AbstractDipole‐dipole relaxation via non‐bonded protons is an important relaxation mechanism for119Sn in tri‐n‐propyltin and tri‐n ‐butyltin compounds. This causes a negative nuclear Overhauser effect, arising from the negative magnetogyric ratio, which in some cases nulls the signal. The relative contributions from the spin‐rotation and dipole‐dipole mechanisms vary: larger molecules have lower spin‐rotation and higher dipolar relaxation rates. The practical significance of large nuclear Overhauser enhancement factors in recording 119Sn spectra and the relation of the dipole‐dipole contribution to the molecular motion and of the spin‐rotation contribution to the absolute shift scale for 119Sn are discussed.