Reactions of Manganese and Rhenium Atoms with NO. Infrared Spectra and Density Functional Calculations of η and η Addition and Insertion Reaction Products

Reactions of thermal and laser-ablated Mn atoms with NO produce the Mn−(η 1 -NO) x complexes ( x = 1−3), a series of η 2 complexes, and in addition, laser-ablated Mn gives the NMnO insertion product. The C 2 v complex Mn(NO) 2 is identified from symmetric (a 1 ) and antisymmetric (b 2 ) N−O ligand stretching modes, which gave triplet mixed isotopic spectra and excellent agreement with DFT calculations. The Mn(NO) 3 complex is shown to have C 3 v symmetry through the observation of mixed isotopic spectra for four vibrational modes, including the symmetric (a 1 ) and antisymmetric (e) N−O ligand stretching modes and a match with DFT calculations of isotopic frequencies. Laser-ablated Re gave similar major products.