All Publications

  • Bimetallic, Silylene-Mediated Multielectron Reductions of Carbon Dioxide and Ethylene. Angewandte Chemie (International ed. in English) Whited, M. n., Zhang, J. n., Conley, A. M., Ma, S. n., Janzen, D. n., Kohen, D. n. 2020


    A metal/ligand cooperative approach to reduction of small molecules by metal silylene complexes (R2Si=M) is demonstrated, whereby silicon activates the incoming substrate and mediates net two-electron transformations via one-electron redox processes at two metal centers. An appropriately tuned cationic pincer cobalt(I) complex featuring a central silylene donor reacts with CO2 to afford a bimetallic siloxane featuring two Co(II) centers with liberation of CO, and reaction with ethylene yields a similar bimetallic complex with an ethylene bridge. Experimental and computational studies suggest a plausible mechanism proceeding via [2+2]-cycloaddition to the silylene complex that is quite sensitive to steric environment. The Co(II)/Co(II) products are further reactive to oxidation and reduction. Taken together, these findings demonstrate a strategy for metal/ligand cooperative small-molecule activation that is well-suited to 3d metals.

    View details for DOI 10.1002/anie.202011489

    View details for PubMedID 32991759

  • Cooperative CO2 Scission by Anomalous Insertion into a Rh-Si Bond ORGANOMETALLICS Whited, M. T., Zhang, J., Donnell, T. M., Eng, V. H., Peterson, P. O., Trenerry, M. J., Janzen, D. E., Taylor, B. H. 2019; 38 (22): 4420–32
  • Synthesis and Reactivity of Pincer-Type Cobalt Silyl and Silylene Complexes ORGANOMETALLICS Zhang, J., Foley, B. J., Bhuvanesh, N., Zhou, J., Janzen, D. E., Whited, M. T., Ozerov, O. V. 2018; 37 (21): 3956–62
  • Silylene-assisted hydride transfer to CO2 and CS2 at a [P2Si]Ru pincer-type complex DALTON TRANSACTIONS Whited, M. T., Zhang, J., Ma, S., Nguyen, B. D., Janzen, D. E. 2017; 46 (43): 14757–61


    The synthesis and characterization of base-stabilized and base-free pincer-type bis(phosphine)/silylene [P2Si]Ru complexes are reported. The base-free complex readily reduces CO2 and CS2via silylene-assisted hydride transfer, affording structurally distinct products with silicon-to-ruthenium formate and dithioformate bridges.

    View details for DOI 10.1039/c7dt03659k

    View details for Web of Science ID 000414775000009

    View details for PubMedID 29052677