Synthesis of a 'Masked' Terminal Zinc Sulfide and Its Reactivity with Bronsted and Lewis Acids

摘要

The "masked" terminal Zn sulfide, [K(2.2.2-cryptand)][(LZn)-L-Me(S)] (2) (L-Me={(2,6-(Pr2C6H3)-Pr-i)NC(Me)}(2)CH), was isolated via reaction of [(LZnSCPh3)-L-Me] (1) with 2.3 equivalents of KC8 in THF, in the presence of 2.2.2-cryptand, at -78 degrees C. Complex 2 reacts readily with PhCCH and N2O to form [K(2.2.2-cryptand)][(LZn)-L-Me(SH)(CCPh)] (4) and [K(2.2.2-cryptand)][(LZn)-L-Me(SNNO)] (5), respectively, displaying both Bronsted 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)][(LNi)-L-tBu(S)] (L-tBu={(2,6-(Pr2C6H3)-Pr-i)NC(Bu-t)}(2)CH).