Abstract
The crystal structures of two manganese(I) complexes with a different coordination mode of the supporting ligand are reported: fac-bromido-tricarbon-yl(4'-phenyl-2,2':6',2''-terpyridine-κ2 N,N')manganese(I), [MnBr(C21H15N3)(CO)3], I, and cis-bromido-dicarbon-yl(4'-phenyl-2,2':6',2''-terpyridine-κ3 N,N',N'')manganese(I), [MnBr(C21H15N3)(CO)2], II. In both complexes, the manganese(I) atom is coordinated by terminal carbonyl ligands, a bromide ion, and a 4'-phenyl-2,2':6',2''-terpyridine ligand within a distorted octa-hedral environment. In I, the metal ion is facially coordinated by three carbonyl ligands and the terpyridine ligand binds in a bidentate fashion. The non-coordinating nitro-gen atom in the terpyridine ligand is positioned on the side opposite to the bromido ligand. In II, the metal ion is coordinated by two carbonyl ligands in a cis configuration and the terpyridine ligand binds in a tridentate fashion; notably, one carbonyl and the trans bromido ligand are mutually disordered over two positions. In I, the complex mol-ecules are linked by C-H⋯Br hydrogen bonds. In II, aromatic π-π contacts are present, as well as pairs of C-H⋯Br and C-H⋯O hydrogen bonds.
Highlights
The crystal structures of two manganese(I) complexes with a different coordination mode of the supporting ligand are reported: fac-bromidotricarbonyl(40phenyl-2,20:60,200-terpyridine-2N,N0)manganese(I), [MnBr(C21H15N3)(CO)3], I, and cis-bromidodicarbonyl(40-phenyl-2,20:60,200-terpyridine-3N,N0,N00)manganese(I), [MnBr(C21H15N3)(CO)2], II
In I, the metal ion is facially coordinated by three carbonyl ligands and the terpyridine ligand binds in a bidentate fashion
In II, the metal ion is coordinated by two carbonyl ligands in a cis configuration and the terpyridine ligand binds in a tridentate fashion; notably, one carbonyl and the trans bromido ligand are mutually disordered over two positions
Summary
Carbonylmanganese(I) complexes with polypyridyl ligands are of particular interest as novel active molecules that are able to release CO in response to photoirradiation (Carrington et al, 2013; Chakraborty et al, 2014; Jimenez et al, 2015) or as electrocatalysts of CO2 reduction (Grills et al, 2018; Stanbury et al, 2017) Among these compounds, studies have concentrated mainly on tricarbonyl complexes comprising bidentate polypyridyl supporting ligands; by contrast, only few reports exist on dicarbonyl complexes bearing tridentate ligands (Compain et al, 2015; Machan & Kubiak, 2016). As indicated by the results of studies focusing on the comparison between carbonylmanganese complexes containing bidentate and tridentate terpyridines (Compain et al, 2015; Machan & Kubiak, 2016), investigating the relationship between reactivity and molecular structure is a key research objective.
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