A one-pot reduction route to bimetallic manganese 1,8-naphthyridine complexes
Michael A Stevens1, Li Feng Lim1, Le Nhan Pham2
1Research School of Chemistry, Australian National University, Canberra, ACT, 2601, Australia. annie.colebatch@anu.edu.au.
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.
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