Abstract
The relative cation−anion position in [Pt(Me)(η2-olefin)(N,N)]BF4 complexes (where N,N = 2,6-(R‘)2C6H3NC(R‘ ‘)C(R‘ ‘)N-2,6-(R‘)2C6H3, R‘ = H, Me, Et, and i-Pr, R‘ ‘ = H, Me; olefin = CH2CHR, R = H, Me, COOMe) in methylene chloride has been investigated by detecting specific interionic dipolar interactions in the 19F{1H}-HOESY NMR spectra. The counterion shows strong interionic contacts with R‘ ‘ and R‘ protons and weak contacts with R and olefinic protons only when R‘ < Et and R‘ ‘ = Me. For R‘ ≥ Et the accessibilty to the metal center is completely inhibited and the counterion is located above or below the backside of the diimine ligand. The same position is also observed when R‘ ‘ = H and R‘ = R = Me despite the limited steric hindrance of the substituents due to specific interactions between H‘ ‘ and the fluorine of BF4-. In the other cases (R‘ < Et), the counterion also interacts with Me, R, and olefinic protons, indicating that the accessibility to the metal center is not forbidden.
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