Diosmacycloalkanes as models for the formation of hydrocarbons from surface methylenes. Progress report, April 1, 1988--March 31, 1989

摘要

We have obtained a neutron diffraction data set for Os(sub 2)(CO)(sub 8)((mu)-C(sub 2)H(sub 4)). While the structure is still being solved, it is already clear that the hybridization at both of the ethylene carbons is sp(sup 3). Our first interpretation of our liquid crystal NMR results had suggested a very acute H-C-H angle. We have also obtained (sup 13)C liquid crystal data for Os(sub 2)(CO)(sub 8)((mu)-C(sub 2)H(sub 4)). Liquid crystal NMR ((sup 13)C as well as (sup 1)H) spectra have been obtained for Os(CO)(sub 4)(C(sub 2)H(sub 4)) and its solution structure determined, in order to test our methodology on a molecule with a rigid structure. The normal modes of Os(CO)(sub 4)((mu)-C(sub 2)H(sub 4)) and its deuterated and (sup 13)C-labelled isotopomers have been completely assigned. A partial vibrational analysis of Os(sub 2)(CO)(sub 8)((mu)-propene), Os(sub 2)(CO)(sub 8)(trans-2-butene), and Os(sub 2)(CO)(sub 8)(1-butene) has been completed. We have prepared Os(CO)(sub 4)((mu)-CH(sub 2)CH(sub 2)CH(sub 2)) and its 3,3-dideuterio analog. In the course of this work the reaction of Na(sub 2)Os(CO)(sub 4) with a number of 1,3-propanediol derivatives has been examined. 1,3-Propanediol ditosylate afforded much better yields of the osmacycle than did either the ditriflate or diiodide. 2,2-Dideutero-1,3-propanediol ditosylate was used to prepare the deuterium-labelled osmacyclobutane.