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DOI: 10.1039/A805303K (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 3501-3510

Alkenyl and alkynyl complexes of osmium(II) derived from [OsH(Cl)(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzothiadiazole)

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Anthony F. Hill and James D. E. T. Wilton-Ely

Abstract

Treatment of [OsH(CA)(NCMe)2(PPh3)2]+ (A = O or S) with [NEt4]Cl and 2,1,3-benzothiadiazole (BTD) provided [OsH(Cl)(CA)(BTD)(PPh3)2] (A = O or S). Under mild conditions, the complex [OsH(Cl)(CO)(BTD)(PPh3)2] hydro-osmiates ethynyltoluene, ethyne and di(4-tolyl)butadiyne to provide vinyl complexes [Os(CH[double bond, length half m-dash]CHR)Cl(CO)(BTD)(PPh3)2] (R = C6H4Me-4), [Os(CH[double bond, length half m-dash]CH2)Cl(CO)(BTD)(PPh3)2] and [Os{C(C[triple bond, length half m-dash]CR)[double bond, length half m-dash]CHR}Cl(CO)(BTD)(PPh3)2]. Complex [OsH(CO)(NCMe)2(PPh3)2]+ reacted with HC[triple bond, length half m-dash]CR to provide [Os(CH[double bond, length half m-dash]CHR)(CO)(NCMe)2(PPh3)2]+ which is converted by [NEt4]Cl into [Os(CH[double bond, length half m-dash]CHR)Cl(CO)(NCMe)(PPh3)2]. Treatment of [Os(CH[double bond, length half m-dash]CHR)Cl(CO)(BTD)(PPh3)2] with CNCMe3 or CO provided [Os(CH[double bond, length half m-dash]CHR)Cl(CO)(L)(PPh3)2] (L = CNCMe3 or CO). The dithiocarbamate complex [Os(CH[double bond, length half m-dash]CHR)(S2CNMe2)(CO)(PPh3)2] and the osmatetraborane [Os(CH[double bond, length half m-dash]CHR)(B3H8)(CO)(PPh3)2] resulted from the reactions of [Os(CH[double bond, length half m-dash]CHR)Cl(CO)(BTD)(PPh3)2] with Na[S2CNMe2] and [NBun4][B3H8], respectively, whereas with K[HB(pz)3] (pz = pyrazolyl) initially [Os(CH[double bond, length half m-dash]CHR)(CO)(PPh3)2{η2-HB(pz)3}] was formed which is converted into [Os(CH[double bond, length half m-dash]CHR)(CO)(PPh3){HB(pz)3}] on heating. No intermediates are however observed in the corresponding reaction with 1,4,7-trithiacyclononane ([9]aneS3) to provide [Os(CH[double bond, length half m-dash]CHR)(CO)(PPh3)([9]aneS3)]+. The alkynyl complex [Os(C[triple bond, length half m-dash]CR)Cl(CO)(BTD)(PPh3)2] was obtained from either (i) the reaction of [OsH(Cl)(CO)(BTD)(PPh3)2] with [Hg(C[triple bond, length half m-dash]CR)2] or (ii) [Os(CH[double bond, length half m-dash]CHR)Cl(CO)(BTD)(PPh3)2] with an excess of HC[triple bond, length half m-dash]CR. Treatment of [Os(C[triple bond, length half m-dash]CR)Cl(CO)(BTD)(PPh3)2] with Na[S2CNMe2] or alternatively [Os(CH[double bond, length half m-dash]CHR)(S2CNMe2)(CO)(PPh3)2] with an excess of HC[triple bond, length half m-dash]CR provided [Os(C[triple bond, length half m-dash]CR)(S2CNMe2)(CO)(PPh3)2], which can also be obtained from [OsH(S2CNMe2)(CO)(PPh3)2] and [Hg(C[triple bond, length half m-dash]CR)2]. The BTD in [Os(C[triple bond, length half m-dash]CR)Cl(CO)(BTD)(PPh3)2] is substituted by CNCMe3 to provide [Os(C[triple bond, length half m-dash]CR)Cl(CO)(CNCMe3)(PPh3)2]. The reaction of [OsH(Cl)(CS)(BTD)(PPh3)2] with HC[triple bond, length half m-dash]CR provided [Os(CH[double bond, length half m-dash]CHR)Cl(CS)(BTD)(PPh3)2] which in contrast to [Os(CH[double bond, length half m-dash]CHR)Cl(CO)(BTD)(PPh3)2] reacts with carbon monoxide to provide the thiocinnamoyl complex [Os(η2-SCCH[double bond, length half m-dash]CHR)Cl(CO)(PPh3)2].

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