Synthesis of Re^Itricarbonyl complexes with various sulfur- and oxygen-donating ligands: crystal structures of two Re^Idinuclear structures bridged by S atoms

Abstract

The synthesis and characterization of two dinuclear complexes, namely fachexacarbonyl-1 3 C,2 3 C-(pyridine-1N)[-2,2 0 -sulfanediyldi(ethanethiolato)-1 2 S 1 ,S 3 :2 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(-2-methoxybenzenethiolato-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 0 -bithiophene-5-carboxylic acid-2 S,S 0 )bromidotricarbonylrhenium(I), (3), and bromidotricarbonyl(methyl benzo[b]thiophene-2-carboxylate-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 ReÁ Á ÁRe nonbonding distance of 3.4879 (5) Å , which is shorter than the distance found for (1) [3.7996 (6)/3.7963 (6) Å ], but still clearly a nonbonding distance. Complex (1) is stabilized by six intermolecular hydrogen-bond interactions and an OÁ Á ÁO interaction, while (2) is stabilized by two intermolecular hydrogen-bond interactions and two OÁ Á Á interactions.

Alkyl 2-Benzothiazolyl Sulfide Ligated Dirhenium Complexes: Syntheses, Structure and Computational Study of [Re2(CO)8{μ,η1,η1-(R)SCNSC6H4}] (R = CH3 and C2H5)

“…For example, the reactions of Re2(CO)10 with pyridine-2-thiol [1], thioacetamide [2], thiobenzamide [2], diaryl disulfides [3], pyrimidine-2-thiol [4], 2-mercaptothiazoline [5], 2mercaptobenzimidazole [5], 2-mercapto-1-methylimidazole [5], and 2-mercaptobenzoxazole [6] have been reported. Recent advances in research reveal the isolation of mixed metal [7][8][9] and mixed ligand [10][11][12][13] rhenium complexes of sulfur-containing ligands. These reactions often involve the oxidative cleavage of the rhenium-rhenium bond together with the reductive S─H, N─H or S─S bond scission in the ligands [1][2][3][4][5][6].…”