Examination of the Coordination Sphere of AlIII in Trifluoromethyl-Heteroarylalkenolato Complex Ions by Gas-Phase IRMPD Spectroscopy and Computational Modelling

TitleExamination of the Coordination Sphere of AlIII in Trifluoromethyl-Heteroarylalkenolato Complex Ions by Gas-Phase IRMPD Spectroscopy and Computational Modelling
Publication TypeJournal Article
Year of Publication2012
AuthorsL. Bruckmann, W. Tyrra, S. Mathur, G. Berden, J. Oomens, A Meijer, M. Schafer
JournalChemphyschem
Volume13
Number8
Pagination2037-2045
Date PublishedJun
Type of ArticleArticle
ISBN Number1439-4235
KeywordsACIDS, action spectroscopy, aluminium(III) complexes, ALUMINUM, ALZHEIMERS-DISEASE, computational chemistry, CONFORMATION, coordination modes, GAS-PHASE, infrared, infrared multiphoton dissociation spectroscopy, mass, METAL CATION SIZE, MULTIPHOTON DISSOCIATION SPECTROSCOPY, SALT-BRIDGE STRUCTURES, spectrometry, TANDEM MASS-SPECTROMETRY, ZWITTERION STABILITY
Abstract

A series of aluminium complex ions with trifluoromethyl-heteroarylalkenolato (TMHA) ligands are studied by gas-phase infrared multiphoton-dissociation (IRMPD) spectroscopy and computational modelling. The selected series of aluminium TMHA complex ions are promising species for the initial study of intrinsic binding characteristics of AlIII cations in the gas phase as corresponding molecular ions. They are readily available for examination by (+) and (-) electrospray ionization mass spectrometry (ESI-MS) by spraying of [Al3+center dot(L-)3] solutions. The complex ions under investigation contain trivalent Al3+ cations with two chelating anionic enolate ligands, [Al3+center dot(L-)2]+, providing insights in the nature of the heteroatom-Al bonds. Additionally, the structure of a deprotonated benzimidazole ligand, L-, and an anionic complex ion of AlIII with two doubly deprotonated benzimidazole ligands, [Al3+center dot(L2-)2]-, are examined by (-)ESI-IRMPD spectroscopy. Experimental and computational results are highly consistent and allow a reliable identification of the ion structures. In all complex ions examined the planar TMHA ligands are oriented perpendicular to each other around the metal ion, leading to a tetrahedral coordination sphere in which aluminium interacts with the enolate oxygen and heteroaryl nitrogen atoms available in each of the bidentate ligands.

URLhttp://onlinelibrary.wiley.com/doi/10.1002/cphc.201200132/abstract;jsessionid=B3183BE25FCDD07A5C25CA9B70F70519.f04t03
DOI10.1002/cphc.201200132
Division

GUTHz

Department

Moldyn

PID

b9563fd17a05de574bcaf468c9874629

Alternate TitleChemPhysChem

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