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Issue 5, 2010
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Syntheses and molecular structures of some tricobalt carbonyl clusters containing 2,4,6-trimethyl-1,3,5-trithiane

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Abstract

Reactions of CCo3 carbonyl clusters Co33-CR)(CO)9 with 2,4,6-trimethyl-1,3,5-trithiane (SMe3) have given Co33-CR)(μ3-SMe3)(CO)6 [R = H (1), C[triple bond, length as m-dash]CSiMe3 (2)]. A small amount of the coupled-alkyne product Me3SiC2[Co2(CO)6]C2[Co2(μ-SMe3)(CO)4]C[triple bond, length as m-dash]CSiMe3 (3) was isolated from the latter reaction. The reaction of Co33-CC[triple bond, length as m-dash]CSiMe3)(μ3-SMe3)(CO)6 (2) with AuCl(PPh3) in the presence of NaOMe gave Co33-CC[triple bond, length as m-dash]CAu(PPh3)}(μ3-SMe3)(CO)6 (4), which in turn reacts with Co33-CBr)(CO)9 in the presence of catalytic amounts of Pd(PPh3)4 and CuI to give {(OC)9Co3}(μ-C[triple bond, length as m-dash]CC[triple bond, length as m-dash]C){Co33-SMe3)(CO)6} (5). Further substitution of 5 with SMe3 gave symmetrical {Co33-SMe3)(CO)6}2(μ-C[triple bond, length as m-dash]CC[triple bond, length as m-dash]C) (6), also obtained from a reaction between {Co3(CO)9}2(μ-C[triple bond, length as m-dash]CC[triple bond, length as m-dash]C) and two equivalents of SMe3. Similar substitution of Co33-C(C[triple bond, length as m-dash]C)2[Ru(dppe)Cp*]}(CO)9 with SMe3 gave Co33-C(C[triple bond, length as m-dash]C)2[Ru(dppe)Cp*]}(μ3-SMe3)(CO)6 (7). In all of these compounds, the SMe3 ligand caps the basal face of the CCo3 cluster on the opposite side to the μ3-CR group. The three S donors occupy axial sites, with all CO groups being in equatorial sites. Reactions of Co33-CBr)(CO)9 with SMe3 gave only Co33-CX)(μ3-SMe3)(CO)6 [X = C(O)NMe2 (8), CO2H (9)]. The redox properties and electronic structure of the C4-bridged bis-cluster 6 have been investigated through a combination of cyclic voltammetry, IR spectroelectrochemistry and DFT calculations, with comparisons made with suitable model systems. Single-crystal X-ray diffraction structure determinations of 1, 2, 3, 4 and 8 are reported.

Graphical abstract: Syntheses and molecular structures of some tricobalt carbonyl clusters containing 2,4,6-trimethyl-1,3,5-trithiane

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Publication details

The article was received on 22 May 2009, accepted on 28 Sep 2009 and first published on 19 Nov 2009


Article type: Paper
DOI: 10.1039/B909708B
Citation: Dalton Trans., 2010,39, 1222-1234
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    Syntheses and molecular structures of some tricobalt carbonyl clusters containing 2,4,6-trimethyl-1,3,5-trithiane

    M. I. Bruce, N. N. Zaitseva, B. W. Skelton, A. H. White, M. A. Fox and P. J. Low, Dalton Trans., 2010, 39, 1222
    DOI: 10.1039/B909708B

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