Lawrence Berkeley National Laboratory
Halide anion discrimination by a tripodal hydroxylamine ligand in gas and condensed phases.
- Author(s): Cheisson, Thibault
- Jian, Jiwen
- Su, Jing
- Eaton, Teresa M
- Gau, Michael R
- Carroll, Patrick J
- Batista, Enrique R
- Yang, Ping
- Gibson, John K
- Schelter, Eric J
- et al.
Published Web Locationhttps://doi.org/10.1039/c9cp03764k
Electrospray ionization of solutions containing a tripodal hydroxylamine ligand, H3TriNOx ([((2-tBuNOH)C6H4CH2)3N]) denoted as L, and a hydrogen halide HX: HCl, HBr and/or HI, yielded gas-phase anion complexes [L(X)]- and [L(HX2)]-. Collision induced dissociation (CID) of mixed-halide complexes, [L(HXaXb)]-, indicated highest affinity for I- and lowest for Cl-. Structures and energetics computed by density functional theory are in accord with the CID results, and indicate that the gas-phase binding preference is a manifestation of differing stabilities of the HX molecules. A high halide affinity of [L(H)]+ in solution was also demonstrated, though with a highest preference for Cl- and lowest for I-, the opposite observation of, but not in conflict with, what is observed in gas phase. The results suggest a connection between gas- and condensed-phase chemistry and computational approaches, and shed light on the aggregation and anion recognition properties of hydroxylamine receptors.