Journal article

Gas phase fragmentation of eta(2) coordinated aldehydes in [VO2(eta(2)-OCHR)](-): aldehyde structure dictates the nature of the products

Tom Waters, George N Khairallah, Richard AJ O'Hair



The gas phase fragmentation reactions of eta2 coordinated aldehydes in [VO2(eta2-OCHR)]-, which have previously been shown to play a role in the catalytic oxidation of alcohols to aldehydes, were examined using a combination of isotope labelling experiments and collision induced dissociation in a quadrupole ion trap mass spectrometer. The experimental data were interpreted with the aid of density functional theory calculations (DFT). The types of fragmentation reactions observed depend on the nature of the R group. When R = H, the dominant fragmentation channel involves formation of [VO2H2]-via loss of CO. Minor losses of H2 and CH2O are also observed. When R = Me, loss of H2 is observed to ..

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Awarded by Australian Research Council

Funding Acknowledgements

TW, and RAJO thank the Australian Research Council for financial support via Grants # DP0772053 and # DP0558430, respectively. TW thanks the Victorian Institute for Chemical Sciences High Performance Computing Facility for allocation of computer time and GK thank the Victorian Partnership for Advanced Computing for allocation of computer time. We thank Hannah O'Riley for repeating some of the experiments and DFT calculations.