189028-37-3Relevant academic research and scientific papers
New five- and six-coordinate nitrosylosmium(O) and nitrosylosmium(II) complexes prepared from the stable 16-electron species [OsCl(NO)(PR3)2]
Werner, Helmut,Fluegel, Ruth,Windmueller, Bettina
, p. 493 - 505 (2007/10/03)
The coordinatively unsaturated starting materials trans[OsCl(NO)(PjPr3)2] (2) and trans-[OsCl(NO)(PJPr2Ph)2] (3), for which a new one-pot synthesis is reported, react with isocyanides, SO2 and O2 to give the corresponding 1:1 adducts [OsCl(NO)(L)(PJPr2R)2] (4-7). The corresponding methyleneosmium complex [OsCl(NO)(=CH2)(PjPr3)2] (9), on treatment with SO2 and HCl, affords the six-coordinate osmium(II) compounds [OsCI(NO){K2(C,O)-CH2S(O)O)(PiPr3)2] (10) and [OsCl2(NO)(CH3)(PJPr3)2] (11), respectively. The reactions of 2 and 3 with HC1, I2, CH3I, CH2=CHBr, R'CO2H, PhSH, CH3OH, PhCOSH, and R'CHO lead by oxidative addition to the corresponding octahedral osmium(II) complexes [OsCl-(NO)(X)(Y)(PiPr2R)2] (12-24). The initially formed compound [OsHCl(NO){SC(=O)Ph)(PjPr3)2] (20a) rearranges smoothly to the more stable S-bonded isomer [OsHCl(NO){OC(=S) Ph)(PjPr3)2] (20b). Alkynyl(hydrido)- and diynyl(hydrido)-osmium(II) complexes 26-31 and 34, 35 are obtained from 2 or 3 and HC≡CCO2Me, propargylic alcohols HC≡CCPh(R')OH or the diyne HC≡CC≡CCPh2OH. The compounds [OsHCl(NO)(C≡CCPh(R')OHJ(PiPr3)2] (30, 31) react with aqueous HCl in benzene to give the ηl-allenylosmium(II) derivatives [OsCl2(NO)(η1-CH=C=C(Ph)R')(PiPr3) 2] (32, 33). [OsHCl(NO)(CsCC≡CCPh2OH)(P/Pr3)2] (34) has been characterized by X-ray structural analysis. VCH Verlagsgesellschaft mbH.
