Chirality-Guided Isomerization of Mn₂S₂ Diamond Core Complexes: A Mechanistic Study

Occasioned by the discovery of a ligand transfer from M(N₂S₂) to Mn^I 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.