Synthesis of a “Masked” Terminal Nickel(II) Sulfide by Reductive Deprotection and its Reaction with Nitrous Oxide

The addition of 1 equiv of KSCPh 3 to [L R NiCl] (L R ={(2,6‐ i Pr 2 C 6 H 3 )NC(R)} 2 CH; R=Me, t Bu) in C 6 H 6 results in the formation of [L R Ni(SCPh 3 )] ( 1 : R=Me; 2 : R= t Bu) in good yields. Subsequent reduction of 1 and 2 with 2 equiv of KC 8 in cold (−25 °C) Et 2 O in the presence of 2 equiv of 18‐crown‐6 results in the formation of “masked” terminal Ni II sulfides, [K(18‐crown‐6)][L R Ni(S)] ( 3 : R=Me; 4 : R= t Bu), also in good yields. An X‐ray crystallographic analysis of these complexes suggests that they feature partial multiple‐bond character in their NiS linkages. Addition of N 2 O to a toluene solution of 4 provides [K(18‐crown‐6)][L t Bu Ni(SNNO)], which features the first example of a thiohyponitrite (κ 2 ‐[SNNO] 2− ) ligand.