Modulating Sterics in Trimethylplatinum(IV) Diimine Complexes To Achieve C–C Bond-Forming Reductive Elimination
作者:Michael P. Lanci、Matthew S. Remy、David B. Lao、Melanie S. Sanford、James M. Mayer
DOI:10.1021/om200508k
日期:2011.7.25
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
The Metal Is the Kinetic Site of Protonation of (Diimine)Pt Dimethyl Complexes
作者:Bror Johan Wik、Martin Lersch、Mats Tilset
DOI:10.1021/ja027649j
日期:2002.10.1
Protonolysis of (diimine)PtMe2 (1) complexes in CD2Cl2 containing CD3CN at -78 degrees C yields (diimine)PtMe2(H)(NCCD3)+ (4), (diimine)PtMe(NCCD3)+ (5), and methane. The relative yields of 5 and methane decrease with increasing concentrations of CD3CN. This is consistent with protonation of 1 occurring directly at the metal, rather than at a methyl group. The principle of microscopic reversibility then implies that the deprotonation in "Shilov-type C-H activation" occurs from a Pt(IV) hydridomethyl intermediate, rather than from a Pt sigma-methane complex.