Occasioned by the discovery of a ligand transfer from M­(N2S2) to MnI in Mn­(CO)5Br, the resulting H2N2S2 ligand-tethered dimanganese complex, (μ4-N,N′-ethylenebis­(mercaptoacetamide))­[Mn2(CO)6], was found to have myriad analogues of the type (μ-S–E)2[Mn2(CO)6], making up an under-studied class containing Mn2S2 rhombs. The attempt to synthesize a nontethered version resulted in a solid-state structure in an anti-conformation. However, a direct comparison of the Fourier-transform infrared spectra of the tethered versus nontethered complexes in combination with theoretical frequency calculation suggested the coexistence of syn- and anti-isomers and their interconversion in solution. Analysis of the syn- versus anti-version of the dimanganese components led to the understanding that whereas the anti-form exists as centrosymmetric RS isomers, the syn-form is restricted by C2 symmetry to be either RR or SS. Molecular scrambling experiments indicated monomeric, pentacoordinate, 16-e– (S–O)­Mn­(CO)3 intermediates with lifetimes sufficiently long to sample R and S monomers. Density functional theory analysis of the mechanistic pathway and a kinetic study corroborated that the proposed isomerization involves the cleavage and reformation of the dimeric structures.