Journal of Physical Chemistry A, Vol.116, No.10, 2484-2489, 2012
Infrared Photodissociation Spectroscopy of Mononuclear Iron Carbonyl Anions
The infrared photodissociation spectroscopy of mass-selected mononuclear iron carbonyl anions Fe(CO)(n)(-) (n = 2-8) were studied in the carbonyl stretching frequency region. The FeCO- anion does not fragment when excited with infrared light. Only a single IR active band was observed for the Fe(CO)(2)(-) and Fe(CO)(3)(-) anions, consistent with theoretical predictions that these complexes have linear D-infinity h and planar D-3h symmetry, respectively. The Fe(CO)(4)(-) anion is the most intense peak in the mass spectra and was characterized to have a completed coordination sphere with high stability. Anion clusters larger than n = 4 were determined to involve a Fe(CO)(4)(-) core anion that is progressively solvated by external CO molecules. Three CO stretching vibrational fundamentals were observed for the Fe(CO)(4)(-) core anion, indicating that the Fe(CO)(4)(-) anion has a C-3v structure. All the carbonyl stretching frequencies of the Fe(CO)(n)(-) anion complexes are red-shifted with respect to those of the corresponding neutrals.