Reactions of manganese and rhenium atoms with NO.: Infrared spectra and density functional calculations of η1 and η2 addition and insertion reaction products

Reactions of thermal and laser-ablated Mn atoms with NO produce the Mn-(eta(1)-NO)(x) complexes (x = 1-3), a series of eta(2) complexes, and in addition, laser-ablated Mn gives the NMnO insertion product. The C-2v 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-3v 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.