Please use this identifier to cite or link to this item: http://hdl.handle.net/10497/17747
Title: Formation of “A-frame” dirhenium(I) hexacarbonyl complexes by trans-1,2-bis(diphenylphosphino)ethylene and bis(bidentate) ligands
Authors: Kee, Chee Leong
Zhou, Feng
Su, Haibin
Yan, Yaw Kai
Keywords: Rhenium(I) carbonyl
1,2-Dithiooxalate
Tetrathiooxalate
Dithiooxamidate
trans-1,2-Bis(diphenylphosphino)ethylene
Chalcogen–chalcogen interaction
Issue Date: 2015
Citation: Kee, C. L., Zhou, F., Su, H., & Yan, Y. K. (2015). Formation of “A-frame” dirhenium(I) hexacarbonyl complexes by trans-1,2-bis(diphenylphosphino)ethylene and bis(bidentate) ligands. Journal of Organometallic Chemistry, 792, 211–219. http://dx.doi.org/10.1016/j.jorganchem.2015.04.046
Abstract: A series of A-frame dirhenium(I) hexacarbonyl complexes bridged by trans-1,2-bis(diphenylphosphino)-ethylene (dppene) and bis(bidentate) ligands (L) were synthesized: [Re2(μ-dppene)(CO)6(μ,η2:η2-L)] (L = 1,2-dithioooxalate, 1; tetrathiooxalate, 2; dithiooxamidate, 3 and oxamidate, 4). X-ray crystallographic analysis of 1–3 confirmed that the dppene ligand adopts a syn bridging conformation with nearly eclipsed P–Re bonds in these complexes. The angle between the phosphorus lone pairs of the diphosphine is adjusted to suit different Re⋯Re distances (5.6–6.4 Å) mainly by twisting the ethylene Cdouble bond; length as m-dashC bond and enlarging the P–Cdouble bond; length as m-dashC angles of the phosphine backbone. Complex 2 forms dimers in the solid state via intermolecular S⋯S interactions (3.39 Å). Proton and 31P NMR data indicate that these dimers persist in chloroform solution but not in DMSO. Natural bond orbital analysis revealed the S⋯S interactions to be between the orbital occupied by the lone pair electrons in each sulphur atom as a donor, and virtual orbitals consisting of S–C σ*, S–Re σ*, and S–C π* states on the acceptor sulphur atom. The binding energy of the dimer was explicitly computed to be 8.14 kcal/mol.
Description: This is the final draft, after peer-review, of a manuscript published in Journal of Organometallic Chemistry. The published version is available online at http://dx.doi.org/10.1016/j.jorganchem.2015.04.046
URI: http://hdl.handle.net/10497/17747
ISSN: 0022-328X
Other Identifiers: 10.1016/j.jorganchem.2015.04.046
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