Studies in aryltin chemistry: Part XIV. Crystal and molecular structures of tris( o-methoxyphenyl)tin(IV) chloride, fluoride and oxide

Abstract

Full crystal structures are reported for the tris( o-methoxyphenyl)tin compounds, ( o-CH 3OC 6H 4) 3SnX [X=Cl ( A), F ( B)] and [( o-CH 3OC 6H 4) 3Sn] 2O ( C), together with both solid-state and solution (CDCl 3) 119Sn NMR data for B and C as well as (Mes) 3SnF and [( o-Tol) 3Sn] 2O. Compound B like A is monomeric with a similar but not identical arrangement of aryl groups around the tin while NMR data indicate that B has almost the same geometry in solution as in the solid state. The anomalously lower frequency δ( 119Sn) value for B is consistent with the more ionic character of the SnF bond compared with other SnX (X=Cl, Br, I) bonds. Compound C is the first (Ar 3Sn) 2O with an SnOSn bond angle between 140 and 180°. The comparison of solid-state with solution 2 J( 119Sn, 119Sn) values for C and [( o-Tol) 3Sn] 2O suggests that the solid state favours structures having larger SnOSn angles. Reacting C with water gives ( o-CH 3OC 6H 4) 3SnOH only in solution, identified by its 13C and 119Sn NMR spectra.