Affordable Access

deepdyve-link deepdyve-link
Publisher Website

Synthesis, characterization, and theoretical studies of metal complexes derived from the chiral tripyridyldiamine ligand Bn-CDPy3.

Authors
Type
Published Article
Journal
Inorganic Chemistry
1520-510X
Publisher
American Chemical Society
Publication Date
Volume
49
Issue
11
Pages
5202–5211
Identifiers
DOI: 10.1021/ic100322p
PMID: 20459127
Source
Medline
License
Unknown

Abstract

Synthesis and characterization of metal complexes of the chiral tripyridyldiamine ligand Bn-CDPy3 (1), derived from trans-1,2-diaminocyclohexane, are described, along with theoretical studies that support the experimental data. These studies confirm that a single coordination geometry, out of five possible, is favored for octahedral complexes of the type [M(Bn-CDPy3)Cl], where M equals Co(III), Fe(II), and Zn(II). A combination of X-ray crystallographic and NMR spectroscopic methods was used to define the structures of the complexes [Co(Bn-CDPy3)Cl]Cl(2) (5), [Fe(Bn-CDPy3)Cl]X (X = FeCl(4), Cl, ClO(4), 6-8), and [Zn(Bn-CDPy3)Cl](2)ZnCl(4) (9) in the solid state and in solution. Experimental and theoretical data indicate that the most stable coordination geometry for all complexes possesses the Cl group trans to a basic amine donor and three pyridyl donors adopting the mer geometry, with two pyridyl N-donors adopting a coplanar geometry with respect to the M-Cl bond and the third pyridyl donor perpendicular to that axis. Calculations indicate that the ability to favor a single geometry is born from the chiral ligand, which prefers to be in a single conformation in metal complexes due to steric interactions and electronic factors. Calculated structures of the complexes were used to locate key interactions among the various diastereomeric complexes that are proposed to create an energetic preference for the coordination geometry observed in the metal complexes of 1.

Statistics

Seen <100 times