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Issue 3, 2004
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Vinyl and carbene ruthenium(II) complexes from hydridoruthenium(II) precursors

Stefan Jung,a  Carsten D. Brandt,a  Justin Wolfa  and  Helmut Werner*a 
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* Corresponding authors

a Institut fur Anorganische Chemie der Universität Würzburg, Am Hubland, Germany
E-mail: helmut.werner@mail.uni-wuerzburg.de

Abstract

The reactions of the hydrido compounds [RuHCl(CO)(L)2] {L = PiPr3 (1), PCy3 (2)} with HC[triple bond, length as m-dash]CR (R = H, Ph, tBu) afforded by insertion of the alkyne into the Ru–H bond the corresponding vinyl complexes [RuCl(CH[double bond, length as m-dash]CHR)(CO)(L)2], 3–8, which upon protonation with HBF4 gave the cationic five-coordinated ruthenium carbenes [RuCl([double bond, length as m-dash]CHCH2R)(CO)(L)2]BF4, 9–14. Subsequent reactions of the carbene complexes with PR3 (R = Me, iPr) and CH3CN led either to deprotonation and re-generation of the vinyl compounds or to cleavage of the ruthenium-carbene bond and the formation of the six-coordinated complexes [RuCl(CO)(CH3CN)2(PiPr3)2]BF4, 17, and [RuH(CO)(CH3CN)2(PiPr3)2]X, 18a,b. The acetato derivative [RuH(κ2-O2CCH3)(CO)(PCy3)2], 19, also reacted with acetylene and phenylacetylene by insertion to yield the related vinyl complexes [Ru(CH[double bond, length as m-dash]CHR)(κ2-O2CCH3)(CO)(PCy3)2], 20, 21, of which that with R = H was protonated with HBF4 to yield the corresponding cationic ruthenium carbene 22. With [RuHCl(H2)(PCy3)2], 25, as the starting material, the five-coordinated chloro(hydrido)ruthenium(II) compounds [RuHCl(PCy3)(dppf)], 26 (dppf = [Fe(η5-C5H4PPh2)2]), [RuHCl{Sb(CH2Ph)3}(PCy3)2], 27, and [RuHCl(CH3CN)(PCy3)2], 30, were prepared. The reactions of 27 with HC[triple bond, length as m-dash]CR (R = H, Ph) gave the hydrido(vinylidene) complexes [RuHCl([double bond, length as m-dash]C[double bond, length as m-dash]CHR)(PCy3)2], 28 and 29, whereas treatment of 30 with HC[triple bond, length as m-dash]CPh afforded the vinyl compound [RuCl(CH[double bond, length as m-dash]CHPh)(CH3CN)(PCy3)2], 31. The molecular structures of 11 (R = tBu, L = PiPr3) and 26 were determined crystallographically.

Graphical abstract: Vinyl and carbene ruthenium(ii) complexes from hydridoruthenium(ii) precursors

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Publication details

The article was received on 10 Nov 2003, accepted on 15 Dec 2003 and first published on 13 Jan 2004


Article type: Paper
DOI: 10.1039/B314425A
Citation: Dalton Trans., 2004,0, 375-383
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    Vinyl and carbene ruthenium(II) complexes from hydridoruthenium(II) precursors

    S. Jung, C. D. Brandt, J. Wolf and H. Werner, Dalton Trans., 2004, 0, 375
    DOI: 10.1039/B314425A

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