Synthesis of a “Masked” Terminal Zinc Sulfide and Its Reactivity with Brønsted and Lewis Acids

The “masked” terminal Zn sulfide, K(2.2.2‐cryptand)]^MeLZn(S)] ( 2 ) (^MeL={(2,6‐ⁱPr₂C₆H₃)NC(Me)}₂CH), was isolated via reaction of ^MeLZnSCPh₃] ( 1 ) with 2.3 equivalents of KC₈ in THF, in the presence of 2.2.2‐cryptand, at ?78 °C. Complex 2 reacts readily with PhCCH and N₂O to form K(2.2.2‐cryptand)]^MeLZn(SH)(CCPh)] ( 4 ) and K(2.2.2‐cryptand)]^MeLZn(SNNO)] ( 5 ), respectively, displaying both Brønsted and Lewis basicity. In addition, the electronic structure of 2 was examined computationally and compared with the previously reported Ni congener, K(2.2.2‐cryptand)]^tBuLNi(S)] (^tBuL={(2,6‐ⁱPr₂C₆H₃)NC(^tBu)}₂CH).