The reaction of azide ions, N3, with metal carbonyl compounds; an electrospray mass spectrometry study

Monoand poly-nuclear metal carbonyls, and substituted analogues, have been analysed in the presence of N3 − ions by negative-ion electrospray mass spectrometry. Most complexes yield the appropriate isocyanate-containing anions by conversion of a CO ligand to an NCO one with elimination of N2. In some cases [M+N3] − ions are observed; for species such as H2Os3(CO)10 or Ru5C(CO)15 these arise from addition at a metal–metal bond, but in other cases they may represent the first-formed adduct from attack of N3 − at a CO ligand. For hydride-containing clusters such as H4Ru4(CO)12, the azide ion can act as a base, abstracting Hand forming [M–H] ions in competition with nucleophilic attack. © 1999 Elsevier Science S.A. All rights reserved.