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dc.contributor.authorSlaughter, Jonathanen
dc.contributor.authorPeel, Andrewen
dc.contributor.authorWheatley, Andrewen
dc.date.accessioned2017-01-20T16:31:48Z
dc.date.available2017-01-20T16:31:48Z
dc.date.issued2017-01-01en
dc.identifier.issn0947-6539
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/261949
dc.description.abstractIn investigating and seeking to mimic the reactivity of trimethylaluminium (TMA) with synthetic, ester-based lubricating oils, the reaction of methyl propionate $\textbf{1}$ was explored with 1, 2 and 3 equivalents of the organoaluminium reagent. Spectroscopic analysis points to the formation of the adduct $\textbf{1}$ (TMA) accompanied only by the low level 1:1 production of Me$_{2}$AlOCEtMe$_{2}$ $\textbf{2}$ and Me$_{2}$AlOMe $\textbf{3}$ when an equimolar amount of TMA is applied. The deployment of excess TMA favours reaction to give $\textbf{2}$ and $\textbf{3}$ over $\textbf{1}$(TMA) adduct formation and spectroscopy reveals that in hydrocarbon solution substitution product $\textbf{2}$ traps unreacted TMA to yield $\textbf{2}$(TMA). The $^{1}$H NMR spectroscopic observation of two Al-Me signals not attributable to free TMA and in the ratio 1:4 suggests the formation of a previously only postulated, symmetrical metallacycle in Me$_{4}$Al$_{2}$ (μ$^{2}$-Me)(μ$^{2}$-OCEtMe$_{2}$ ). In the presence of $\textbf{3}$, $\textbf{2}$(TMA) undergoes thermally induced exchange to yield Me$_{4}$Al$_{2}$(μ$^{2}$-OMe)(μ$^{2}$-OCEtMe$_{2}$) $\textbf{4}$ and TMA. The reaction of methyl phenylacetate $\textbf{5}$ with TMA allows isolation of the crystalline product Me$_{2}$AlOCBnMe$_{2}$ (TMA) $\textbf{6}$(TMA), which allows the first observation of the Me$_{}$ Al$_{2}$(μ$^{2}$-Me)(μ$^{2}$-OR) motif in the solid state. Distances of 2.133(3) Å (Al-Me$_{bridging}$) and 1.951 Å (mean Al-Me$_{terminal}$) are recorded. The abstraction of TMA from $\textbf{6}$(TMA) by the introduction of Et$_{2}$O has yielded $\textbf{6}$, which exists as a dimer.
dc.description.sponsorshipThis work was supported by Cambridge Refrigeration Technology (J.S.). The U.K. EPSRC are acknowledged for grant EP/J500380/1 (A.J.P.).
dc.languageengen
dc.language.isoenen
dc.publisherWiley
dc.rightsAttribution 4.0 Internationalen
dc.rightsAttribution 4.0 Internationalen
dc.rightsAttribution 4.0 Internationalen
dc.rightsAttribution 4.0 Internationalen
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.subjectestersen
dc.subjectNMR spectroscopyen
dc.subjectnucleophilic additionen
dc.subjectsolid-state structuresen
dc.subjecttrimethylaluminiumen
dc.titleReactions of Trimethylaluminium: Modelling the Chemical Degradation of Synthetic Lubricantsen
dc.typeArticle
prism.endingPage175
prism.issueIdentifier1en
prism.publicationDate2017en
prism.publicationNameChemistry - A European Journalen
prism.startingPage167
prism.volume23en
dc.identifier.doi10.17863/CAM.7182
dcterms.dateAccepted2016-10-28en
rioxxterms.versionofrecord10.1002/chem.201604553en
rioxxterms.versionVoRen
rioxxterms.licenseref.urihttp://creativecommons.org/licenses/by/4.0/en
rioxxterms.licenseref.startdate2017-01-01en
dc.contributor.orcidPeel, Andrew [0000-0003-4690-5019]
dc.contributor.orcidWheatley, Andrew [0000-0002-2624-6063]
dc.identifier.eissn1521-3765
rioxxterms.typeJournal Article/Reviewen
pubs.funder-project-idEPSRC (EP/K039520/1)
cam.issuedOnline2016-12-05en
datacite.issupplementedby.doi10.17863/CAM.6118en
cam.orpheus.successThu Jan 30 10:20:25 GMT 2020 - The item has an open VoR version.*
rioxxterms.freetoread.startdate2100-01-01


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Attribution 4.0 International
Except where otherwise noted, this item's licence is described as Attribution 4.0 International