Molecular Wheels of Ruthenium and Osmium with Bridging Chalcogenolate Ligands: Edge‐Shared‐Octahedron Structures and Metal‐Ion Binding

Inventing new wheels : Reaction of [M 3 (CO) 12 ] (M=Ru, Os) with 4‐RC 6 H 4 SH afforded [{M(S‐4‐RC 6 H 4 ) 2 (CO) 2 } 8 ] (R=H; I ) or [{M(S‐4‐RC 6 H 4 ) 2 (CO) 2 } 6 ] (R=Me, i Pr; II ; see scheme), all of which have been structurally characterized. The octamers I are unique metal molecular wheels featuring skew‐edge‐shared octahedra with a central planar M 8 octagon. [{Ru(S‐4‐ i PrC 6 H 4 ) 2 (CO) 2 } 6 ] selectively binds a Cu + or Ag + ion to form [M′{Ru(S(4‐ i Pr‐C 6 H 4 )) 2 (CO) 2 } 6 ] + ( III ).