Synthesis and Structure of a Macrocyclic Dinickel Complex Incorporating a Hypercoordinated Sulfenium(II) Cation

The synthesis and structure of a macrocyclic dinickel complex incorporating a hypercoordinated sulfenium(II) cation are reported. The novel complex [Ni 2 L 3 (Cl)] 2+ was obtained from a reaction of the per‐hydroxyethylated N 6 S 2 macrocycle H 2 L 2 with NiCl 2 (H 2 O) 6 in the presence of air, and isolated as its ClO 4 or BPh 4 salt. The structure reveals a three‐coordinate sulfenium cation that is stabilized by two intramolecularly coordinating amino groups. The N–S bonds are 2.087(7) Å and 2.105(6) Å and the N–S–N bond angle is 168.2(2)°. The bonding is best described by a N , N ‐chelated sulfur(II) atom (3c–4e bond) bearing two lone pairs and a formal charge of +1.