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dc.contributor.author | Fraser, Roan![]() |
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dc.contributor.author | Van Rooyen, Petrus H.![]() |
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dc.contributor.author | Landman, Marile![]() |
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dc.date.accessioned | 2016-10-27T09:52:36Z | |
dc.date.issued | 2016-09 | |
dc.description.abstract | Homo- and heteronuclear bimetallic carbene complexes of group VII transition metals (Mn and Re), with cymantrene or cyclopentadienyl rhenium tricarbonyl as the starting synthon, have been synthesized according to classic Fischer methodology. Crystal structures of the carbene complexes with general formula [RC5 H4 M'(CO)2 {C(OEt)(C5 H4 M(CO)3 )}], where M = M′ = Mn, R = H (1), R = Me (2); M = Mn, M′ = Re, R = H (3); M = M′ = Re, R = H (4); and M = Re, M′ = Mn, R = H (5), are reported. A density functional theory (DFT) study was undertaken to determine natural bonding orbitals (NBOs) and conformational as well as isomeric aspects of the binuclear complexes. Application of second-order perturbation theory (SOPT) of the NBO method revealed stabilizing interactions between the methylene C–H bonds and the carbonyl ligands of the carbene metal moiety. Energy calculations in the gas phase of the cis and trans conformations of the Cp rings relative to one another are comparable, with the trans conformation slightly lower in energy. The theoretical findings have also been confirmed with single-crystal X-ray diffraction, and all solid-state structures are found in the trans geometry. | en_ZA |
dc.description.department | Chemistry | en_ZA |
dc.description.embargo | 2017-09-30 | |
dc.description.librarian | hb2016 | en_ZA |
dc.description.sponsorship | The South African National Research Foundation [grant number 93638] and the University of Pretoria. | en_ZA |
dc.description.uri | http://www.tandfonline.com/loi/gcoo20 | en_ZA |
dc.identifier.citation | Roan Fraser, Petrus H. Van Rooyen & Marilé Landman (2016) Conformational preferences of heteronuclear Fischer carbene complexes of cymantrene and cyclopentadienyl rhenium tricarbonyl, Journal of Coordination Chemistry, 69:19, 2972-2987, DOI: 10.1080/00958972.2016.1227071. | en_ZA |
dc.identifier.issn | 0095-8972 (print) | |
dc.identifier.issn | 1029-0389 (online) | |
dc.identifier.other | 10.1080/00958972.2016.1227071 | |
dc.identifier.uri | http://hdl.handle.net/2263/57528 | |
dc.language.iso | en | en_ZA |
dc.publisher | Taylor and Francis | en_ZA |
dc.rights | © 2016 Informa UK Limited, trading as Taylor & Francis Group. This is an electronic version of an article published in Journal of Coordination Chemistry, vol. 69, no. 19, pp. 2972-2987, 2016. doi : 10.1080/00958972.2016.1227071. Journal of Coordination Chemistry is available online at : http://www.tandfonline.com/loi/gcoo20. | en_ZA |
dc.subject | Fischer carbene | en_ZA |
dc.subject | Cymantrenyl | en_ZA |
dc.subject | Cyclopentadienyl rhenium tricarbonyl | en_ZA |
dc.subject | Density functional theory (DFT) | en_ZA |
dc.subject | Second-order perturbation theory (SOPT) | en_ZA |
dc.subject | Natural bonding orbitals (NBOs) | en_ZA |
dc.title | Conformational preferences of heteronuclear Fischer carbene complexes of cymantrene and cyclopentadienyl rhenium tricarbonyl | en_ZA |
dc.type | Postprint Article | en_ZA |