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[Display omitted] • Five novel rhenium(I) complexes were synthesized. • All complexes were characterized fully by 1H NMR, FTIR, UV–Vis and X-ray diffraction. • A rare four-membered Re 2 Cl 2 bridging ring was observed. • The ligands all coordinated in a monodentate fashion. The reactivity of the rhenium(I) precursor fac -[Re(CO) 5 Cl] with various benzo-fused ligands were studied. 2-Aminobenzothiazole (abt), mercaptobenzimidazole (mbi), N -(1,3-benzothiazol-2-yl)-2-chloroacetamide (bct), ethyl-(1 H -benzimidazol-2-yl-sulfanyl)acetate (bsa) and (dibenzothiazol-2-yl)tetraazathiapentalene (dbt) were chosen as the ligands of interest, where all ligands coordinated in a monodentate mode. The novel complexes isolated were fully characterized, with abt, mbi and dbt (L) resulting in rhenium complexes of the type fac -[ReCl(L) 2 (CO) 3 ]. However, the ligands bct and bsa produced [ReCl(bct)(CO) 3 (NCMe)] and the bridged species (µ-Cl) 2 [Re(bsa)(CO) 3 ] respectively. [ABSTRACT FROM AUTHOR]

The reaction of pyrazole-benzothiazole hybrids towards [Re(CO) 5 Cl], trans -[ReOCl 3 (PPh 3) 2 ] and cis -[ReO 2 I(PPh 3) 2 ] were studied. The structures of the rhenium(I) and rhenium(V) complexes were determined by X-ray diffraction methods and confirmed spectroscopically. The reaction of the pyrazole-benzothiazole hybrids 2-(3,5-dimethylpyrazol-1-yl)benzothiazole (dmp) and 2-(2-benzothiazolyl)-4,5,6,7-tetrahydro-2 H -indazol-3-ol (Hbth) with [Re(CO) 5 Cl] resulted in the formation of neutral complexes with the general formula [ReCl(CO) 3 (HL)] (HL = dmp (1), Hbth (2)). 1-(Benzo[ d ]thiazol-2-yl)-4-methyl-1 H -pyrrol-2-ol (Hbtm) gave the trimeric species [Re(btm)(CO) 3 ] 3 (3) by reaction with [Re(CO) 5 Cl]. Reaction with [ReVOCl 3 (PPh 3) 2 ] led to the isolation of the oxo-bridged dimeric compound (µ-O)[ReOCl 2 (dmp)] 2 (4) and [ReOCl(bth)(bth 1)] (5) [bth 1 = 2-(benzo[ d ]thiazol-2-yl)-1,2,4,5,6,7-hexahydro-3 H -indazol-3-one] by reaction with dmp and Hbth, respectively. The reactivity of Hbtm with trans -[ReOCl 3 (PPh 3) 2 ] in ethanol gave [ReOCl(btm)(btm 1)] (6) [btm 1 = 2-(benzo[ d ]thiazol-2-yl)-5-methyl-1,2-dihydro-3 H -pyrazol-3-one], whereas [ReOCl(btm 1)(btz)] (7) [btz = 1-(benzo[ d ]thiazol-2-yl)-4-(1-iminoethyl)-3-methyl-1 H -pyrazol-5ol] formed in acetonitrile using the same reactants. The rhenium(V) complexes [ReO(OMe)(btm)(btm 1)] (8) and [ReO(OEt) 0.96 (I) 0.04 (btm)(btm 1)] (9) were isolated upon reacting Hbtm with cis -[ReO 2 I(PPh 3) 2 ] in methanol and ethanol, respectively. The structures of complexes 1 – 9 were determined by X-ray diffraction methods and confirmed spectroscopically. [ABSTRACT FROM AUTHOR]