How to tame an oxidant: the mysteries of “tpap” (tetra-n-propylammonium perruthenate).

DOI: 10.14469/hpc/2921 Metadata

Created: 2017-08-18 08:18

Last modified: 2017-08-18 08:41

Author: Henry Rzepa

License: Creative Commons: Public Domain Dedication 1.0

Funding: (none given)


tpap, as it is affectionately known, is a ruthenium-based oxidant of primary alcohols to aldehydes discovered by Griffith and Ley. Whereas ruthenium tetroxide (RuO4) is a voracious oxidant[2], its radical anion countered by a tetra-propylammonium cation is considered a more moderate animal[3]. In this post, I want to try to use quantum mechanically derived energies as a pathfinder for exploring what might be going on (or a reality-check if you like). The calculations are at the (u)wB97Xd/Def2-SVP level, with a pseudopotential for Ru.

Member of collection / collaboration

10.14469/hpc/177 Computation data for Henry Rzepa's blog

Associated DOIs

Current dataset ...DOIDescription
References 10.14469/hpc/2920 Blog post
References 10.6084/m9.figshare.105482.v1 Gaussian Job Archive for C2H6O5Ru, TS2
References 10.6084/m9.figshare.105494.v1 Gaussian Job Archive for C2H6O5Ru, TS1
References 10.6084/m9.figshare.105496.v1 Gaussian Job Archive for C6H18NO5Ru(2), TS2, doublet
References 10.6084/m9.figshare.105596.v1 Gaussian Job Archive for C2H6O5Ru(3), triplet
References 10.6084/m9.figshare.105597.v1 Gaussian Job Archive for C2H6O5Ru, TS3
References 10.6084/m9.figshare.105600.v1 Gaussian Job Archive for C6H18NO5Ru(4), TS2, quartet
References 10.6084/m9.figshare.105613.v1 Gaussian Job Archive for C6H18NO5Ru(2)