The complexes trans-[OsCl2(L){(S,S)-Pr-i-pybox}] ((S, S)-Pr-i-pybox = 2,6-bis[4'-(S)-isopropyloxazolin-2'-yl]pyridine; L = CNBn (3), CNCy (4) and MeCN (7)) and trans-[OsCl2(L){(R, R)-Ph-pybox}] ((R, R)-Ph-pybox = 2,6-bis[4'-(R)-phenyloxazolin-2'-yl] pyridine, L = CNBn (5), CNCy (6) and MeCN (8)) have been stereoselectively synthesized from the complexes trans-[OsCl2(eta(2)-C2H4)(R-pybox)] (R = (S, S)-Pr-i (1), (R, R)-Ph (2)), via substitution of ethylene, under reflux or microwave irradiation conditions. The complex trans-[OsCl2(eta(2)-MeO2CC CCO2Me){(S, S)-Pr-i-pybox}] (9) has been analogous prepared from complex 1. The activation of terminal alkynes and alkynols by olefin complex 1, under toluene reflux conditions, has been achieved to give vinylidene trans-[OsCl2{=C=C(H)Ph}{(S, S)-Pr-i-pybox}] (10), allenylidene trans[OsCl2(=C=C=C(R)Ph){(S, S)-Pr-i-pybox}] (R = Ph (11), H (12)) and cyclic carbene complexes trans[OsCl2{(S, S)-Pr-i-pybox}] (13). (C) 2013 Elsevier B. V. All rights reserved.