ISSN:
0009-2940
Keywords:
Osmium(0) complexes
;
Nitrosyl complexes
;
Oxidative addition reactions
;
Alkynyl(hydrido)osmium complexes
;
Diynyl(hydrido)osmium complexes
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The coordinatively unsaturated starting materials trans-[OsCl(NO)PiPr3)2] (2) and trans- [(sCl(NO)(PiPr2Ph)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)(P)(PiPr2R)2) (4-7). The corresponding methyleneosmium complex [OsCl(NO)(=CH2)(PiPr3)2] (9), on treatment with SO2 and HCl, affords the six-coordinate osmium(II) compounds [OsCl(NO)(K2(C,O)-CH2S(O)O)()iPr3)2] (10) and [OsCl2(NO)(CH3(PiPr3)2]2] (11), respectively. The reactions of 2 and 3 with HCl, 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}(PiPr3)2] (20a) rearranges smoothly to the more stable S-bonded isomer [OsHCl(NO){OC(=S)Ph}(PiPr3)2] (20b). Alkynyl(hydrid)- and diynyl(hydrido)-osmium(II) complexes 20-31 and 34, 35 are obtained from 2 or 3 and HC≡CCO2/sb〉Me, propargylic alcohols HC≡CCPh-(R')OH or the diyne HC≡CC≡CCPh2OH. The compounds [OsHCl(NO)[C≡CCPh(R')OH)(PiPr3)2] (30, 31) react with aqueous HCl in benzene to give the η1-allenylosmium(II) derivatives [OsCl2(NO)(η1-CH=C=C(Ph)R'](PiPr3)2] (32, 33). [OsHCl(NO)(C≡CC≡CCPh2OH)(PiPR3)2] (34) has been characterized by X-ray structural analysis.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19971300409
