Abstract
The structures of gas-phase group nine cation-nitrous oxide metal-ligand complexes, M+(N2O)n (M = Co, Rh, Ir; n = 2-7) have been determined by a combination of infrared photodissociation spectroscopy and density functional theory. The infrared spectra were recorded in the region of the N2O asymmetric (N[double bond, length as m-dash]N) stretch using the inert messenger technique and show spectroscopically distinct features for N- and O-bound isomers. The evolution of the spectra with increasing ligand number is qualitatively different for each of the metal ions studied here with only Co+(N2O)n complexes behaving similarly to the coinage metal complexes studied previously. The rich variety of electronic and isomeric structures identified make these species attractive targets for infrared-driven, isomer selective intra-complex chemistry.
Highlights
Accounting for 5% of anthropogenic greenhouse emissions, nitrous oxide (N2O) is a potent greenhouse gas[1,2] with a warming potential 300 times greater than carbon dioxide
One effective route to reducing emissions is via metal-catalysed N2O reduction[5,6] and this has been an active area of research in conventional heterogeneous catalysis and cluster science.[7]
We recently reported a spectroscopic study of M+(N2O)n (M = Cu, Ag, Au) complexes in which infrared photodissociation (IRPD) spectroscopy was combined with quantum chemical calculations to identify common structural binding motifs.[24]
Summary
Accounting for 5% of anthropogenic greenhouse emissions, nitrous oxide (N2O) is a potent greenhouse gas[1,2] with a warming potential 300 times greater than carbon dioxide. In addition to its climate change potential, as the primary source of stratospheric NOx, surface N2O emissions represent the dominant ozonedepleting emissions of the 21st century.[1,2] Human actions such as manufacturing, fossil fuel use, and agriculture have given rise to increased emissions and N2O concentrations are rising by 0.5–0.9 ppb per volume per year.[3]. Unregulated by the Montreal Protocol,[4] as a result of its negative environmental impact there is considerable interest in reducing N2O emissions. One effective route to reducing emissions is via metal-catalysed N2O reduction[5,6] and this has been an active area of research in conventional heterogeneous catalysis and cluster science.[7]. In terms of reactions of N2O with metal ions, M+/0/À(N2O)n complexes represent model entrance-channel species in which the fundamental interactions can be studied
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
