✦ LIBER ✦

On the Reactivity of [(Mes)Os(CO)Cl2] Toward Grignard Reagents. Unexpected Formation and X-ray Crystal Structure of [(Mes)Os(cyclohexene)(CO)]

✍ Scribed by Werner, Helmut ;Stahl, Stefan ;Schulz, Michael

Publisher: Wiley (John Wiley & Sons)
Year: 1991
Tongue: English
Weight: 538 KB
Volume: 124
Category: Article
ISSN: 0009-2940
DOI: 10.1002/cber.19911240406

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✦ Synopsis

Osmium mesitylene complexes / 0 s -R bonds, formation of / Osmium aryl hydrido compounds / Cyclohexene, generation from C6Hl1MgX I01 Reaction of [(Mes)Os(CO)Cl,] (3) with PhLi in benzene gives the diphenylosmium compound [(Mes)OsPh,(CO)] (6) whereas with PhMgBr [(Mes)OsPh(CO)Br] (7) is obtained. Treatment of 3 with TolMgBr in benzene or ether affords almost exclusively the monoaryl complex [(Mes)OsTol(CO)Br] (8). Compound 3 reacts with C6H1,MgC1 to give both [(Mes)Os(C,H,,),(CO)] (9) and [(Mes)Os(C,H,,)(CO)] (10) in 60 and 30% yield, respectively. With C6H11MgBrr complex 10 is mainly obtained. Reaction of 7 and 8 with Na/Hg in THF/EtOH gives nearly quantitatively the arylhydridoosmium complexes [(Mes)Os-C,H,R(CO)H] (14, 15). The analogous hydrido methyl compound [(Mes)OsCH,(CO)H] (13) reacts with CC1, to produce

[(Mes)OsCH,(CO)Cl] (lY), which is not accessible from 3 and LiCH3 or CH3MgX. The X-ray structure analysis of 10 reveals that the cyclohexene is coordinated in the endo configuration.

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