Pourreau, Daniel B.; Geoffroy, Gregory L.; Rheingold, Arnold L., Organometallics, 1986, vol. 5, # 7, p. 1337 - 1345
作者:Pourreau, Daniel B.、Geoffroy, Gregory L.、Rheingold, Arnold L.、Geib, Steven J.
DOI:——
日期:——
Synthesis and Characterization of Osmium Polyhydrides. X-ray Crystal Structures of (C<sub>5</sub>Me<sub>5</sub>)OsH<sub>5</sub> and (C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>Os<sub>2</sub>H<sub>4</sub>
作者:Christopher L. Gross、Gregory S. Girolami
DOI:10.1021/om060920b
日期:2007.1.1
Treatment of (C5Me5)(2)Os2Br4 with LiAlH4 in Et2O followed by addition of MeOH at -78 degrees C affords two products: the osmium(VI) pentahydride (C5Me5)OsH5 and the dinuclear osmium(III) tetrahydride (C5Me5)(2)Os2H4. The X-ray crystal structures reveal that (C5Me5)OsH5 adopts a pseudo-octahedral geometry with one axial and four equatorial hydride ligands, whereas all four hydride ligands in (C5Me5)(2)Os2H4 bridge the osmium-osmium axis. Treatment of (C5Me5)OsH5 with HBF4 center dot Et2O affords the osmium(VIII) hexahydride [(C5Me5)OsH6][BF4], which evidently adopts a classical polyhydride structure, as judged from variable-temperature T-1 studies. Treatment of (C5Me5)OsH5 with tert-butyllithium in the presence of N,N,N',N' ',N' '-pentamethyldiethylenetriamine (pmdeta) affords the osmium(IV) tetrahydride salt [Li(pmdeta)][(C5Me5)OsH4], which is proposed to adopt a four-legged piano stool geometry. IR and NMR studies of the Os-D analogues of these new osmium hydrides are also discussed.