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Reactions of the dihydrogen complex OsCl2(.eta.2-H2)(CO)(PiPr3)2 with terminal alkynes: Synthesis of carbene, vinylcarbene, and .mu.-Bis-carbene osmium (II) derivatives

AuthorsEsteruelas, Miguel A. ; Lahoz, Fernando J. ; Oñate, Enrique ; Oro, Luis A.
Issue Date1995
PublisherAmerican Chemical Society
CitationJournal of the American Chemical Society 117(30): 7935-7942 (1995)
AbstractThe dihydrogen complex OsCl2(η2-H2)(CO)(PiPr3) 2 (1) has been prepared by reaction of the monohydride OsHCl(CO)(PiPr3)2 (2) with HCl. Complex 1 reacts with carbon monoxide and tert-butyl isocyanide to give OsHCl-(CO)(L)(PiPr3)2 (L = CO (3), tBuNC (4)) and HCl. The reaction of 1 with phenylacetylene affords the carbene derivative OsCl2(=CHCH2Ph)(CO)(PiPr3)2 (5), which can be also obtained by reaction of Os{(E)-CH=CHPh}Cl-(CO)(PiPr3)2 (6) with HCl. The molecular structure of 5 has been determined by X-ray crystallography. Crystals of 5 are orthorhombic, space group Pbca, with unit cell dimensions a =13.641(2) Å, b =15.698(2) Å, and c = 29.059(4) Å. The structure was solved and refined using 3185 unique, observed reflections, R = 0.0412 and Rw = 0.0380. The coordination around the osmium atom can be described as a distorted octahedron with the two triisopropylphosphine ligands occupying trans positions. The PhCH2CH moiety, clearly bonded to the metal through an Os-C double bond, is situated in a relative trans position to a chloride ligand. Complex 1 reacts with 2-methyl-1-buten-3-yne to give OsCl2{=CHCH=C(CH3)2}(CO)(PiPr3) 2 (7). The reaction of 2 with 2-methyl-1-buten-3-yne leads to Os{(E)-CH=C(H)(CH3)=CH2}Cl(CO)(PiPr3) 2 (8), which gives 7 by reaction with HCl. Complex 1 also reacts with 1,7-octadiyne. The reaction produces a mixture of products from which the binuclear μ-bis-carbene compound [(PiPr3)2(CO)Cl2Os]{=CH(CH2) 6CH=}[OsCl2(CO)(PiPr3)2] (11) was identified by NMR spectroscopy. Complex 11 can be prepared as an analytically pure solid by reaction of [(PiPr3)2(CO)ClOs]{CH=CH(CH2) 4CH=CH}-[OsCl(CO)(PiPr3)2] (12) with HCl. Complex 12 was obtained from the reaction of 2 with 1,7-octadiyne.
Identifiersdoi: 10.1021/ja00135a011
issn: 0002-7863
e-issn: 1520-5126
Appears in Collections:(ICMA) Artículos
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