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

Michael A. Stevens; Li Feng Lim; Le Nhan Pham; Nicholas Cox; Michelle L. Coote; Annie L. Colebatch

doi:10.1039/d3dt03709f

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

Michael A. Stevens, Li Feng Lim, Le Nhan Pham, Nicholas Cox, Michelle L. Coote, Annie L. Colebatch

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Abstract

Reaction of the dinucleating ligand 2,7-bis(6-methyl-2-pyridyl)-1,8-naphthyridine (^MeL) with the Mn^I and Mn^II 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 Mn^II complex coupled to two open shell singlet ligands [Mn^II₂(^MeL²⁻)₂]. X-ray crystallography, UV-Vis spectroscopy and DFT analysis support this finding.

Original language	English
Pages (from-to)	1284-1294
Number of pages	11
Journal	Dalton Transactions
Volume	53
Issue number	3
Early online date	13 Dec 2023
DOIs	https://doi.org/10.1039/d3dt03709f
Publication status	Published - 21 Jan 2024

Keywords

bimetallic transition metal complexes
manganese 1,8-naphthyridine
bimetallic manganese complexes

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title = "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.",

keywords = "bimetallic transition metal complexes, manganese 1,8-naphthyridine, bimetallic manganese complexes",

author = "Stevens, {Michael A.} and Lim, {Li Feng} and Pham, {Le Nhan} and Nicholas Cox and Coote, {Michelle L.} and Colebatch, {Annie L.}",

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T1 - A one-pot reduction route to bimetallic manganese 1,8-naphthyridine complexes

AU - Stevens, Michael A.

AU - Lim, Li Feng

AU - Pham, Le Nhan

AU - Cox, Nicholas

AU - Coote, Michelle L.

AU - Colebatch, Annie L.

PY - 2024/1/21

Y1 - 2024/1/21

N2 - 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.

AB - 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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KW - manganese 1,8-naphthyridine

KW - bimetallic manganese complexes

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

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