Towards rational syntheses of the elusive metallocarbohedrenes: Density functional prescriptions for electronic and geometric structures

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dc.contributor.authorDance, I.
dc.contributor.authorWenger, E.
dc.contributor.authorHarris, H.
dc.date.issued2002
dc.descriptionCopyright © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
dc.description.abstractThe metallocarbohedrenes are binary molecular clusters containing metal atoms linked by acetylenediide C2 groups. Hundreds of these molecules have been generated, detected and reacted in the gas phase since the prototype, [Ti8(C2)6], was reported in 1992, but none has yet been synthesised pure in bulk: the time gap between detection and preparation increasingly exceeds that of the fullerenes. We report here the results of density functional calculations of geometrical and electronic structure of more than 150 postulated metallocarbohedrenes, stabilised by terminal ligation, in order to recognise the more electronically favourable and less reactive targets. At least 38 metallocarbohedrenes have been identified as having a spin singlet ground state, with a relatively large (> 0.5 eV) energy gap between HOMO and LUMO, and an appropriate HOMO energy. In addition, a considerable number of electronically stable metallocarbohedrenes are predicted to have highly paramagnetic ground states, potentially useful in molecular magnetism. The geometrical principles for enclosing but unstrained coordination of metal sites by terminal ligands are outlined. Mechanisms for rational syntheses are considered in the context of reaction type and precursor selection, including issues of oxidation and reduction, and kinetic versus thermodynamic control. This leads to many diverse reactions suggested for the rational syntheses of metallocarbohedrenes. Some preliminary experimental results are presented.
dc.description.statementofresponsibilityIan Dance, Eric Wenger, Hugh Harris
dc.identifier.citationChemistry - A European Journal, 2002; 8(15):3497-3511
dc.identifier.doi10.1002/1521-3765(20020802)8:15<3497::AID-CHEM3497>3.0.CO;2-W
dc.identifier.issn0947-6539
dc.identifier.issn1521-3765
dc.identifier.orcidHarris, H. [0000-0002-3472-8628]
dc.identifier.urihttp://hdl.handle.net/2440/47114
dc.language.isoen
dc.publisherWiley-V C H Verlag GMBH
dc.source.urihttp://www3.interscience.wiley.com/journal/97516119/abstract
dc.subjectcluster compounds
dc.subjectdensity functional calculations
dc.subjectelectronic structure
dc.subjectgeometric structure
dc.subjectligands
dc.subjectmetallocarbohedrenes
dc.subjectsynthesis design
dc.titleTowards rational syntheses of the elusive metallocarbohedrenes: Density functional prescriptions for electronic and geometric structures
dc.typeJournal article
pubs.publication-statusPublished

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