Selective synthesis and crystal structures of manganese(I) complexes with a bi- or tridentate terpyridine ligand

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.