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https://hdl.handle.net/2440/59953
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Type: | Journal article |
Title: | Syntheses and molecular structures of some tricobalt carbonyl clusters containing 2,4,6-trimethyl-1,3,5-trithiane |
Author: | Bruce, M. Zaitseva, N. Skelton, B. White, A. Fox, M. Low, P. |
Citation: | Dalton Transactions: an international journal of inorganic chemistry, 2010; 39(5):1222-1234 |
Publisher: | Royal Soc Chemistry |
Issue Date: | 2010 |
ISSN: | 1477-9226 1477-9234 |
Statement of Responsibility: | Michael I. Bruce, Natasha N. Zaitseva, Brian W. Skelton, Allan H. White, Mark A. Fox and Paul J. Low |
Abstract: | Reactions of CCo3 carbonyl clusters Co3(mu3-CR)(CO)9 with 2,4,6-trimethyl-1,3,5-trithiane (SMe3) have given Co3(mu3-CR)(mu3-SMe3)(CO)6 [R = H (1), C[triple bond]CSiMe3 (2)]. A small amount of the coupled-alkyne product Me3SiC2[Co2(CO)6]C2[Co2(mu-SMe3)(CO)4]C[triple bond]CSiMe3 (3) was isolated from the latter reaction. The reaction of Co3(mu3-CC[triple bond]CSiMe3)(mu3-SMe3)(CO)6 (2) with AuCl(PPh3) in the presence of NaOMe gave Co3{mu3-CC[triple bond]CAu(PPh3)}(mu3-SMe3)(CO)6 (4), which in turn reacts with Co3(mu3-CBr)(CO)9 in the presence of catalytic amounts of Pd(PPh3)4 and CuI to give {(OC)9Co3}(mu-C[triple bond]CC[triple bond]C){Co3(mu3-SMe3)(CO)6} (5). Further substitution of 5 with SMe3 gave symmetrical {Co3(mu3-SMe3)(CO)6}2(mu-C[triple bond]CC[triple bond]C) (6), also obtained from a reaction between {Co3(CO)9}2(mu-C[triple bond]CC[triple bond]C) and two equivalents of SMe3. Similar substitution of Co3{mu3-C(C[triple bond]C)2[Ru(dppe)Cp*]}(CO)9 with SMe3 gave Co3{mu3-C(C[triple bond]C)2[Ru(dppe)Cp*]}(mu3-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 mu3-CR group. The three S donors occupy axial sites, with all CO groups being in equatorial sites. Reactions of Co3(mu3-CBr)(CO)9 with SMe3 gave only Co3(mu3-CX)(mu3-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. |
Rights: | © Royal Society of Chemistry 2010 |
DOI: | 10.1039/b909708b |
Grant ID: | ARC |
Published version: | http://dx.doi.org/10.1039/b909708b |
Appears in Collections: | Aurora harvest 5 Chemistry and Physics publications |
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