| Abstract: | The ability of the tetraaza‐dithiophenolate ligand H2L2 (H2L2 = N,N′‐Bis‐[2‐thio‐3‐aminomethyl‐5‐tert‐butyl‐benzyl]propane‐1,3‐diamine) to form dinuclear chromium(III) complexes has been examined. Reaction of CrIICl2 with H2L2 in methanol in the presence of base followed by air‐oxidation afforded cis,cis‐[(L2)CrIII2(μ‐OH)(Cl)2]+ ( 1a ) and trans,trans‐[(L2)CrIII2(μ‐OH)(Cl)2]+ ( 1b ). Both compounds contain a confacial bioctahedral N2ClCrIII(μ‐SR)2(μ‐OH)CrIIIClN2 core. The isomers differ in the mutual orientation of the coligands and the conformation of the supporting ligand. In 1a both Cl? ligands are cis to the bridging OH function. In 1b they are in trans‐positions. Reaction of the hydroxo‐bridged complexes with HCl yielded the chloro‐bridged cations cis,cis‐[(L2)CrIII2(μ‐Cl)(Cl)2]+ ( 2a ) and trans,trans‐[(L2)CrIII2(μ‐Cl)(Cl)2]Cl ( 2b ), respectively. These bridge substitutions proceed with retention of the structures of the parent complexes 1a and 1b . |
