Activation of C-H and C-C Bonds in Alkanes by Heterodinuclear Metal Cluster Ions in the Gas Phase

  • Y. Huang
  • S. W. Buckner
  • B. S. Freiser


We report on the special reactivity of RhFe+, RhCo+, and LaFe+ with alkanes and oxygen containing compounds. These three clusters are the first hetero-dinuclear transition metal cluster ions observed to activate C-H and C-C bonds in alkanes. All three cluster ions react with alkanes larger than methane mainly via dehydrogenation. In this respect, the reactivity of RhFe+, RhCo, and LaFe is more like that of Rh+ and La+ than that of Fe+ and Co+. RhFe and RhCo show similar patterns of reactivity with multiple dehydro-genation of alkanes larger than ethane, while LaFe+ shows less extensive dehydro genat ion. n-Pentane and cyclopentane react with RhFe and RhCo to split the cluster and form RhC5H6 and RhC5H5 +, presumably the cyclopenta-diene- and cyclopentadienyl-rhodium cations. These reactions imply D°(Rh+-cyclopentadienyl)>189 kcal/mol. Other thermochemical limits are reported including D°(RhCo+-CH2)>93 kcal/mol, D°(RhFe+-CH2)>78 kcal/mol, and D°(RhFe+-benzene)>60 kcal/mol. The special reactivity is discussed in terms of reduced overlap in cluster ions containing a second or third row metal bound to a first row metal relative to clusters containing two first row metals. Finally, oxide abstraction is observed for reaction of the clusters with ethylene oxide suggesting D°(MM’+-O)>89 kcal/mol.


Ethylene Oxide Metal Carbonyl Fourier Transform Mass Spectrometry Phase Transition Metal Mass Spectrometry Instrumentation 
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Copyright information

© Plenum Press, New York 1987

Authors and Affiliations

  • Y. Huang
    • 1
  • S. W. Buckner
    • 1
  • B. S. Freiser
    • 1
  1. 1.Department of ChemistryPurdue UniversityW. LafayetteUSA

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