Synthesis of Re I I tricarbonyl complexes with various sulfur‐ and oxygen‐donating ligands: crystal structures of two Re I I dinuclear structures bridged by S atoms

摘要

The synthesis and characterization of two dinuclear complexes, namely fac ‐hexacarbonyl‐1κ 3 C ,2κ 3 C ‐(pyridine‐1κ N )[μ‐2,2′‐sulfanediyldi(ethanethiolato)‐1κ 2 S 1 , S 3 :2κ 3 S 1 , S 2 , S 3 ]dirhenium(I), [Re 2 (C 4 H 8 S 3 )(C 5 H 5 N)(CO) 6 ], ( 1 ), and tetraethylammonium fac ‐tris(μ‐2‐methoxybenzenethiolato‐κ 2 S : S )bis[tricarbonylrhenium(I)], (C 8 H 20 N)[Re 2 (C 7 H 7 OS) 3 (CO) 6 ], ( 2 ), together with two mononuclear complexes, namely (2,2′‐bithiophene‐5‐carboxylic acid‐κ 2 S , S ′)bromidotricarbonylrhenium(I), ( 3 ), and bromidotricarbonyl(methyl benzo[ b ]thiophene‐2‐carboxylate‐κ 2 O , S )rhenium(I), ( 4 ), are reported. Crystals of ( 1 ) and ( 2 ) were characterized by X‐ray diffraction. The crystal structure of ( 1 ) revealed two Re—S—Re bridges. The thioether S atom only bonds to one of the Re I metal centres, while the geometry of the second Re I metal centre is completed by a pyridine ligand. The structure of ( 2 ) is characterized by three S‐atom bridges and an Re…Re nonbonding distance of 3.4879?(5)??, which is shorter than the distance found for ( 1 ) [3.7996?(6)/3.7963?(6)??], but still clearly a nonbonding distance. Complex ( 1 ) is stabilized by six intermolecular hydrogen‐bond interactions and an O…O interaction, while ( 2 ) is stabilized by two intermolecular hydrogen‐bond interactions and two O…π interactions.