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>).