Modulating Sterics in Trimethylplatinum(IV) Diimine Complexes To Achieve C–C Bond-Forming Reductive Elimination

Tuning the aryl substituents of N,N′-diaryl-2,3-dimethyl-1,4-diaza-1,3-butadiene (DAB) ligands promotes the challenging C–C bond-forming reductive elimination from Pt^IV diimine complexes [(DAB)Pt(CH₃)₃(solvent)]⁺ (2) 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^–1, but too much steric bulk inhibits the formation of 2 in the one-electron outersphere oxidation of (DAB)Pt(CH₃)₂ (1).