10.1021/om200508k.s001
Michael P. Lanci
Michael P.
Lanci
Matthew S. Remy
Matthew S.
Remy
David B. Lao
David B.
Lao
Melanie S. Sanford
Melanie S.
Sanford
James M. Mayer
James M.
Mayer
Modulating Sterics in Trimethylplatinum(IV) Diimine Complexes To Achieve C–C Bond-Forming Reductive Elimination
American Chemical Society
2011
Modulating Sterics
reductive elimination
DAB
aryl substituents
steric bulk
Experimental results
2011-07-25 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Modulating_Sterics_in_Trimethylplatinum_IV_Diimine_Complexes_To_Achieve_C_C_Bond_Forming_Reductive_Elimination/2629072
Tuning the aryl substituents of <i>N</i>,<i>N</i>′-diaryl-2,3-dimethyl-1,4-diaza-1,3-butadiene (DAB) ligands promotes the challenging C–C bond-forming reductive elimination from Pt<sup>IV</sup> diimine complexes [(DAB)Pt(CH<sub>3</sub>)<sub>3</sub>(solvent)]<sup>+</sup> (<b>2</b>) under mild conditions. Experimental results and density functional calculations indicate that 2,6-aryl substitution promotes reductive elimination by facilitating dissociation of the coordinating solvent by close to 10 kcal mol<sup>–1</sup>, but too much steric bulk inhibits the formation of <b>2</b> in the one-electron outersphere oxidation of (DAB)Pt(CH<sub>3</sub>)<sub>2</sub> (<b>1</b>).