Show simple item record

dc.contributor.authorStokes, Francesca Aen
dc.contributor.authorKloo, Larsen
dc.contributor.authorHarford, Philip Jen
dc.contributor.authorPeel, Andrewen
dc.contributor.authorLess, Robert Jen
dc.contributor.authorWheatley, Andrewen
dc.contributor.authorWright, Dominicen
dc.date.accessioned2014-07-25T10:23:37Z
dc.date.available2014-07-25T10:23:37Z
dc.date.issued2014-07-10en
dc.identifier.citationAustralian Journal of Chemistry 67(7) 1081-1087. DOI: http://dx.doi.org/10.1071/CH14271en
dc.identifier.issn0004-9425
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/245571
dc.description.abstractReactions of Cp2M (Cp = cyclopentadienyl, M = Mn, Ni) with lithium amidinates and guanidinates are reported. The highly oxophilic nature of Mn leads to the isolation of the interstitial oxide Mn4O(MeN···CH···NMe)6 (4) in preference to the intended paddle-wheel homodimer Mn2(MeN···CH···NMe)4 when employing the sterically uncongested amidinate [MeN···CH···NMe]– ligand. In contrast, an analogous reaction using Cp2Ni yielded Ni2(MeN···CH···NMe)4 (5). The use of monoprotic guanidinate ligands also gave contrasting results for Mn and Ni. In the first case, the highly unusual spirocycle Mn{μ-NC(NMe2)2}4Li2·3THF (6) was produced in low yield. For M = Ni, use of the [hpp]– (1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinate) ligand gives results comparable with the synthesis of 5, with Ni2(hpp)4 (7) isolated. In contrast to recent data obtained using Cp2Cr, the guanidinate ligands do not sequester coformed CpLi. Density functional theory analysis corroborates the view that the intermetal distance in each of the reported dinickel paddle-wheel complexes (2.4846(8) and 2.3753(5) Å in 5 and 7 respectively) is defined by the geometric parameters of the bidentate ligands and that intermetal bonding is not present.
dc.description.sponsorshipThis work was supported by the Engineering and Physical Sciences Research Council [grant number EP/P504856/1] and the Leverhulme Trust.
dc.languageEnglishen
dc.language.isoenen
dc.publisherCSIRO Publishing
dc.titleTowards the Synthesis of Guanidinate- and Amidinate-Bridged Dimers of Mn and Nien
dc.typeArticle
dc.provenanceOA-1080
dc.description.versionThis is the accepted manuscript. The final published version is available at http://www.publish.csiro.au/?paper=CH14271.en
prism.endingPage1087
prism.publicationDate2014en
prism.publicationNameAustralian Journal of Chemistryen
prism.startingPage1081
prism.volume67en
dc.rioxxterms.funderEPSRC
dc.rioxxterms.projectidEP/P504856/1
rioxxterms.versionofrecord10.1071/CH14271en
rioxxterms.licenseref.urihttp://www.rioxx.net/licenses/all-rights-reserveden
rioxxterms.licenseref.startdate2014-07-10en
dc.contributor.orcidPeel, Andrew [0000-0003-4690-5019]
dc.contributor.orcidWheatley, Andrew [0000-0002-2624-6063]
dc.contributor.orcidWright, Dominic [0000-0002-9952-3877]
dc.identifier.eissn1445-0038
rioxxterms.typeJournal Article/Reviewen


Files in this item

Thumbnail

This item appears in the following Collection(s)

Show simple item record