Effect of Tethered, Axial Thioether Coordination on Rhodium(II)-Catalyzed Silyl-Hydrogen Insertion

25 June 2019, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The effect of tethering a thioether to a rhodium paddlewheel complex are evaluated in diazo-mediated Si–H insertion reactions. This study provides further evidence for the benefits of incorporating thioethers into the rhodium paddlewheel motif. When compared to a non-tethered complex, the in situ carbenoid formation and subsequent Si–H insertion are not impeded by the thioether tether, improves yields by up to 12%, and is more selective for diazo compounds when compared to non-tethered catalysts. Computational modeling of the complexes at the M06-2X/def2-TZVPP level of theory is also presented in order to rationalize the results.


Silyl insertion
thioether ligands
axial coordination

Supplementary materials

SuppInfo Si H Sheffield et al ChemRxiv


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.