A series of [(TmM)-M-Me(A-Cl)]2 and TmRMCl( Tm-R) = tris( mercaptoimidazolyl) borate; R) Me, Bu-t, Ph, 2,6- (Pr2C6H3)-Pr-i ( Ar); M) Mn, Fe, Co, Ni) complexes have been prepared by treatment of NaTmMe or LiTmR with an excess amount of metal(II) chlorides, MCl2. Treatment of TmRMCl ( R) tBu, Ph, Ar) with NaI led to a halide exchange to afford (TmMI)-M-R. The molecular structures of [ (TmM)-M-Me( A- Cl)](2) ( M) Mn, Ni), [ (TmNi)-Ni-Me( A- Br)](2), (TmMCl)-M-tBu ( M) Fe, Co), (TmMCl)-M-Ph ( M) Mn, Fe, Co, Ni), (TmMCl)-M-Ar ( M) Mn, Fe, Co, Ni), (TmMI)-M-Ph (M) Mn, Co), and (TmMI)-M-Ar (M) Fe, Co, Ni) have been determined by X- ray crystallography. The Tm-R ligands occupy the tripodal coordination site of the metal ions, giving a square pyramidal or trigonal bipyramidal coordination geometry for [ TmMeM( A- Cl)](2) and a tetrahedral geometry for the (TmMCl)-Cl-R complexes, where the S - M - S bite angles are larger than the reported N - M - N angles of the corresponding hydrotris( pyrazolyl) borate ( Tp(R)) complexes. Treatment of (Tm2Fe)-Fe-Ph with excess FeCl2 affords TmPhFeCl, indicating that (Tm2M)-M-R as well as (TmMCl)-M-R is formed at the initial stage of the reaction between MCl2 and the Tm-R anion.