Issue 3, 2024

A one-pot reduction route to bimetallic manganese 1,8-naphthyridine complexes

Abstract

Reaction of the dinucleating ligand 2,7-bis(6-methyl-2-pyridyl)-1,8-naphthyridine (MeL) with the MnI and MnII precursors MnBr(CO)5 and MnCl2 resulted in the formation of the monometallic complexes [MnBr(CO)3(MeL)] (1) and [MnCl2(MeL)] (3). In both cases, formation of bimetallic manganese complexes could be achieved by reduction with KC8, yielding the carbonyl-bridged complex [Mn2(CO)6(MeL)] (2) and the helicate complex [Mn2(MeL)2] (4), respectively. EPR results demonstrate that 4 represents a novel, weakly antiferromagnetically coupled homovalent dimer (J = −0.85 cm−1). The two formally Mn0 ions are both high spin (S = 3/2) and exhibit a zero-field splitting of ≈1 cm−1, suggesting reduction of the complex is substantially ligand centered, and may be better described as a MnII complex coupled to two open shell singlet ligands [MnII2(MeL2−)2]. X-ray crystallography, UV-Vis spectroscopy and DFT analysis support this finding.

Graphical abstract: A one-pot reduction route to bimetallic manganese 1,8-naphthyridine complexes

Supplementary files

Article information

Article type
Paper
Submitted
06 noy 2023
Accepted
12 dek 2023
First published
13 dek 2023

Dalton Trans., 2024,53, 1284-1294

A one-pot reduction route to bimetallic manganese 1,8-naphthyridine complexes

M. A. Stevens, L. F. Lim, L. N. Pham, N. Cox, M. L. Coote and A. L. Colebatch, Dalton Trans., 2024, 53, 1284 DOI: 10.1039/D3DT03709F

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