Counterion Dependent Coordination in Complexes of Divalent Group 12 Metals with Organic Ligand Tris[(6-methyl-2-pyridyl)methyl]amine

Complexes of type [M(TLA)Cln](ClO4)2-n (TLA = tris[(6-methyl-2-pyridyl)methyl]amine) have been isolated and characterized by X-ray crystallography and NMR for M = Zn, Cd, Hg and n= 1, 2. Across all three M, the metal-ligand binding motifs depend on n. When n = 1, TLA is tetradentate with all three of the pyridyl nitrogen binding sites coordinated to M. M is five or six coordinate, coordinated to four amines and one or two chlorides. When n = 2, one of the three pyridyl amines of TLA does not bind and the pyridyl ring is positioned away from the coordinated chlorides. M is five coordinate, coordinated to three nitrogen and two chlorine atoms. Crystalline structures are stabilized by offset face to face pi stacking. Despite coordination differences in crystal structures, solution state NMR suggests that complexes of n=1 and n=2 are similar in solution. This thesis expands understanding of group 12 metal coordination in varying chemical environments, with biological and crystallographic applications.

Publication Details

Journal
W&M Publish (College of William & Mary)
Published
2025-05-01
Primary Topic
Inorganic and Organometallic Chemistry
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article
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article

Counterion Dependent Coordination in Complexes of Divalent Group 12 Metals with Organic Ligand Tris[(6-methyl-2-pyridyl)methyl]amine

W&M Publish (College of William & Mary)
Inorganic and Organometallic Chemistry
article

Counterion Dependent Coordination in Complexes of Divalent Group 12 Metals with Organic Ligand Tris[(6-methyl-2-pyridyl)methyl]amine

article en

Abstract

Complexes of type [M(TLA)Cln](ClO4)2-n (TLA = tris[(6-methyl-2-pyridyl)methyl]amine) have been isolated and characterized by X-ray crystallography and NMR for M = Zn, Cd, Hg and n= 1, 2. Across all three M, the metal-ligand binding motifs depend on n. When n = 1, TLA is tetradentate with all three of the pyridyl nitrogen binding sites coordinated to M. M is five or six coordinate, coordinated to four amines and one or two chlorides. When n = 2, one of the three pyridyl amines of TLA does not bind and the pyridyl ring is positioned away from the coordinated chlorides. M is five coordinate, coordinated to three nitrogen and two chlorine atoms. Crystalline structures are stabilized by offset face to face pi stacking. Despite coordination differences in crystal structures, solution state NMR suggests that complexes of n=1 and n=2 are similar in solution. This thesis expands understanding of group 12 metal coordination in varying chemical environments, with biological and crystallographic applications.

W&M Publish (College of William & Mary)
Openalex Percentile: Top 47%
Inorganic and Organometallic Chemistry
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