Reaktionen von Metallkomplexen mit kleinen Ringen, XI [1] Ringöffnung von Aziridinen mit Metallcarbonylhydriden; β-Aminoacylchelat-Komplexe von Mangan, Molybdän, Wolfram und Cobalt / Reactions of Metal Complexes with Small Rings, XI [1] Ring Opening of Aziridines by Metal Carbonyl Hydrides; β-Aminoacyl Chelate Complexes of Manganese, Molybdenum, Tungsten and Cobalt

Abstract

<jats:p>The metal carbonyl hydrides HM(CO)<jats:sub>3</jats:sub>(π-C<jats:sub>5</jats:sub>H<jats:sub>5</jats:sub>) (M = Mo, W), HMn(CO)<jats:sub>4</jats:sub>L, HCo(CO)<jats:sub>3</jats:sub>L (L - CO, PPh<jats:sub>3</jats:sub>) react with aziridines by protonation of aziridine, nucleophilic attack of the corresponding carbonyl metallate and CO insertion to give the β-aminoacyl complexes 2-7. The ring opening of C-substituted aziridines is regiospecific. With alkyl substituted aziridines the nucleophilic attack of the carbonyl metallate occurs at the sterically less hindered carbon atom, with phenyl substituted aziridines at the phenyl substituted carbon atoms. From the reactions of HM(CO)<jats:sub>3</jats:sub>(π-C<jats:sub>5</jats:sub>H<jats:sub>5</jats:sub>) with optically active aziridines, which afford complexes with an asymmetric metal atom, only one diastereomer could be observed. The mechanism of these reactions is discussed and the spectral data (IR, <jats:sup>1</jats:sup>H NMR, MS) of the complexes are reported. β-Aminoacyl complexes have also been obtained by addition of amines to [(π-C<jats:sub>5</jats:sub>H<jats:sub>5</jats:sub>)(CO)<jats:sub>3</jats:sub>M(alkene)]<jats:sup>+</jats:sup>BF<jats:sub>4</jats:sub><jats:sup>-</jats:sup> (M = Mo, W).</jats:p><jats:p>The methyl complex H<jats:sub>3</jats:sub>CMn(CO)<jats:sub>5</jats:sub> reacts with aziridine to give the acetyl complexes H<jats:sub>3</jats:sub>CC(O)Mn(CO)<jats:sub>4</jats:sub>(aziridine) and H<jats:sub>3</jats:sub>CC(O)Mn(CO)<jats:sub>3</jats:sub>(aziridine)<jats:sub>2</jats:sub>, respectively</jats:p>