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Katalytische Carbonylierung von Aceton-oxim an Bisoximato-diruthenium-Komplexen: Ein einfacher Zugang zu wasserfreiem Acetonin. Isolierung und Molekülstruktur von [Ru2(CO)5(Me2CNO)2(Me2CNOH)]

✍ Scribed by Meinhard Langenbahn; Helen Stoeckli-Evans; Georg Süss-Fink


Publisher
John Wiley and Sons
Year
1991
Tongue
German
Weight
312 KB
Volume
74
Category
Article
ISSN
0018-019X

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✦ Synopsis


In the presence of catalytic amounts of [Ru,(CO),(Me2CNO)2(Me2CNOH)2] (l), acetone oxime reacts with carbon monoxide to give 2,3,4,5-tetrahydro-2,2,4,4,6-pentamethylpyrimidine ('acetonine'), CO,, and NH,. The reaction proceeds presumably via carbonylation of Me,C=NOH to the unstable intermediate Me,C=N-OCHO which undergoes decarboxylation to give the corresponding imine Me,C=NH. The final product is assumed to result from the cyclotrimerisation of Me,C=NH with elimination of NH,. Evidence for the intermediacy of the imine comes from the analogous reaction of acetophenone oxime, PhMeC=NOH, which gives the corresponding imine PhMeC=NH as a stable product. The isolation of the complex [RU~(CO)~(M~~CNO),(M~~CNOH)] (2) suggests the carbonylation to take place at the bridging oximato ligand of 1.