Synthesis and characterisation of twelve SnIV diaryls and formation of a SnIII triaryl

Ten new crystalline compounds of formula (i) [{Sn(ArN2)2(μ-E)}2] [E = O (2), S (3), Se (4), Te (5)], (ii) [Sn(ArN2)2(ER)2] [ER = SCH2Ph (6), SePh (7), TePh (8)], (iii) [Sn(ArN2)2(Br)R] [R = CH(SiMe3)2 (9), But (10)] and (iv) [Sn(ArN2)2{CH(SiMe3)2}][BPh4] [ArN2 = C6H3(NMe2)2-2,6 (11)] have been prepared and identified by microanalysis, EI-mass spectrometry and multinuclear NMR spectroscopy, and for 2, 5, 6, 8 and 11 by single crystal X-ray diffraction. Whereas in the solid state, each of the latter five has only one of its two NMe2 substituents of each [ArN2]− ligand close to the tin atom (<3.1 A), in solution at ambient temperature the NMe2 groups are characterised by a single 1H and 13C signal. The known compounds [Sn(ArN2)2(NCE)2] [E = O (12), S (13)] were synthesised by a new route: the redox reaction between [Sn(ArN2)2] (1) and 2AgNCE. Irradiation of a toluene solution of 1 at 298 K afforded a persistent radical assigned as [˙Sn(ArN2)3] (14).