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Steric influence of salicylaldehyde-based Schiff base ligands on the formation of trans-[Re(PR3)2(Schiff base)]+ complexes

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Abstract

Complexes of the type trans-[Re(PR3)2(Schiff base)]+ (R = ethyl and/or phenyl) 2–7 were prepared by the reaction of (nBu4N)[ReOCl4] with H2sal2en or H2sal2ibn followed by addition of a tertiary phosphine. The trans-[Re(PR3)2(sal2en)]+ complexes 2–4 were stable in solution, whereas the trans-[Re(PR3)2(sal2ibn)]+ complexes 6–7 were observed to convert to their corresponding cis-[ReO(PR3)(sal2ibn)]+ products through a process involving ligand dissociation, metal oxidation, and Schiff base ligand rearrangement. The conversion of the trans-[Re(PR3)2(sal2ibn)]+ complexes is likely driven by steric interactions between the bulky backbone gem-dimethyl groups of the sal2ibn ligand and the phosphine ligands. These complexes were isolated and characterized by 1H and 13C NMR, FT-IR spectroscopy, cyclic voltammetry, and single crystal X-ray diffraction. The results reported herein provide insight into the factors that drive trans-[Re(PR3)2(Schiff base)]+ complex formation. This will aid in the development of novel 186/188Re therapeutic agents and the design of novel bifunctional N2O2 Schiff base ligands.

Graphical abstract: Steric influence of salicylaldehyde-based Schiff base ligands on the formation of trans-[Re(PR3)2(Schiff base)]+ complexes

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Publication details

The article was received on 21 Jun 2019, accepted on 02 Aug 2019 and first published on 08 Aug 2019


Article type: Paper
DOI: 10.1039/C9DT02630D
Dalton Trans., 2019, Advance Article

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    Steric influence of salicylaldehyde-based Schiff base ligands on the formation of trans-[Re(PR3)2(Schiff base)]+ complexes

    J. E. Baumeister, A. W. Mitchell, S. P. Kelley, C. L. Barnes and S. S. Jurisson, Dalton Trans., 2019, Advance Article , DOI: 10.1039/C9DT02630D

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