Assessing weak intramolecular donor-acceptor interactions using 1H-117Sn J-HMQC spectroscopy

It is demonstrated that long-range J(H-1,Sn-117) coupling constants down to 0.3 Hz, can be accurately quantified from non-linear fitting of the sine modulation of the associated H-1-Sn-117 correlation cross-peak intensities sampled as a function of the heteronuclear antiphase coherence preparation time in the H-1-Sn-117 J-HMQC pulse sequence. The contribution of additional, undesired modulations is illustrated and assessed using the product operator formalism, and is traced back to contributions that arise from miss-setting of the wandering 180degrees pulse angle in the constant time period. The power of the method and its use in the characterization of weak intramolecular donor-acceptor interactions are illustrated by the determination of long-range J(H-1,Sn-117) coupling constants of bis[3-(dimethylamino)propyl]tin derivatives, [Me2N(CH2)(3)](2)SnR2 (2, R = Me; 3, R = Ph; 4, R = t-Bu). By comparing these with the values found for the corresponding bis(4-methylpentyl)tin derivatives, [Me2CH(CH2)(3)](2)SnR2 (2', R = Me; 3', R = Ph), which lack such interactions, the use of long-range coupling constants to detect intramolecular donor-acceptor interactions is evaluated. It is concluded that J(H-1,Sn-117) couplings up to six bonds through an organic carbon chain can be quantified., whether donor-acceptor interactions are present or not. Furthermore, evidence is presented that, when two scalar coupling pathways co-exist, the pathway involving an intramolecular donor-acceptor interaction can have opposite sign, thus decreasing the overall coupling constant to a value smaller than that actually measured in the absence of a donor-acceptor interaction, where only one coupling pathway is active. There is nevertheless clear numerical value discrimination in the series of compounds investigated between long-range couplings in derivatives without weak intramolecular donor-acceptor interactions and those where such interactions can exist. Copyright (C) 2004 John Wiley Sons, Ltd.