Time-resolved infrared diode laser spectroscopy of the ν1 band of the iron carbonyl radical (FeCO) produced by the ultraviolet photolysis of Fe(CO)5

Abstract

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Probing C–O bond activation on gas-phase transition metal clusters: Infrared multiple photon dissociation spectroscopy of Fe, Ru, Re, and W cluster CO complexes

“…The stretching frequency of gas phase CO bound to a single Fe atom is found at 1946 cm -1 and CO adsorbed at low coverage to atop sites on Fe(110) has a vibrational frequency of 1890 cm -1 . 21,22 In our previous studies on CO adsorption to neutral cobalt and rhodium clusters the stretching frequency for atop bound CO on the clusters were systematically red shifted from values reported for CO bound to a single atom or adsorbed to surfaces by 30-70 cm -1 ; 7 and we now find a similar shift for iron clusters.…”

“…33 It predicts that two, three, and four-fold coordinated CO species form the most stable binding geometry in Fe 3,4 , Fe 5 , and Fe 6 , respectively. The reported CO stretching frequencies for these species are significantly below our experimental values for CO atop bound to Fe [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] , as would be expected. Unfortunately, we were unable to measure clusters this small to confirm the transition from high coordination binding in small clusters to atop binding in large clusters, that has some parallels in rhodium cluster CO complexes.…”

Time-resolved infrared diode laser spectroscopy of the ν1 (C–O stretch) band of the CoCO radical

“…The time-resolved infrared diode laser spectrometer employed for the present experiment has been described in our previous papers [1,3]. A 2-m long Pyrex tube with a diameter of 120 mm was used as an absorption cell and ultraviolet laser beam from a 193-nm ArF excimer laser was introduced through a quartz window at an end of the cell.…”

“…In our previous papers, for example, we have reported the infrared diode laser spectroscopy of the m 1 (C-O stretch) band [1] and the millimeter-wave spectroscopy [2] of the iron monocarbonyl radical (FeCO) generated by the 193 nm ArF excimer laser photolysis of Fe(CO) 5 . The observed spectral lines, split as triplets by the spin-spin interaction, provided a direct evidence for the 3 R À electronic ground state of FeCO to settle the controversy whether the ground electronic state of this radical is 3 R À or 5 R À [16][17][18][19][20][21][22].…”

“…Extensive spectroscopic and kinetic studies have been reported on unsaturated iron carbonyl complexes Fe(CO) n (n ¼ 1 À 4) [1][2][3][4], because they are prototypical examples of transition metal carbonyl radicals M n (CO) m [4][5][6][7][8][9][10][11][12][13][14][15], where M represents a transition metal element. In our previous papers, for example, we have reported the infrared diode laser spectroscopy of the m 1 (C-O stretch) band [1] and the millimeter-wave spectroscopy [2] of the iron monocarbonyl radical (FeCO) generated by the 193 nm ArF excimer laser photolysis of Fe(CO) 5 .…”