75346-83-7Relevant academic research and scientific papers
Synthesis and Some Reactions of a Terminal Carbyne Complex of Osmium. Crystal Structures of Os(CR)Cl(CO)(PPh3)2 and Os(=C(AgCl)R)Cl(CO)(PPh3)2
Clark, G. R.,Cochrane, C. M.,Marsden, K.,Roper, W. R.,Wright, L. J.
, p. 211 - 230 (1986)
The reaction of two equivalents of LiR (R=p-tolyl) with the dichlorocarbene complex OsCl2(=CCl2)(CO)(PPh3)2 gives the carbyne complex Os(CR)Cl(CO)(PPh3)2 (I) in good yield.X-ray crystal structure determination shows that I is mononuclear with an OsC distance of 1.78(2) Angstroem.The OsC bond reacts with electrophiles rather than nucleopiles.Thus, HCl adds to give the alkylidene complex OsCl2(=CHR)(CO)(PPh3)2, Cl2 forms OsCl2(=CClR)(CO)(PPh3)2 and sulphur, selenium and tellurium react to yield to corresponding dihapto-chalcoacyls Os(η2-CR)Cl(CO)(PPh3)2 (X= S, Se, Te).Group Ib metal halides also add to the OsC bond form the adducts OsR)Cl(CO)(PPh3)2 (MX= CuI, AgCl, AuCl).The X-ray crystal structure determination of OsR)Cl(CO)(PPh3)2 (II) suggest that this complex can be considered as a dimetallacyclopropene derivative.Crystals of I are monoclinic, space group P21/n, a 17.030(2), b 12.774(1), c 18.315(3) Angstroem β 107.96 grad, V 3793.2 Angstroem3, Z= 4, Dm 1.53(1), Dc 1.54.Crystal of II are monoclinic, space group P21/n, a 13.021(2), b 23.714(2), c 12.999(2) Angstroem, β 90.556(2) grad, V 4013.7 Angstroem3, Z=4, Dm 1.705(5), Dc 1.695.The structures were solved by conventional heavy-atom methods, and refined by full-matrix least-squares employing anisotropic thermal parameters for all non-hydrogen atoms except for the carbon atoms of phenyl rings.Phenyl hydrogen atoms were included in calculated positions.Final residuals R were 0.040 and 0.037, respectively.
