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

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.

SUBMITTER: Wadayama K

PROVIDER: S-EPMC7336785 | biostudies-literature | 2020 Jul

REPOSITORIES: biostudies-literature

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

Wadayama Kosei K Takase Tsugiko T Oyama Dai D

Acta crystallographica. Section E, Crystallographic communications 20200626 Pt 7

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)<sub ...[more]

PMID: 32695468

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Project description:We have used x-ray crystallography to determine the structures of sperm whale myoglobin (Mb) in four different ligation states (unligated, ferric aquomet, oxygenated, and carbonmonoxygenated) to a resolution of better than 1.2 A. Data collection and analysis were performed in as much the same way as possible to reduce model bias in differences between structures. The structural differences among the ligation states are much smaller than previously estimated, with differences of <0.25 A root-mean-square deviation among all atoms. One structural parameter previously thought to vary among the ligation states, the proximal histidine (His-93) azimuthal angle, is nearly identical in all the ferrous complexes, although the tilt of the proximal histidine is different in the unligated form. There are significant differences, however, in the heme geometry, in the position of the heme in the pocket, and in the distal histidine (His-64) conformations. In the CO complex the majority conformation of ligand is at an angle of 18 +/- 3 degrees with respect to the heme plane, with a geometry similar to that seen in encumbered model compounds; this angle is significantly smaller than reported previously by crystallographic studies on monoclinic Mb crystals, but still significantly larger than observed by photoselection. The distal histidine in unligated Mb and in the dioxygenated complex is best described as having two conformations. Two similar conformations are observed in MbCO, in addition to another conformation that has been seen previously in low-pH structures where His-64 is doubly protonated. We suggest that these conformations of the distal histidine correspond to the different conformational substates of MbCO and MbO(2) seen in vibrational spectra. Full-matrix refinement provides uncertainty estimates of important structural parameters. Anisotropic refinement yields information about correlated disorder of atoms; we find that the proximal (F) helix and heme move approximately as rigid bodies, but that the distal (E) helix does not.

Dataset Information

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

Publications

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

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