Reactions of [Mn2(μ-pyS)2(CO)6] with bidentate N-donor ligands: Crystal structure of [Mn(η1-pyS)(bipy)(CO)3] (bipy = 2,2′-bipyridyl, pySH = pyridine-2-thiol)

The dimeric complex [Mn2(μ-pyS)2(CO)6] (1) reacted with 2 equivalents of 2,2′-bipyridyl (bipy), 1,10-phenanthroline (phen), and ethylenediamine (en) to give the corresponding monomeric complexes [Mn(η1-pyS)(bipy)(CO)3] (2), [Mn(η1-pyS)(phen)(CO)3] (3), and [Mn(η 1-pyS)(en)(CO)3] (4). The pyS ligand in these complexes acts as a monodentate, two-electron donor ligand, which coordinates to manganese through the sulfur atom. This is confirmed by an X-ray structure determination of 2, which contains two structural isomers in the asymmetric unit. Crystals of this compound are the monoclinic, space group P21/c, a = 21.593(4), b = 10.463(2), c = 16.385(3) Å, β = 102.468(13)°, V = 3614.5(12) Å3, and Z = 8. The three CO groups are facially distributed in both isomers, but the relative positions of the pyS and bipy ligands are different.