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)][Me LZn(S)] (2) (Me L={(2,6-i Pr2 C6 H3 )NC(Me)}2 CH), was isolated via reaction of [Me LZnSCPh3 ] (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 N2 O to form [K(2.2.2-cryptand)][Me LZn(SH)(CCPh)] (4) and [K(2.2.2-cryptand)][Me LZn(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)][tBu LNi(S)] (tBu L={(2,6-i Pr2 C6 H3 )NC(t Bu)}2 CH).