Abstract
Manganese carbonyl cations of the form Mn(CO) + n (n = 1−9) are produced in a molecular beam by laser vaporization in a pulsed nozzle source. Mass selected infrared photodissociation spectroscopy in the carbonyl stretching region is used to study these complexes and their “argon-tagged” analogues. The geometries and electronic states of these complexes are determined by comparing their infrared spectra to theoretical predictions. Mn(CO) +6 has a completed coordination sphere, consistent with its predicted 18-electron stability. It has an octahedral structure in its singlet ground state, similar to its isoelectronic analogue Cr(CO)6. Charge-induced reduction in π back-bonding leads to a decreased red-shift in Mn(CO) +6 (υCO = 2106 cm−1) compared with Cr(CO)6 (υCO = 2003 cm−1). The spin multiplicity of Mn+(CO) n complexes gradually decreases with progressive ligand addition. MnCO+ is observed as both a quintet and a septet, Mn(CO) +2 is observed only as a quintet, while Mn(CO) +3,4 are both observed as triplets. Mn(CO) +5 and Mn(CO) +6 are both singlets, as are all larger complexes.
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Reed, Z.D., Duncan, M.A. Infrared spectroscopy and structures of manganese carbonyl cations, Mn(CO) + n (n = 1−9). J Am Soc Mass Spectrom 21, 739–749 (2010). https://doi.org/10.1016/j.jasms.2010.01.022
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DOI: https://doi.org/10.1016/j.jasms.2010.01.022