Study on the reactivity of organoplatinum complexes with chelating 1, 2-bis(diphenylphosphino)ethane in presence of air

The Metal – Carbon bonds are among the strongest sigma bonds in organometallic complexes. Activation of these bonds with harsh conditions and reagents were common [1], but under mild conditions was unprecedent. In this work we suggest a straight forward reaction to activate these strong bonds (Scheme.1). Platinum complexes Pt(dppe)(R)(C^N) (dppe=bis(diphenylphosphino)ethane, R=Me or p-tollyl, C^N=2-phenylpyridne or benzo[h]quinoline) were synthesized and reacted in presence of air in different solvents such as: benzene, acetonitrile, dmso, acetone, ethanol, water/acetone and methanol. Mechanistic studies employed by Gaussian09 with B3LYP method and LANL2DZ basis set for Platinum atom and 6-31G (d) basis set for the rest of atoms.Also similar reaction with acid reagent were carried out before, NMR spectra and Crystal structure of the products obtained. We compared NMR spectra of the resulting complex with previous work and it was revealed that the signals of the R group on Platinum complex are not present and also these data showed C^N chelate is closed. DFT calculation proposed the probable mechanism of this transformation. [2]In conclusion, by using the milder condition we activate strong Pt – C bond. NMR spectra confirms formation of the products and DFT calculations proposed probable mechanism of this transformation. Also this process yields the ROH byproduct.