In:
Physical Chemistry Chemical Physics, Royal Society of Chemistry (RSC), Vol. 25, No. 12 ( 2023), p. 8507-8514
Abstract:
In a solution of sorbitol (SBT) and Ga(OTf) 3 compounds, the coordination of sorbitol (SBT) to [Ga(OTf) n ] 3− n ( n = 0–3) has been investigated, using both ESI-MS spectra and density functional theory (DFT) calculations at the M06/6-311++g(d,p), aug-cc-pvtz level using a polarized continuum model (PCM-SMD). In sorbitol solution, the most stable conformer of sorbitol includes three intramolecular H-bonds, i.e. , O2H⋯O4, O4H⋯O6, and O5H⋯O3. Through ESI-MS spectra, in a tetrahydrofuran solution of both SBT and Ga(OTf) 3 compounds, five main species are observed, i.e. , [Ga(SBT)] 3+ , [Ga(OTf)] 2+ , [Ga(SBT) 2 ] 3+ , [Ga(OTf)(SBT)] 2+ , and [Ga(OTf)(SBT) 2 ] 2+ . Through DFT calculations, in a solution of sorbitol (SBT) and Ga(OTf) 3 compounds, the Ga 3+ cation tends to form five six-coordination complexes, i.e. , [Ga(η2O,O-OTf) 3 ], [Ga(η3O2–O4-SBT) 2 ] 3+ , [(η2O,O-OTf)Ga(η4O2–O5-SBT)] 2+ , [(η1O-OTf)(η2O2,O4-SBT)Ga(η3O3–O5-SBT)] 2+ , and [(η1O-OTf)(η2O,O-OTf)Ga(η3O3–O5-SBT)] + , which are in good agreement with the experimental observation of the ESI-MS spectra. For both [Ga(OTf) n ] 3− n ( n = 1–3) and [Ga(SBT) m ] 3+ ( m = 1, 2) complexes, the negative charge transfer from ligands to the Ga 3+ -center plays an important role in their stability, because of the strong polarization of the Ga 3+ cation. For [Ga(OTf) n (SBT) m ] 3− n ( n = 1, 2; m = 1, 2) complexes, the negative charge transfer from ligands to the Ga 3+ -center plays an essential role in their stability, accompanied by an electrostatic interaction between the Ga 3+ -center and ligands and/or spatial inclusion of ligands toward the Ga 3+ -center.
Type of Medium:
Online Resource
ISSN:
1463-9076
,
1463-9084
Language:
English
Publisher:
Royal Society of Chemistry (RSC)
Publication Date:
2023
detail.hit.zdb_id:
1476283-3
detail.hit.zdb_id:
1476244-4
detail.hit.zdb_id:
1460656-2
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