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dc.contributor.authorGarcía-Rodríguez, Raúlen
dc.contributor.authorWright, Dominicen
dc.date.accessioned2015-07-24T14:21:26Z
dc.date.available2015-07-24T14:21:26Z
dc.date.issued2015-08-25en
dc.identifier.citationChemistry: A European Journal 2015, 21(42), 14949–14957. doi: 10.1002/chem.201502156
dc.identifier.issn0947-6539
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/249070
dc.description.abstractIntroducing substituents in the 6-position of the 2-pyridyl rings of tris-pyridyl aluminate anions, of the type [EtAl(2-py´)3]- (py´ = a substituted 2-pyridyl group), has a large impact on their metal coordination characteristics. This is seen most remarkably in the desolvation of the THF solvate [EtAl(6-Me-2-py)3Li•THF] to give the monomer [EtAl(6-Me-2-py)3Li] (1), containing a pyramidal, three-coordinate Li+ cation. Similar monomeric complexes are observed for [EtAl(6-CF3-2-py)3Li] (2) and [EtAl(6-Br-2-py)3Li] (3), containing CF3 and Br substituents (R). This steric influence can be exploited in the synthesis of a new class of terminal Al-OH complexes, as is seen in the controlled hydrolysis of 2 and 3 to give [EtAl(OH)(6-R-2-py)2]- anions, as in the dimer [EtAl(OH)(6-Br-2-py)2Li]2 (5). Attempts to deprotonate the Al-OH group of 5 using Et2Zn led only to the formation of the zincate complex [LiZn(6-Br-py)3]2 (6), while reactions of the 6-Br substituted 3 and the unsubstituted complex [EtAl(2-py)3Li] with MeOH give [EtAl(OMe)(6-Br-2-py)2Li]2 (7) and [EtAl(OMe)(2-py)2Li]2 (8), respectively, having similar dimeric arrangements to 5. The combined studies presented here provide key synthetic tools for the functionalization and elaboration of tris-pyridyl aluminate ligands.
dc.description.sponsorshipWe thank the EU for a Marie Curie Intra European Fellowship within the seventh European Community Framework Programme for R.G.-R. and an Advanced Investigator Award for D.S.W.
dc.languageEnglishen
dc.language.isoenen
dc.publisherWiley
dc.titleSteric effects on the structures, reactivity and coordination chemistry of tris(2-pyridyl)aluminatesen
dc.typeArticle
dc.description.versionThis is the author accepted manuscript. The final version is available from Wiley via http://dx.doi.org/10.1002/chem.201502156en
prism.endingPage14957
prism.publicationDate2015en
prism.publicationNameChemistry: A European Journalen
prism.startingPage14949
prism.volume21en
rioxxterms.versionofrecord10.1002/chem.201502156en
rioxxterms.licenseref.urihttp://www.rioxx.net/licenses/all-rights-reserveden
rioxxterms.licenseref.startdate2015-08-25en
dc.contributor.orcidWright, Dominic [0000-0002-9952-3877]
dc.identifier.eissn1521-3765
rioxxterms.typeJournal Article/Reviewen
rioxxterms.freetoread.startdate2016-08-25


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