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Two rhenium complexes, namely, fac-tricarbonyl(triphenylphosphane-κP)(tropolonato-κ 2 O,O')rhenium(I), [Re(C 7 H 5 O 2 )(C 18 H 15 P)(CO) 3 ] or fac-[Re(Trop)(PPh 3 )(CO) 3 ] (1), and fac-tricarbonyl(3,5,7-tribromotropolonato-κ 2 O,O')(triphenylphosphane-κP)rhenium(I), [Re(C 7 H 2 Br 3 O 2 )(C 18 H 15 P)(CO) 3 ] or fac-[Re(TropBr 3 )(PPh 3 )(CO) 3 ] (2) (TropH is tropolone and and TropBr 3 H is tribromotropolone), were synthesized and their crystal and molecular structures confirmed by single-crystal X-ray diffraction. Both crystallized in the space group P-1 and display an array of inter- and intramolecular interactions which were confirmed by solid-state 13 C NMR spectroscopy using cross polarization magic angle spinning (CPMAS) techniques, as well as Hirshfeld surface analysis. The slightly longer Re-P distance of 1 [2.4987 (5) versus 2.4799 (11) Å for 1 and 2, respectively] suggests stronger back donation from the carbonyl groups in the former case, possibly due to the stronger electron-donating ability of the unsubstituted tropolonate ring system. However, this is not supported in the Re-CO bond distances of 1 and 2., (open access.)

The synthesis and characterization of two dinuclear complexes, namely fac-hexacarbonyl-1κ 3 C,2κ 3 C-(pyridine-1κN)[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) 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 O...O interaction, while (2) is stabilized by two intermolecular hydrogen-bond interactions and two O...π interactions.