieved. Herein we describe the formation of rare diphosphan-1-ide anions from a P ligand by treatment with cyanide. Cobalt diorganopentaphosphido complexes have been synthesized by a stepwise reaction sequence involving a low-valent diimine cobalt complex, white phosphorus, and diorganochlorophosphanes. The reactions of the complexes with tetraalkylammonium or potassium cyanide afford a cyclotriphosphido cobaltate anion 5 and 1-cyanodiphosphan-1-ide anions [R PPCN] (6-R). The molecular structure of a related product 7 suggests a novel reaction mechanism, where coordination of the cyanide anion to the cobalt center induces a ligand rearrangement. This is followed by nucleophilic attack of a second cyanide anion at a phosphorus atom and release of the P fragment.
PubMed: 31573718
DOI: 10.1002/anie.201908744 -
Ultrasonics Sonochemistry May 2020We studied sonochemical reactions resulting from ultrasonic treatment of potassium hexacyanoferrate(II) in aqueous solutions using a custom-built apparatus working at...
We studied sonochemical reactions resulting from ultrasonic treatment of potassium hexacyanoferrate(II) in aqueous solutions using a custom-built apparatus working at 536 kHz. We concluded that primary reactions are completely dominated by oxidation of Fe(II) to Fe(III) and did not find any evidences for degradation of cyanide. At the highest concentration used in the present study (0.1 M) we detected formation of pentacyanoaquaferrate(II) complex, which is most probably formed in reactions between hexacyanoferrate(III) anions and hydrogen atoms or hydrated electrons formed in sonochemical processes. We also determined that hydroxyl radicals formation rate in our system, (8.7 ± 1.5)∙10 M∙s, is relatively high compared to other reported experiments. We attribute this to focusing of the ultrasonic wave in the sample vessel. Finally, we suggest that oxidation rate of hexacyanoferrate(II) anions can be a convenient benchmark of efficiency of sonochemical reactors.
PubMed: 31945577
DOI: 10.1016/j.ultsonch.2019.104912