716323-52-3Relevant academic research and scientific papers
Hydrocarbyl ligand tuning of the PtII/IV redox potential
Vedernikov, Andrei N.,Pink, Maren,Caulton, Kenneth G.
, p. 3642 - 3646 (2008/10/09)
The potentially tridentate macrocycle [2.1.1]-(2,6)-pyridinophane (L) enables the transient LPtII(CH3)+ to cleave the C-H bond of two molecules of C6F5H. The resulting product has two aryl groups on Pt but, in contrast to nonfluorinated analogue, varies in its location of the cleaved H, as is evident from the two products (HL+)PtIIR2 and (η3-L)-pt IVH(R)2+. At equilibrium, the related example where R = CH3 is purely the PtIV redox isomer, which with R = C6H5 shows detectable populations of both isomers, and with R = C6F5 is purely the pyridine-protonated (HL+)PtII redox isomer. All species show a hydrogen bond from the pyridinium proton to PtII. Consistent with the idea that electron-withdrawing R makes platinum(II) more resistant to oxidation (i.e., a proton on Pt), and thus less Bronsted basic, the 1J ptH coupling constant falls in the series R = Me (90 Hz), R = C 6H5 (86 Hz), and R = C6F5 (63 Hz).
