A series of rhenium(I) complexes with monodentate benzazole ligands containing the fac-[Re(CO)3]+ was synthesized. The rhenium(I) compound [ReCl(Hmbt)2(CO)3] was prepared from the reaction of [Re(CO)5Cl] and 2-aminobenzothiazole (Hmbt) in toluene. The ligand coordinates in a monodentate manner via the thiazole nitrogen atom. A similar reaction between [Re(CO)5Cl] and N-(1,3-benzothiazol-2-yl)-2- chloroacetamide (Hbct) resulted in the formation of [ReCl(Hbct)(CO)3(NCMe)], where only one ligand binds per rhenium in a monodentate fashion. The reaction of ligands 2-mercaptobenzimidazole (Hmbi) (dibenzothiazol-2-yl)tetraazathiapentalene (Hdbt) with rhenium(I) gave [ReCl(Hmbi)2(CO)3] and [ReCl(Hdbt)2(CO)3] respectively. The study on the coordination behaviour between ethyl-(1H-benzimidazol-2-yl-sulfanyl) acetate (Hbsa) and [Re(CO)5Cl] surprisingly gave the dimeric species (μ-Cl)2[Re(Hbsa)(CO)3]2, where the two rhenium atoms are bridged by two chloro ligands. The coordination of Hbsa occurs through the imidazole nitrogen, leaving the ethoxy tail free on each Hbsa ligand. The coordination behaviour of benzimidazole and benzothiazole derivatives gave rhenium complexes in oxidation states I, III and V, where all the ligands coordinate as bidentate N,N-chelating ligands. The study on 2-(2-aminophenyl)-1-benzothiazole (Hapt) and 2-(2-aminophenyl)-1-benzimidazole (H2apz) with [ReVOCl3(PPh3)2] resulted in the formation of [ReVOCl2(apt)(OPPh3)] and [ReVCl2(apz)(PPh3)2](ReO4), respectively. 1,2-Bis(2-benzimidazole)-1,2-ethanediol (Hbed) and 2,6-bis(2- benzimidazol-2-yl)pyridine (H2bip) were studied towards rhenium(I) and rheniumV) respectively. The former gave a dimeric species (μ-bbi)[Re(CO)4]2 (H2bbi – bisbenzimidazole) by reaction with [Re(CO)5Cl], whereas H2bip produced the rhenium(III) cationic salt [ReCl3(H3bip)(PPh3)]Cl, where the ligand coordinates as a cationic H3bip+ with protonation of an uncoordinated imidazole nitrogen atom. The pyridine derivatives 2-hydrazino-pyridinyl-2-benzothiazole (Hhpt) and (E)-1-benzo[d]thiazol-2-yl)-2- (pyridin-2-ylmethylene)hydrazine (btp) were reacted with [Re(CO)5Cl]. The neutral complex [ReCl(Hhpt)(CO)3] was isolated upon reaction with Hhpt, where Hhpt coordinates as a neutral bidentate ligand. The reaction of [Re(CO)5Cl] with btp gave two different complexes when using different solvents. In methanol, [ReCl(btp)(CO)3] was isolated, whereas in toluene, the conjugate of btp (btp1) was formed which resulted in the formation of [ReCl(btp1)(CO)3]. The study on potentially bidentate thiourea derivatives containing a benzothiazole moiety towards [ReI(CO)3]+ and [ReVO]3+ cores gave rise to a wide variety of complexes. The reaction of [Re(CO)5Cl] with N-phenyl-N-(2-benzothiazole)thiourea (Hpbt) produced the rhenium(I) complex [Re(Hpbt)(pbt)(CO)3]. Hpbt coordinates both as a monodentate neutral ligand and as a bidentate monoanionic chelate. The study of the reaction between trans-[ReOCl3(PPh3)2] and Hpbt gave the rhenium(V) product [ReOCl2(pbt)(PPh3)], with pbt acting as a bidentate ligand. The reaction of 1-(1,3- benzothiazol-2-yl)-3-benzoylthiourea (Hbbt) with [Re(CO)5Cl] led to the isolation of [ReCl(Hbbt)(CO)3]. Similar reaction of Hbbt with trans-[ReOCl3(PPh3)2] gave the unique compound [ReOCl2(Hbnt)(PPh3)], where the ligand coordinates via the ketonic oxygen and a methine carbon. The complex [Re(Hmby)(mby)(CO)3] was isolated upon reacting [Re(CO)5Cl] with methylbenzothiazol-2-ylidenecarbamodithioate (Hmby), with Hmby coordinating as a monodentate neutral ligand and mby as a bidentate monoanionic chelate. The coordination behaviour of N-(benzothiazol-2-yl)-S,S’- dimethyldithiocarboimine (Hbdc) towards rhenium(I) led to the formation of [ReCl(Hbdc)(CO)3]. The reactivity of 1-(benzothiozol-2-yl)-3,3-dimethylthiourea (Hbdm), a derivative of Hmby, was studied with trans-[ReOCl3(PPh3)2] and trans- [ReO(OEt)I2(PPh3)2] producing the square pyramidal compound [ReOCl(bdm)2] and the salt [Re(bdm)2(MeCN)2]I3, respectively. Pyrazole derivatives containing a benzothiazole ring were studied towards rhenium in oxidation states +I and +V. The reaction between 2-(3,5-dimethylpyrazol-1-yl)benzothiazole (Hdmp) and [Re(CO)5Cl] gave the neutral rhenium complex [ReCl(Hdmp)(CO)3], whereas its reaction with [ReOCl3(PPh3)2] surprisingly results in the formation of a dimeric complex (μ-O)[ReOCl2(Hdmp)]2. The study on the reactivity of 1-(benzo[d]thiazol-2-yl)-4-methyl-1H-pyrrol-2-ol (Hbtm) with [Re(CO)5Cl] gave the unexpected trimer [Re(btm)(CO)3]3 containing the fac-[Re(CO)3]+ core. The ligand btm forms a bridge between each rhenium metal, serving as a bidentate ligand to one rhenium, and a monodentate ligand to another rhenium atom. The study on the coordination chemistry between trans-[ReOCl3(PPh3)2] and Hbtm gave two different complexes when using different solvents. In ethanol, [ReOCl(btm)(btm1)] formed, whereas [ReOCl(btm1)(btz)] (Hbtz = 1-(benzo[d]thiazol-2-yl)-4-(1-iminoethyl)-3- methyl-1H-pyrazol-5-ol) was isolated in acetonitrile. The reaction of cis-[ReO2I(PPh3)2] also gave two different products when using different solvents, where the respective solvents coordinate to the metal. The rhenium(V) compound [ReO(OMe)(btm)(btm1)] was formed in methanol, whereas [ReO(OEt)(btm)(btm1)] was formed in ethanol. The coordination chemistry of 2-(2-Benzothiazoleyl)-4,5,6,7-tetrahydro-2H-indazol-3-ol (Hbth) was studied towards [Re(CO)5Cl] and trans-[ReOCl3(PPh3)2]. The resulting complexes which formed are [ReCl(Hbth)(CO)3] and [ReOCl(bth)(bth1)] respectively. The reactivity of potentially tridentate Schiff base ligands towards rhenium(I) and (V) was studied. The rhenium(I) precursor [Re(CO)5Cl] was reacted with (E)-1- (benzo[d]thiazol-2-yl)-2-(phenol-2-ylmethylene)hydrazine (H3bph) to give [ReCl(CO)3(H3bph)], which contains the kinetically inert fac-[Re(CO)3]+ core coordinated to a neutral bidentate ligand. The reaction of [ReO2(py)4Cl] with H3bph gave the dimeric species (μ-O)[ReO(Hbph)(py)]2, where the ligand coordinates as a tridentate dianionic chelate. A similar complex was isolated with (E)-1- (benzo[d]thiazol-2-yl)-2-(2,4-dihydroxy-2-ylmethylene)hydrazine (H3bdh) to give (μ-O)[ReO(Hbdh)(py)]2. The reaction of trans-[ReOCl3(PPh3)2] with H3bph afforded [Re(abt)(imp)Cl2(PPh3)] (abt = 2-aminobenzothiazole, imp = 2-(iminomethyl)phenol), where the ligand broke up into two fragments, both of which coordinated without any modification. The dioxo rhenium precursor cis-[ReO2I(PPh3)2] gave [ReO(Hbdh)(imp)] upon reaction with H3bdh. Ligand imp coordinates as a bidentate monoanionic ligand via the imine nitrogen and deprotonated phenolic oxygen and ligand Hbdh coordinatesas a tridentate dianionic chelate.
| Identifer | oai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:nmmu/vital:29467 |
| Date | January 2017 |
| Creators | Van Niekerk, Xandri |
| Publisher | Nelson Mandela Metropolitan University, Faculty of Science |
| Source Sets | South African National ETD Portal |
| Language | English |
| Detected Language | English |
| Type | Thesis, Doctoral, PhD |
| Format | xi, 270 leaves, pdf |
| Rights | Nelson Mandela Metropolitan University |
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