Synthesis and structures of halides and pseudohalides of bis[2,6-bis(dimethylamino)phenyl]tin(IV)

Oxidative addition reactions of Sn{C6H3(NMe2)2-2,6}2 [≡ Sn(ArN2)2] (1) with XeF2, HgCl2 or TeCl4, dabco·2Br2, I2, or SiMe3N3 afforded [Sn(ArN2)2F2] (3), [Sn(ArN2)2Cl2] (4), [Sn(ArN2)2Br2] (5), [Sn(ArN2)2I2] (6), or [Sn(ArN2)2{N(SiMe3)2}N3] (7), respectively. Compound 3 was also obtained from 6 and aqueous KF. Treatment of 4, under phase transfer conditions using [NBnEt3]Cl in H2O, with NaN3, KOCN, or KSCN yielded [Sn(ArN2)2(N3)2] (8), [Sn(ArN2)2(NCO)2] (9), or [Sn(ArN2)2(NCS)2] (10), respectively. Alternative pathways to 7 are suggested. Excellent (3–7, 9 and 10) and satisfactory (8) yields were recorded; each compound was characterised by C, H, N microanalysis, mass spectra and multinuclear NMR solution spectra at ambient temperature, which invariably showed equivalent NMe21H and 13C signals for the two NMe2 groups. The X-ray structures of crystalline [Sn(ArN2)Cl] (2), 4, 6, 7, 8 and 10 showed that only one of the 2- and 6-Me2N substituents of an (ArN2) group was in a close Sn⋯N contact. Reaction of 2 with Li[AlMe4] or LiMe gave [Sn(ArN2)(μ-Me)2AlMe2] (11) or c-(SnMe2)6, respectively.