Rapid 2e(-) N- transfer reactions occur between both cis- and trans-[Os-VI(tpy)(Cl)(2)(N)](+) and Me2C6H3SH to give cis- and trans-[Os-IV(tpy)(Cl)(2)(NS(H)C6H3Me2)](+) with retention of stereo chemistry. These complexes undergo further reactions With PPh3 or p-MeOC6H4NH2 by net 2e(-), NSC6H3Me22- group transfer reactions to give the solvento complexes, cis- and trans- [Os-II(tpy)(Cl)(2)(NCCH3)], and the organic products, Ph3PNSC6H3Me2 and p-MeOC6H4N(H)NS(H)C6H3Me2, respectively. The sequential atom/group transfer reactions at the nitrido nitrogen atom provide a new stepwise synthetic route to PNS and NNS heteroatom compounds. [GRAPHICS]