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

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journal contribution
posted on 25.07.2011, 00:00 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).