X-ray diffraction and solid-state 119 Sn CP-MAS NMR studies of some triaryltin(IV) chlorides

The solid-state 119 Sn cross-polarization (CP) magic angle spinning (MAS) NMR spectra of a series of triaryltin chlorides of the form Ar 3 SnCl have been acquired. The indirect spin-spin coupling constants (J( 119 Sn- 35 Cl)), quadrupolar-dipolar shifts (d( 119 Sn- 35 Cl)), and the 119 Sn chemical shift tensors were extracted. For the spectrum of triphenyltin chloride (I) the validity of the first-order perturbation approximation was tested by comparing results of both the perturbation and cubic-equation approaches and a variable-temperature NMR study undertaken to investigate the influence of the previously reported molecular motion in the solid. The X-ray crystal structures of the tris(o-tolyl)tin chloride (II) and tris(p-tolyl)tin chloride (IV) complexes have been examined. They belong to the monoclinic and triclinic space groups P2 1 /n and P[Formula: see text], respectively, which are different from the previously reported tris(m-tolyl)tin chloride (III) complex, which crystallizes in the space group R3 and has threefold molecular symmetry. The structures and NMR properties of the complexes with meta-substituents are quite different from those with ortho- or para-substituents having axially symmetric shift tensors with small spans and larger J values.Key words: aryltin chlorides, magic angle spinning NMR, tin-chlorine spin-spin coupling, 119 Sn chemical shift tensor, crystal structure.