Structure, Spectroscopy, and Electrochemistry of Manganese(I) and Rhenium(I) Quinoline Oximes

Creators: Ngo, Danh X.; Kramer, Wesley W.; McNicholas, Brendon J.; Gray, Harry B.; Brennan, Bradley J.

Abstract

Reactions of α- and β-diimine quinoline aldoximes with Mn(I) and Re(I) tricarbonyl halides afford quinoline oxime complexes. Both Mn(I) and Re(I) complexes experience severe geometric strain due to ligand steric interactions: 6-membered metallocycles exhibit more pronounced distortions than 5-membered ones, consistent with density functional theory structural analyses. Such distortions likely also affect reactivity patterns, as evidenced by Re(I)-induced deoximation of a quinoline variant containing a CF_3-ketoxime.

Additional Information

© 2018 American Chemical Society. Received: October 13, 2018; Published: December 21, 2018. We thank Larry Henling, Michael Takase, David VanderVelde, Mona Shahgholi, and Naseem Torian for experimental assistance and discussions. This work was funded by NSF CCI Solar Fuels (CHE-130124). Additional support was provided by the Resnick Sustainability Institute at Caltech and a Dr. and Mrs. Daniel C. Harris SURF Fellowship. Accession Codes: CCDC 1567369–1567373 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, by emailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033. The authors declare no competing financial interest.

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