Stitching together SNx units in the coordination sphere of zirconium: assembly of a tris(imido)sulfite and a hydrazidobis(imido)sulfiteElectronic supplementary information (ESI) available: Characterisation and crystallographic data for 1, 3 and 4; computational details and further discussion. CCDC 857217 and 857218. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2cc17594k

Reaction of a zirconium imido and a hydrazinediido complex with bis(trimethylsilyl)sulfur diimide yielded the corresponding formal [2+2] cycloaddition products, the trisimidosulfito complex and the hydrazidobis(imido)sulfito complex containing an unprecedented SN 2 (NN) unit. Trisimidosulfito and hydrazidobis(imido)sulfito zirconium complexes are obtained by [2+2] cycloaddition of bis(trimethylsilyl)sulfur diimide with a zirconium imide or hydrazinediide.