Komplexchemie reaktiver organischer verbindungen. VIII. Über die bildung von μ-carbin-und π-alkin-komplexen aus mercurierten diazoverbindungen

Pentacarbonylmanganese bromide reacts with α-diazomercurials to form binuclear carbonylmanganese complexes, ethoxycarbonylcarbyne and t-butoxycarbonylcarbyne, respectively, acting as neutral three-electron bridging ligands. Octahedral, disubstituted carbonyl complexes are also described, the IR spectra of which show the two ligands ROOCCCCOOR and HgBr to be in cis positions; the ¹H NMR spectra establish a hindered rotation of the alkyne ligand around bond axis to the central metal. As a result of mercury insertion into the manganese-bromine bond of pentacarbonylmanganese bromide, pentacarbonylmanganese mercuric bromide is formed which is shown by IR and mass spectra to have a monomeric structure.