Towards Carbohydrate Derivatives of the Re I (CO) 3 Fragment

With the [Re(CO) 3 Br 3 ] 2− ion as a precursor for the Re I (CO) 3 fragment, the diols (1 R ,2 R )‐cyclohexane‐1,2‐diol [(1 R ,2 R )‐Chxd], anhydroerythritol (AnEryt), and (1 S ,2 S )‐cyclopentane‐1,2‐diol [(1 S ,2 S )‐Cptd] form dinuclear monoanions in the salts (NBu 4 )[(Re 2 (CO) 6 {μ‐(1 R ,2 R )‐ChxdH −1 } 3 ] ( 1 ), [K([18]crown‐6)][Re 2 (CO) 6 (μ‐OMe) 2 (μ‐AnErytH −1 )] ( 2 ) and (NBu 4 )[Re 2 (CO) 6 {μ‐(1 S ,2 S )‐CptdH −1 } 3 ] ( 3 ). The monoanionic diolato ligands in these triply bridged dirhenates( I ) are monodentate. Bridging triolato ligation in the trirhenates( I ) is supported by the anions of glycerol (Glyc) and methyl β‐ D ‐ribopyranoside (Me‐β‐ D ‐Rib p ), the latter binding in its 1 C 4 conformation, in (DBUH) 2 [Re 3 (CO) 9 (μ 3 ‐O)(μ 3 ‐GlycH −3 )]⋅0.5 MeCN ( 4 a ), (NEt 4 )[Re 3 (CO) 9 (μ 3 ‐OMe)(μ 3 ‐GlycH −3 )] ( 4 b ) and (DBUH)[Re 3 (CO) 9 (μ 3 ‐OMe)(μ 3 ‐ 1 C 4 ‐Me‐β‐ D ‐Rib p 2,3,4H −3 )] ( 5 ). The chiral sugar alcohols L ‐threitol ( L ‐Thre) and D ‐arabitol ( D ‐Arab) act as tetra‐ and pentadentate ligands, respectively, in (NEt 4 )[Re 2 (CO) 6 ( L ‐ThreH −3 )]⋅MeCN ( 6 ) and (NEt 4 ) 2 (DBUH) 2 [Re 6 (CO) 18 ( D ‐ArabH −5 ) 2 ] ( 7 ). Complexes 6 and 7 are free of supporting oxo or methoxo ligands and use solely the O‐atom pattern of the polyol for the connection of the Re I (CO) 3 moieties.