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DOI: 10.25415/ujhb.12040554
title: Triazolyl RuII, RhIII, OsII, and IrIII Complexes as Potential Anticancer Agents: Synthesis, Structure Elucidation, Cytotoxicity, and DNA Model Interaction Studies. Organometallics, 2019

description: Novel conjugated ruthenium(II), rhodium-<br>(III), and iridium(III) organometallic complexes of triazoles<br>1 and 2 synthesized and evaluated for anticancer activity<br>against cervical (HeLa), kidney (HEK293), nonsmall lung<br>cancer (A549), and leukemia (MT4) cancer cell lines are<br>reported herein. The complexes are κ2-N,C coordinated and<br>have the formula [ML(Ar)Cl] (where L is 1-benzyl-4-phenyl-<br>1H-1,2,3-triazole for 1 and 1-benzyl-4-hydroxymethyl-1H-<br>1,2,3-triazole for 2, Ar is p-cymene for RuII and OsII and Cp*<br>for RhIII and IrIII, and M is metal). NMR studies, including<br>HMBC and NOESY, were employed to unambiguously<br>elucidate their structures and provide their conformational information in solution. Single-crystal X-ray diffraction data have<br>been used to establish the solid-state structures of selected complexes, which further confirm the structural elucidation by NMR.<br>Dynamic NMR studies, such as differential transferred NOE, have been employed to distinguish between isomers 1a_I and<br>1a_II of ruthenium(II) complexes of triazole 1. The rhodium(III) (1b) and iridium(III) (1c) complexes exhibited good<br>cytotoxic activities (CC50 = 4−6 μM) comparable to that of the drug auranofin against lung cancer A549 cell lines (CC50 = 4.69<br>μM). While triazole 1 based ruthenium(II) (1a) and osmium(II) (1d) complexes displayed modest anticancer activities against<br>HeLa and HEK293 cell lines, the analogous rhodium(III) and iridium(III) complexes exhibited good potential (CC50 = 9−54<br>μM versus auranofin (3−9 μM)) against these cancer cell lines. Insightful NMR studies on the interaction between the DNA<br>model guanosine 5′-GMP and the complexes 1b,c reveal a possible mode of action of the aquated complexes involving<br>carbenylation with DNA bases or purines through the triazolyl proton H-5. From the findings, these complexes could possibly<br>confer their cytotoxic activities through intercalation with the DNA of pathological cells. Therefore, carbenylation of the<br>triazolylrhodium(III) and iridium(III) complexes by DNA guanosine 5′-GMP is proposed as a novel mode of DNA<br>intercalation of these complexes in cancer cells.<br>
DOI: 10.25415/ujhb.12055209.v1
title: Hydrogenation of carbon dioxide to formate by α-diimine RuII, RhIII, IrIIIcomplexes as catalyst precursors Journal of Organometallic Chemistry

description: The conversion of CO2 into valuable chemicals has been of major interest because it is cheap and readily<br>available. The concept of reducing CO2 pollution via its utilization into valuable products has inspired us<br>to synthesise novel 4,4'-((1Z)-butane-2,3-diylidenebis(azanylylidene))dibenzoic acid (L) metal complexes<br>{[(L)RuII] (C1), [(L)RhIII] (C2), [(L]IrIII (C3)} complexes for catalytic hydrogenation of CO2. The adiimine<br>metal complexes (C1eC3) were characterised using several analytical techniques, including:<br>NMR spectroscopy and single crystal X-ray crystallography. In a mixture of THF/H2O and a base, all three<br>catalyst precursors were able to hydrogenate CO2 cleanly to formate as a product. However, the best<br>combination of catalyst precursor and a base was C1 and DBU that selectively produced formate at a<br>moderate temperature of 120 ?C and at 60 bar. The best productivity under these conditions is TOF of 35<br>h?1 within 2 h and a TON of 322. This work is significant because it provides a one-step synthesis for<br>formate from CO2 using a-diimine-based complexes which can be synthesised in a one-step reaction. The<br>density functional theory calculations on C1 supports that RueH is the active species in the process of<br>CO2 hydrogenation to formate with the insertion of the CO2 to RueH being the rate determining step.
DOI: 10.25415/ujhb.12040554.v1
title: Triazolyl RuII, RhIII, OsII, and IrIII Complexes as Potential Anticancer Agents: Synthesis, Structure Elucidation, Cytotoxicity, and DNA Model Interaction Studies. Organometallics, 2019

description: Novel conjugated ruthenium(II), rhodium-<br>(III), and iridium(III) organometallic complexes of triazoles<br>1 and 2 synthesized and evaluated for anticancer activity<br>against cervical (HeLa), kidney (HEK293), nonsmall lung<br>cancer (A549), and leukemia (MT4) cancer cell lines are<br>reported herein. The complexes are κ2-N,C coordinated and<br>have the formula [ML(Ar)Cl] (where L is 1-benzyl-4-phenyl-<br>1H-1,2,3-triazole for 1 and 1-benzyl-4-hydroxymethyl-1H-<br>1,2,3-triazole for 2, Ar is p-cymene for RuII and OsII and Cp*<br>for RhIII and IrIII, and M is metal). NMR studies, including<br>HMBC and NOESY, were employed to unambiguously<br>elucidate their structures and provide their conformational information in solution. Single-crystal X-ray diffraction data have<br>been used to establish the solid-state structures of selected complexes, which further confirm the structural elucidation by NMR.<br>Dynamic NMR studies, such as differential transferred NOE, have been employed to distinguish between isomers 1a_I and<br>1a_II of ruthenium(II) complexes of triazole 1. The rhodium(III) (1b) and iridium(III) (1c) complexes exhibited good<br>cytotoxic activities (CC50 = 4−6 μM) comparable to that of the drug auranofin against lung cancer A549 cell lines (CC50 = 4.69<br>μM). While triazole 1 based ruthenium(II) (1a) and osmium(II) (1d) complexes displayed modest anticancer activities against<br>HeLa and HEK293 cell lines, the analogous rhodium(III) and iridium(III) complexes exhibited good potential (CC50 = 9−54<br>μM versus auranofin (3−9 μM)) against these cancer cell lines. Insightful NMR studies on the interaction between the DNA<br>model guanosine 5′-GMP and the complexes 1b,c reveal a possible mode of action of the aquated complexes involving<br>carbenylation with DNA bases or purines through the triazolyl proton H-5. From the findings, these complexes could possibly<br>confer their cytotoxic activities through intercalation with the DNA of pathological cells. Therefore, carbenylation of the<br>triazolylrhodium(III) and iridium(III) complexes by DNA guanosine 5′-GMP is proposed as a novel mode of DNA<br>intercalation of these complexes in cancer cells.<br>
DOI: 10.25415/ujhb.12054930.v1
title: Direct and indirect CO2 hydrogenation catalyzed by Ir (III), Rh (III), Ru (II), and Os (II) half-sandwich complexes to generate formates and N, N-diethylformamide Journal of CO2 Utilization, 2020 Item

description: As a contribution to the valorization of carbon dioxide, new N,O-coordinated Ir(III), Rh(III), Ru(II), and Os(II)<br>half-sandwich complexes have been designed, synthesized, and applied as homogeneous pre-catalysts in the<br>experiments for direct and indirect CO2 hydrogenation under basic conditions. The complexes contain a N,Odonor<br>Schiff base ligand derived from N-(β-naphthyl)-2-oxy-1-naphthaldimine that assisted by partitioning the<br>catalysts to the organic layer in biphasic mixtures, enabling catalyst separation. In the presence of DBU, the Os<br>(II) half-sandwich complex N,O-Os(II) (C2) gave a TON of 889 for [DBUH][HCO2] formation under a partial<br>pressure of 60 bar CO2/H2 at 120 °C over 48 h, assisted by heterogeneous side reactions. Complexes N,O-Rh(III)<br>(C3) and N,O-Ir(III) (C4) exhibited great efficiency in the homogeneous hydrogenation of carbon dioxide to<br>afford formate and N,N-diethylformamide in the presence of DBU and diethylamine, respectively. Group 9 halfsandwich<br>complexes eminently qualify as useful in the direct and indirect hydrogenation of CO2 to afford reaction<br>intermediates that can be used to make carbon-neutral fuel.<br>
DOI: 10.25415/ujhb.12055209
title: Hydrogenation of carbon dioxide to formate by α-diimine RuII, RhIII, IrIIIcomplexes as catalyst precursors Journal of Organometallic Chemistry

description: The conversion of CO2 into valuable chemicals has been of major interest because it is cheap and readily<br>available. The concept of reducing CO2 pollution via its utilization into valuable products has inspired us<br>to synthesise novel 4,4'-((1Z)-butane-2,3-diylidenebis(azanylylidene))dibenzoic acid (L) metal complexes<br>{[(L)RuII] (C1), [(L)RhIII] (C2), [(L]IrIII (C3)} complexes for catalytic hydrogenation of CO2. The adiimine<br>metal complexes (C1eC3) were characterised using several analytical techniques, including:<br>NMR spectroscopy and single crystal X-ray crystallography. In a mixture of THF/H2O and a base, all three<br>catalyst precursors were able to hydrogenate CO2 cleanly to formate as a product. However, the best<br>combination of catalyst precursor and a base was C1 and DBU that selectively produced formate at a<br>moderate temperature of 120 ?C and at 60 bar. The best productivity under these conditions is TOF of 35<br>h?1 within 2 h and a TON of 322. This work is significant because it provides a one-step synthesis for<br>formate from CO2 using a-diimine-based complexes which can be synthesised in a one-step reaction. The<br>density functional theory calculations on C1 supports that RueH is the active species in the process of<br>CO2 hydrogenation to formate with the insertion of the CO2 to RueH being the rate determining step.
DOI: 10.25415/ujhb.12055221
title: Rhodium(I) metallacycles based on alkylated-PTA scaffolds: Synthesis and evaluation as hydroformylation catalyst precursors

description: A series of rhodium(I) metallacycles based on alkylated PTA complexes were synthesised and fully characterised<br>using a range of spectroscopic and analytical techniques. These mononuclear Rh(I) complexes were evaluated in<br>the aqueous biphasic (water-toluene) hydroformylation of 1-octene, showing chemoselectivity to aldehydes
DOI: 10.25415/ujhb.12055221.v1
title: Rhodium(I) metallacycles based on alkylated-PTA scaffolds: Synthesis and evaluation as hydroformylation catalyst precursors

description: A series of rhodium(I) metallacycles based on alkylated PTA complexes were synthesised and fully characterised<br>using a range of spectroscopic and analytical techniques. These mononuclear Rh(I) complexes were evaluated in<br>the aqueous biphasic (water-toluene) hydroformylation of 1-octene, showing chemoselectivity to aldehydes
DOI: 10.25415/ujhb.12059475.v1
title: Highly selective and efficient solvent-free transformation of bio-derived levulinic acid to γ-valerolactone by Ru(II) arene catalyst precursors

description: The selective and efficient solvent-free hydrogenation of bio-based levulinic acid (LA) to γ-valerolactone (GVL)<br>was achieved with new pyridylimine ruthenium(II) complexes as catalyst precursors. The hydrogenation reactions<br>were performed in the presence of formic acid as hydrogen source using a catalyst loading as low as 0.1 mol<br>% with potassium hydroxide or triethylamine (Et3N). 4-Hydroxyvaleric acid (HVA) was produced only when<br>KOH was used, whereas reactions involving Et3N were selective to GVL. At 150 °C,&gt;96% LA conversions were<br>achieved with 100% GVL selectivity. Recyclability of catalyst precursors was demonstrated by running three<br>consecutive reactions where 100% conversion and selectivity was maintained. In-situ NMR studies show that<br>hydrogen gas is formed by the decomposition of formic acid to carbon dioxide and hydrogen. Ru-hydride species<br>have been detected, by 1H NMR, and are believed to be the catalytically active species, and a mechanism of the<br>reaction has been proposed.
DOI: 10.25415/ujhb.12055383.v1
title: Bis (pyrazolyl) palladium (II) complexes as catalysts for Mizoroki–Heck cross-coupling reactions

description: Recent progress in carbon–carbon cross-coupling reactions has resulted in the discovery of highly active<br>catalysts for carrying out such transformations. However, due to the wide array of applications of the<br>products from cross-coupling reactions, there is the need to design suitable catalysts that permit the<br>practical and economical synthesis of the cross-coupled products. Palladium complexes with bulky<br>and electron-donating ligands have served as excellent (pre)catalysts for the Mizoroki–Heck cross-coupling<br>reaction. By using bulky pyrazole-based ligands, we have prepared palladium(II) complexes with<br>controlled steric and electronic properties of the metal center. We have used these bulky bis(pyrazolyl)-<br>palladium(II) complexes as (pre)catalysts for the Mizoroki–Heck cross-coupling reaction. The (pre)catalysts<br>displayed high activity and selectivity, giving high catalytic conversions at a low (pre)catalyst<br>loading and short reaction times. A mercury poisoning test confirmed that the (pre)catalysts promoted<br>the Mizoroki–Heck cross-coupling homogenously and do not decompose into palladium black during<br>the reactions. The catalytic systems were also tolerant to the presence of functional groups, such as 4-<br>CF3, 4-CH3, 4-CO2Me and 4-CO2Et, on the alkene substrates.
DOI: 10.25415/ujhb.12059475
title: Highly selective and efficient solvent-free transformation of bio-derived levulinic acid to γ-valerolactone by Ru(II) arene catalyst precursors

description: The selective and efficient solvent-free hydrogenation of bio-based levulinic acid (LA) to γ-valerolactone (GVL)<br>was achieved with new pyridylimine ruthenium(II) complexes as catalyst precursors. The hydrogenation reactions<br>were performed in the presence of formic acid as hydrogen source using a catalyst loading as low as 0.1 mol<br>% with potassium hydroxide or triethylamine (Et3N). 4-Hydroxyvaleric acid (HVA) was produced only when<br>KOH was used, whereas reactions involving Et3N were selective to GVL. At 150 °C,&gt;96% LA conversions were<br>achieved with 100% GVL selectivity. Recyclability of catalyst precursors was demonstrated by running three<br>consecutive reactions where 100% conversion and selectivity was maintained. In-situ NMR studies show that<br>hydrogen gas is formed by the decomposition of formic acid to carbon dioxide and hydrogen. Ru-hydride species<br>have been detected, by 1H NMR, and are believed to be the catalytically active species, and a mechanism of the<br>reaction has been proposed.
DOI: 10.25415/ujhb.12059574
title: Synthesis, characterisation and reactivity of water-soluble ferrocenylimine-Rh(I) complexes as aqueous-biphasic hydroformylation catalyst precursors

description: Water-soluble complexes based on monosodium 5-sulfonato salicylaldimine (3) and 3-tbutyl-5-<br>sulfonatosalicylaldimine have been synthesised via sulfonation and Schiff base condensation reactions.<br>The ligand (3) and the new water-soluble mononuclear 5-sulfonatosalicylaldimine-ferrocenylimine<br>complexes (4 and 5) have been synthesised and characterised fully using 1H NMR, 13C{1H} NMR, and FTIR<br>spectroscopy, elemental analysis as well as mass spectrometry. Subsequently, the Rh(I) heterobimetallic<br>complexes (6 and 7) were synthesised from [RhCl(COD)]2 (COD ¼ 1,5-cyclooctadiene) and the<br>ferrocenylimine metalloligands (4 and 5) and characterised using various analytical and spectroscopic<br>techniques. These complexes were applied as catalyst precursors in aqueous biphasic hydroformylation<br>reactions. Optimal conditions were established at 95 ?C (40 bar), showing the best chemoselectivity for<br>aldehydes. The mononuclear ferrocenyl pre-catalysts (4 and 5) were inactive in the aqueous-biphasic<br>hydroformylation of 1-octene. The heterobimetallic catalyst precursors (6 and 7) displayed good activity<br>and could be recycled for at least 4 runs under the investigated conditions for the aqueous biphasic<br>hydroformylation of 1-octene.
DOI: 10.25415/ujhb.12059574.v1
title: Synthesis, characterisation and reactivity of water-soluble ferrocenylimine-Rh(I) complexes as aqueous-biphasic hydroformylation catalyst precursors

description: Water-soluble complexes based on monosodium 5-sulfonato salicylaldimine (3) and 3-tbutyl-5-<br>sulfonatosalicylaldimine have been synthesised via sulfonation and Schiff base condensation reactions.<br>The ligand (3) and the new water-soluble mononuclear 5-sulfonatosalicylaldimine-ferrocenylimine<br>complexes (4 and 5) have been synthesised and characterised fully using 1H NMR, 13C{1H} NMR, and FTIR<br>spectroscopy, elemental analysis as well as mass spectrometry. Subsequently, the Rh(I) heterobimetallic<br>complexes (6 and 7) were synthesised from [RhCl(COD)]2 (COD ¼ 1,5-cyclooctadiene) and the<br>ferrocenylimine metalloligands (4 and 5) and characterised using various analytical and spectroscopic<br>techniques. These complexes were applied as catalyst precursors in aqueous biphasic hydroformylation<br>reactions. Optimal conditions were established at 95 ?C (40 bar), showing the best chemoselectivity for<br>aldehydes. The mononuclear ferrocenyl pre-catalysts (4 and 5) were inactive in the aqueous-biphasic<br>hydroformylation of 1-octene. The heterobimetallic catalyst precursors (6 and 7) displayed good activity<br>and could be recycled for at least 4 runs under the investigated conditions for the aqueous biphasic<br>hydroformylation of 1-octene.
DOI: 10.25415/ujhb.12055383
title: Bis (pyrazolyl) palladium (II) complexes as catalysts for Mizoroki–Heck cross-coupling reactions

description: Recent progress in carbon–carbon cross-coupling reactions has resulted in the discovery of highly active<br>catalysts for carrying out such transformations. However, due to the wide array of applications of the<br>products from cross-coupling reactions, there is the need to design suitable catalysts that permit the<br>practical and economical synthesis of the cross-coupled products. Palladium complexes with bulky<br>and electron-donating ligands have served as excellent (pre)catalysts for the Mizoroki–Heck cross-coupling<br>reaction. By using bulky pyrazole-based ligands, we have prepared palladium(II) complexes with<br>controlled steric and electronic properties of the metal center. We have used these bulky bis(pyrazolyl)-<br>palladium(II) complexes as (pre)catalysts for the Mizoroki–Heck cross-coupling reaction. The (pre)catalysts<br>displayed high activity and selectivity, giving high catalytic conversions at a low (pre)catalyst<br>loading and short reaction times. A mercury poisoning test confirmed that the (pre)catalysts promoted<br>the Mizoroki–Heck cross-coupling homogenously and do not decompose into palladium black during<br>the reactions. The catalytic systems were also tolerant to the presence of functional groups, such as 4-<br>CF3, 4-CH3, 4-CO2Me and 4-CO2Et, on the alkene substrates.
DOI: 10.25415/ujhb.12310217.v1
title: Acridine‐containing RuII, OsII, RhIII and IrIII Half‐Sandwich Complexes: Synthesis, Structure and Antiproliferative Activity

description: Research aimed at enhancing the efficacy of organometallic complexes against<br>cancer, has shown that attaching bio‐active molecules to (metallo)drugs often<br>enhances their biological properties. New salicylaldimine and 2‐pyridylimine<br>ligands (L2 and L3), containing a bio‐active acridine scaffold, were synthesized<br>and complexed to Rh(III), Ir(III), Ru(II) and Os(II) metal ion centers. The resulting<br>acridine‐containing half‐sandwich complexes have been characterized fully by<br>elemental analysis, FT‐IR and NMR spectroscopy, HR‐ESI mass spectrometry as<br>well as single crystal X‐ray diffraction, for the Rh(III) N^N bidentate complex<br>[RhCp*Cl(L3)][BPh4]. The antiproliferative activity of the ligands (L2 and L3)<br>and complexes (C1 to C9) were evaluated in vitro against human promyelocytic leukemia<br>cells (HL60) and normal skin fibroblast cells (FG0). The compounds exhibit<br>good activities against HL60 cells and are consistently selective towards cancerous<br>cells over non‐tumorous cells. This study demonstrates the potential of such hybrid<br>compounds to target cancer cells specifically. The most active complex,<br>[RhCp*Cl(L2)], exhibited binding to DNA model guanosine‐5’‐monophosphate<br>(5’‐GMP) which suggests a mode of action involving interaction of the complex<br>with 5’‐GMP found on DNA backbone
DOI: 10.25415/ujhb.12231191
title: Neutral and cationic osmium(II)-arene metallodendrimers: Synthesis, characterisation and anticancer activity

description: Two neutral and two cationic half-sandwich Os(II)-arene metallodendrimers, of general formula [DABPPI-{(<br>g6-p-cym)Os((C7H5NO)-j2-N,O)Cl}n] and [DAB-PPI-{(g6-p-cym)Os((C6H5N2)-j2-N,N)Cl}n][PF6]n<br>(where n = 4 (G1) or 8 (G2)) have been synthesised. In addition, two cationic half-sandwich Os(II)-arene<br>metallodendrimers, containing PTA (1,3,5-triaza-7-phosphatricyclo[3.3.1.1.] decane), of general formula<br>[DAB-PPI-{(g6-p-cym)Os((C7H5NO)-j2-N,O)PTA}n][PF6]n are also reported. All complexes have been characterised<br>using analytical (i.e. HR-ESI or EI mass spectrometry and elemental analysis) and spectroscopic<br>(i.e. 1H, 13C{1H} NMR and infrared) methods. Model mononuclear analogues have been prepared and their<br>molecular structures determined by single-crystal X-ray crystallography. The cytotoxicity of the complexes<br>were evaluated against the A2780 and A2780cisR human ovarian carcinoma cell lines and some<br>display moderate activity.
DOI: 10.25415/ujhb.12231191.v1
title: Neutral and cationic osmium(II)-arene metallodendrimers: Synthesis, characterisation and anticancer activity

description: Two neutral and two cationic half-sandwich Os(II)-arene metallodendrimers, of general formula [DABPPI-{(<br>g6-p-cym)Os((C7H5NO)-j2-N,O)Cl}n] and [DAB-PPI-{(g6-p-cym)Os((C6H5N2)-j2-N,N)Cl}n][PF6]n<br>(where n = 4 (G1) or 8 (G2)) have been synthesised. In addition, two cationic half-sandwich Os(II)-arene<br>metallodendrimers, containing PTA (1,3,5-triaza-7-phosphatricyclo[3.3.1.1.] decane), of general formula<br>[DAB-PPI-{(g6-p-cym)Os((C7H5NO)-j2-N,O)PTA}n][PF6]n are also reported. All complexes have been characterised<br>using analytical (i.e. HR-ESI or EI mass spectrometry and elemental analysis) and spectroscopic<br>(i.e. 1H, 13C{1H} NMR and infrared) methods. Model mononuclear analogues have been prepared and their<br>molecular structures determined by single-crystal X-ray crystallography. The cytotoxicity of the complexes<br>were evaluated against the A2780 and A2780cisR human ovarian carcinoma cell lines and some<br>display moderate activity.
DOI: 10.25415/ujhb.12310217
title: Acridine‐containing RuII, OsII, RhIII and IrIII Half‐Sandwich Complexes: Synthesis, Structure and Antiproliferative Activity

description: Research aimed at enhancing the efficacy of organometallic complexes against<br>cancer, has shown that attaching bio‐active molecules to (metallo)drugs often<br>enhances their biological properties. New salicylaldimine and 2‐pyridylimine<br>ligands (L2 and L3), containing a bio‐active acridine scaffold, were synthesized<br>and complexed to Rh(III), Ir(III), Ru(II) and Os(II) metal ion centers. The resulting<br>acridine‐containing half‐sandwich complexes have been characterized fully by<br>elemental analysis, FT‐IR and NMR spectroscopy, HR‐ESI mass spectrometry as<br>well as single crystal X‐ray diffraction, for the Rh(III) N^N bidentate complex<br>[RhCp*Cl(L3)][BPh4]. The antiproliferative activity of the ligands (L2 and L3)<br>and complexes (C1 to C9) were evaluated in vitro against human promyelocytic leukemia<br>cells (HL60) and normal skin fibroblast cells (FG0). The compounds exhibit<br>good activities against HL60 cells and are consistently selective towards cancerous<br>cells over non‐tumorous cells. This study demonstrates the potential of such hybrid<br>compounds to target cancer cells specifically. The most active complex,<br>[RhCp*Cl(L2)], exhibited binding to DNA model guanosine‐5’‐monophosphate<br>(5’‐GMP) which suggests a mode of action involving interaction of the complex<br>with 5’‐GMP found on DNA backbone
DOI: 10.25415/ujhb.13643009.v1
title: RSOS RAW DATA.zip

description: Raw data
DOI: 10.25415/ujhb.13643009
title: RSOS RAW DATA.zip

description: Raw data