The First Heterobimetallic Metallasilsesquioxane Derivatives of Manganese

The reaction of ( c ‐C 6 H 11 ) 7 Si 7 O 9 (ONa) 3 , prepared in situ from ( c ‐C 6 H 11 ) 7 Si 7 O 9 (OH) 3 ( 1 ), and MnCl 2 (THF) 2 in THF solution resulted in formation of the novel heterobimetallic Mn/Na metallasilsesquioxane complex [( c ‐C 6 H 11 ) 7 Si 7 O 9 (O 3 Mn)Na(Et 2 O)] 2 ·Et 2 O ( 2 ) which was isolated in the form of colorless crystals in 64 % yield. Similar treatment of MnCl 2 (THF) 2 with in situ prepared ( c ‐C 6 H 11 ) 7 Si 7 O 9 (OLi) 3 afforded the unusual tetramanganese silsesquioxane complex [( c ‐C 6 H 11 ) 7 Si 7 O 9 (O 3 Mn 2 Br)LiBr(THF)(Et 2 O)] 2 ( 3 ) in high yield (81 %). Both 2 and 3 were structurally characterized by single‐crystal X‐ray diffraction.