We use cookies to ensure that we give you the best experience on our website. By continuing to browse this repository, you give consent for essential cookies to be used. You can read more about our Privacy and Cookie Policy.

Durham Research Online
You are in:

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

Bruce, M.I. and Zaitseva, N.N. and Skelton, B.W. and White, A.H. and Fox, M.A. and Low, P.J. (2010) 'Syntheses and molecular structures of some tricobalt carbonyl clusters containing 2,4,6-trimethyl-1,3,5-trithiane.', Dalton transactions., 39 (5). pp. 1222-1234.


Reactions of CCo3 carbonyl clusters Co3(μ3-CR)(CO)9 with 2,4,6-trimethyl-1,3,5-trithiane (SMe3) have given Co3(μ3-CR)(μ3-SMe3)(CO)6 [R = H (1), CCSiMe3 (2)]. A small amount of the coupled-alkyne product Me3SiC2[Co2(CO)6]C2[Co2(μ-SMe3)(CO)4]CCSiMe3 (3) was isolated from the latter reaction. The reaction of Co3(μ3-CCCSiMe3)(μ3-SMe3)(CO)6 (2) with AuCl(PPh3) in the presence of NaOMe gave Co3{μ3-CCCAu(PPh3)}(μ3-SMe3)(CO)6 (4), which in turn reacts with Co3(μ3-CBr)(CO)9 in the presence of catalytic amounts of Pd(PPh3)4 and CuI to give {(OC)9Co3}(μ-CCCC){Co3(μ3-SMe3)(CO)6} (5). Further substitution of 5 with SMe3 gave symmetrical {Co3(μ3-SMe3)(CO)6}2(μ-CCCC) (6), also obtained from a reaction between {Co3(CO)9}2(μ-CCCC) and two equivalents of SMe3. Similar substitution of Co3{μ3-C(CC)2[Ru(dppe)Cp*]}(CO)9 with SMe3 gave Co3{μ3-C(CC)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 Co3(μ3-CBr)(CO)9 with SMe3 gave only Co3(μ3-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.

Item Type:Article
Full text:Full text not available from this repository.
Publisher Web site:
Record Created:10 Jan 2012 12:35
Last Modified:20 Nov 2014 11:05

Social bookmarking: del.icio.usConnoteaBibSonomyCiteULikeFacebookTwitterExport: EndNote, Zotero | BibTex
Usage statisticsLook up in GoogleScholar | Find in a UK Library