Synthesis and structural characterization of tin(IV) N-nitroso-N-phenylhydroxylaminato complexes: Crystal structures of Sn(O2N2Ph)(4), Ph2Sn(O2N2Ph)(2) and [Me2Sn(O2N2Ph)(2)](2)

Reaction of cupferron [NH4L, L = PhN(O)NO-] with tin(IV), diphenyltin(IV) a nd dimethyltin(IV) halides yields the cupferronato complexes SnL4 (1), Ph2S nL2 (L) and [Me2SnL2](2) (3). All were characterized by FT-IR, FT-Raman, NM R (H-1, C-13 and Sn-119) spectroscopic methods and X-ray structural analysi s. An almost ideal, very rare dodecahedral geometry is found in the structu re of 1. The hexacoordinated tin center exhibits a bicapped tetrahedral geo metry in complex 2. The tin centers are heptacoordinated in a pentagonal bi pyramidal geometry in the dimeric complex 3. These complexes incorporate fi ve-membered SnO2N2 and four-membered Sn2O2 inorganic rings. Vibrational spe ctral data are consistent with the structures determined. The Sn-119 NMR sp ectra indicate that in solution 1 retains its octacoordinated nature; in co mpound 2 the tin atom is hexacoordinated, while in 3 the tin atom is pentac oordinated.