Work

Iterative Mass Spectrometry and X-Ray Crystallography to Study Ion-Trapping and Rearrangements by a Flexible Cluster

Year: 2013

Type: article

Abstract: An important aspect of chemical reactions involves understanding the intermediate steps from reactants to products. The iterative use of mass spectrometry and X-Ray crystallography is demonstrated to be a powerful combination in this respect. We have applied them in identifying molecular clusters in solution followed by their solid-state structural characterizations. We used a key ligand, 2-[(2-hydroxy-3-methoxy-benzylidene)-amino]-ethanesulfonate (L), which serves as chelating/bridging units to stabilize the precursor [Li₄Ni₆(OH)₂(L)₆(CH₃CN)₆](ClO₄)₂·4CH₃CN. The results of subsequent reactions witness a cascade of processes involving fragmentation, inner bridging ligand substitution (OH⁻ to OCH₃⁻), changing modes of binding (chelate to monodentate) of the key ligand, ion-trapping and exchange (Li⁺, Na⁺ and Ca²⁺) and their site preferences, coordinating and non-coordinating solvents (CH₃CN to CH₃OH, H₂O and EtOH) replacement. The flexibility of the Ni₃OL₃ species in solution permits the formation of six derivatives. The complimentary techniques open a broader prospect for cluster design and applications.

Source: Scientific Reports

DOI: 10.1038/srep03516

Authors: Kun Zhang, Mohamedally Kurmoo, Lian-Qiang Wei, Ming-Hua Zeng