om200508k_si_001.pdf (2.3 MB)

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

Download (2.3 MB)
journal contribution
posted on 25.07.2011 by Michael P. Lanci, Matthew S. Remy, David B. Lao, Melanie S. Sanford, James M. Mayer
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 PtIV 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).