Mass spectra of inorganic molecules. Part III. Some transition-metal carbonyl halide and thiol compounds

Abstract

The mass spectra of a number of transition-metal carbonyl halides and thiol derivatives have been investigated With the monomeric compounds Mn(CO)₅X, Re(CO)₅X (X = Cl or l), and Fe(CO)₄l₂ the primary fragmentation involves the loss of both carbon monoxide and halogen. The halogen-bridged dimers, Mn₂(CO)₈l₂, Re₂(CO)₈Cl₂, Re₂(CO)₈l₂, and Rh₂(CO)₄Cl₂, and the related thiol-bridged compounds Fe₂(CO)₆S₂R₂(R = Me, Et, Buⁿ, or Ph), Mn₂(CO)₈S₂R₂(R = Et or Buⁿ), and Re₂(CO)₈S₂Ph₂ lose carbonyl groups preferentially with the preservation of the M₂X₂ or M₂S₂ nucleus. Evidence is also presented for the formation of tetrameric thiol compounds M₄(CO)₁₂S₄R₄(M = Mn; R = Et or Buⁿ; M = Re; R = Ph) and a trimeric rhenium compound Re₃(CO)₉S₃Rh₃.