Benjamin, E.

Chui, S.

Draganjac, Mark

Rougaeu, B.

ScholarWorks@UARK

Journal of the Arkansas Academy of ScienceVolume 63 Article 242009Microwave Syntheses and Thermal GravimetricAnalysis of trans-Hydrogenbis(dimethylsulfoxide)tetrachlororuthenate(III)S. ChuiArkansas State UniversityMark DraganjacArkansas State University, mdraganj@astate.eduBenjamin E. MarkArkansas State UniversityBenjamin RougeauArkansas State UniversityFollow this and additional works at: http://scholarworks.uark.edu/jaasPart of the Physical Chemistry CommonsThis article is available for use under the Creative Commons license: Attribution-NoDerivatives 4.0 International (CC BY-ND 4.0). Users are able toread, download, copy, print, distribute, search, link to the full texts of these articles, or use them for any other lawful purpose, without asking priorpermission from the publisher or the author.This General Note is brought to you for free and open access by ScholarWorks@UARK. It has been accepted for inclusion in Journal of the ArkansasAcademy of Science by an authorized editor of ScholarWorks@UARK. For more information, please contact scholar@uark.edu.Recommended CitationChui, S.; Draganjac, Mark; Mark, Benjamin E.; and Rougeau, Benjamin (2009) "Microwave Syntheses and Thermal GravimetricAnalysis of trans-Hydrogen bis(dimethylsulfoxide)tetrachlororuthenate(III)," Journal of the Arkansas Academy of Science: Vol. 63 ,Article 24.Available at: http://scholarworks.uark.edu/jaas/vol63/iss1/24Journal of the Arkansas Academy of Science, Vol. 63, 2009180Microwave Syntheses and Thermal Gravimetric Analysis of trans-Hydrogenbis(dimethylsulfoxide)tetrachlororuthenate(III)S. Chui, M. Draganjac1, E. Benjamin and B. RougeauDepartment of Chemistry and Physics, Arkansas State University, State University, AR 724671 Correspondence: mdraganj@astate.eduThe Ru(dmso)2Cl4- anion has been prepared by thereaction of RuCl3 with HCl in dimethyl sulfoxide(DMSO) at elevated temperatures (Alessio et al. 1991).The successful microwave synthesis of RuCl2(dmso)4(Harvey et al. 2009) led us to explore the use ofmicrowave technologies for improving the synthesis oftrans-[H(dmso)2][Ru(dmso)2Cl4].The starting material, RuCl3.xH2O, ethanol,aqueous HCl and dimethyl sulfoxide were purchasedfrom Aldrich Chemical Company. All reagents wereused as purchased without further purification. AnAgilent 8453 UV-Visible spectrophotometer was usedfor the analysis of the compounds. Thermal analysiswas done on a Seiko DT/TGA 320 Thermoanalyzerunder Ar gas (300ml/min) with copper reference andsample pans. The sample of trans-[H(dmso)2][Ru(dmso)2Cl4] (8.252 mg) was heatedfrom 30 – 350 oC at 5 oC/min. The microwavesynthesis was performed using a CEM DiscoverMicrowave Reactor. 1H NMR spectra were obtained ona Bruker Avance 300 NMR spectrophotometer using d-chloroform with TMS as an internal standard.Three methods were employed for the microwavesynthesis of trans-[H(dmso)2][Ru(dmso)2Cl4]:Method A: A 0.15 g (0.57 mmol) sample ofRuCl3.xH2O was dissolved in 0.7 mL DMSO and 0.1mL 37% aqueous HCl, and the mixture was placed inthe microwave reactor and heated to 80 °C for 2 min.A red-orange solution was obtained and after additionof 5 mL acetone and setting for several hours at roomtemperature, red crystals formed. The product wasfiltered, washed with acetone and vacuum dried; yield= 95 %, melting point (mp) = 120 oC.Method B: A 0.10 g (0.38 mmol) sample ofRuCl3.xH2O was placed in the microwave reaction tubewith 2 mL ethanol, and the mixture was heated in themicrowave reactor to 75 °C for 15 min. Then 0.2 mLDMSO and 0.1 mL 37% aqueous HCl was added andthe mixture was heated in the microwave to 75 °C for 3min. The resulting red-orange solution formed redcrystals after addition of acetone and leaving forseveral hours at room temperature. The product wasfiltered, washed with acetone and vacuum dried; yield= 79 %, mp = 120 oC.Method C: The reaction was done by placing the fourreagents, 0.10 g (0.38 mmol) RuCl3.xH2O, 0.2 mLDMSO, 0.1 mL 37% aqueous HCl, and 2 mL ethanoltogether in the reaction tube and the mixture washeated in the microwave reactor to 75 °C for 18 min.After the 18 min reaction time, a red-orange colorformed in the solution. After addition of acetone, andleaving for several hours at room temperature, redcrystals precipitated from solution. The product wasfiltered, washed with acetone and vacuum dried; yield= 67 %, mp = 120 oC.The visible spectrum (Figure 1) and melting pointsof the products from all three microwave methodsmatched the literature values for trans-[H(dmso)2][Ru(dmso)2Cl4] (Alessio et al. 1991).Proton NMR spectra of the products obtained from themicrowave reactions were identical to the NMRspectrum obtained for trans-[H(dmso)2][Ru(dmso)2Cl4]prepared following the methods of Alessio andcoworkers (Alessio et al. 1991).Figure 1. Visible spectra of trans-[H(dmso)2][Ru(dmso)2Cl4]prepared using microwave techniques.Microwave synthesis of trans-(Ph4P)[Ru(dmso)2Cl4],Ph = phenylA 0.15 g (0.57 mmol) sample of RuCl3.xH2O wasdissolved in 0.7 mL DMSO and 2 mL ethanol, and180Journal of the Arkansas Academy of Science, Vol. 63 [2009], Art. 24Published by Arkansas Academy of Science, 2009Microwave Syntheses and Thermal Gravimetric Analysis of trans-Hydrogenbis(dimethylsulfoxide)tetrachlororuthenate(III)Journal of the Arkansas Academy of Science, Vol. 63, 20091810.22 g (0.57 mmol) Ph4PCl (tetraphenylphosphoniumchloride) was added. The mixture was placed in themicrowave reactor and heated to 100 oC for 2 min.Upon reaction completion, an orange precipitateformed. The product was filtered and dried; yield =54 %, mp = 120 oC. The visible spectrum matched thevalues reported in the literature for trans-[H(dmso)2][RuCl4(dmso)2] (Alessio et al. 1991).Microwave Syntheses. Three methods for themicrowave synthesis of the title compound wereinvestigated. The first two microwave methodsmirrored the preparations reported in the literature(Alessio et al. 1991). Microwave Method C variesfrom Method A by the addition of ethanol. Ethanolwas used by Alessio to improve solubility of the RuCl3before reaction with DMSO.The microwave techniques provide a possiblealternate preparative route for the synthesis of trans-[H(dmso)2][Ru(dmso)2Cl4]. Method A (95 % yield)gave a better yield than the literature preparation (80%).Method B showed a comparable yield to that reportedin the literature and Method C had a lower yield thanthe literature (Alessio et al. 1991). In particular,method A provides the best synthetic route for the titlecompound as seen by the increase in yield and thedecrease in reaction times (2 min vs 30 min).Addition of PPh4Cl as a chloride source alsoprovided a counterion for the Ru(dmso)2Cl4- ion.Though lower yields are obtained, trans-PPh4[Ru(dmso)2Cl4] precipitates from solution and caneasily be isolated.Thermal Analysis of trans-[H(dmso)2][Ru(dmso)2Cl4]. The thermaldecomposition of trans-[H(dmso)2][Ru(dmso)2Cl4] canbe seen in Figure 2. With an onset temperature of108.4 oC, the trans-[H(dmso)2][RuCl4(dmso)2]complex decomposes in five steps, starting with theinitial loss of HCl. Subsequent loss of the fourremaining DMSO moieties occurs in a stepwisemanner. Thermal decomposition of trans-[H(dmso)2][Ru(dmso)2Cl4] occurs between 100 and300 oC as the title compound loses mass stepwise untilRuCl3 remains. Understanding the thermal propertiesof trans-[H(dmso)2][Ru(dmso)2Cl4] may lead toimproved syntheses of other Ru(III) complexes(Alessio et al. 1991).Figure 2. Thermal Gravimetric Analysis plot for trans-[H(dmso)2][Ru(dmso)2Cl4]AcknowledgmentsFunding for the TG/DTA provided by the NationalScience Foundation (Grant No. DUE-9351560). Theauthors thank the Arkansas State University and theDepartment of Chemistry and Physics for their supportof this project.Literature CitedAlessio E, G Balducci, M Calligaris, G Costa andWM Attia. 1991. Synthesis, molecular structure,and chemical behavior of hydrogen trans-bis(dimethyl sulfoxide)-tetrachlororuthenate(III)and mer-trichloro-tris(dimethyl sulfoxide)ruthenium(III): the first fully characterizedchloride-dimethyl sulfoxide-ruthenium(III)complexes. Inorganic Chemistry 30(4):609-18.Harvey A, SK Chiu, R Snell, M Draganjac, and EBenjamin. 2009. Microwave synthesis of cis-dichlorotetrakis(dimethylsulfoxide)ruthenium(II).Journal of the Arkansas Academy of Science63:185.181Journal of the Arkansas Academy of Science, Vol. 63 [2009], Art. 24http://scholarworks.uark.edu/jaas/vol63/iss1/24

Microwave Syntheses and Thermal Gravimetric Analysis of trans-Hydrogen bis(dimethylsulfoxide)tetrachlororuthenate(III)

UARK (University of Arkansas )

Journal of the Arkansas Academy of Science Volume 63 Article 24 2009 Microwave Syntheses and Thermal Gravimetric Analysis of trans-Hydrogen bis(dimethylsulfoxide)tetrachlororuthenate(III) S. Chui Arkansas State University Mark Draganjac Arkansas State University, mdraganj@astate.edu E. Benjamin Arkansas State University B. Rougaeu Arkansas State University Follow this and additional works at: https://scholarworks.uark.edu/jaas  Part of the Physical Chemistry Commons Recommended Citation Chui, S.; Draganjac, Mark; Benjamin, E.; and Rougaeu, B. (2009) "Microwave Syntheses and Thermal Gravimetric Analysis of trans-Hydrogen bis(dimethylsulfoxide)tetrachlororuthenate(III)," Journal of the Arkansas Academy of Science: Vol. 63 , Article 24. Available at: https://scholarworks.uark.edu/jaas/vol63/iss1/24 This article is available for use under the Creative Commons license: Attribution-NoDerivatives 4.0 International (CC BY-ND 4.0). Users are able to read, download, copy, print, distribute, search, link to the full texts of these articles, or use them for any other lawful purpose, without asking prior permission from the publisher or the author. This General Note is brought to you for free and open access by ScholarWorks@UARK. It has been accepted for inclusion in Journal of the Arkansas Academy of Science by an authorized editor of ScholarWorks@UARK. For more information, please contact scholar@uark.edu. Journal of the Arkansas Academy of Science, Vol. 63, 2009180Microwave Syntheses and Thermal Gravimetric Analysis of trans-Hydrogenbis(dimethylsulfoxide)tetrachlororuthenate(III)S. Chui, M. Draganjac1, E. Benjamin and B. RougeauDepartment of Chemistry and Physics, Arkansas State University, State University, AR 724671 Correspondence: mdraganj@astate.eduThe Ru(dmso)2Cl4- anion has been prepared by thereaction of RuCl3 with HCl in dimethyl sulfoxide(DMSO) at elevated temperatures (Alessio et al. 1991).The successful microwave synthesis of RuCl2(dmso)4(Harvey et al. 2009) led us to explore the use ofmicrowave technologies for improving the synthesis oftrans-[H(dmso)2][Ru(dmso)2Cl4].The starting material, RuCl3.xH2O, ethanol,aqueous HCl and dimethyl sulfoxide were purchasedfrom Aldrich Chemical Company. All reagents wereused as purchased without further purification. AnAgilent 8453 UV-Visible spectrophotometer was usedfor the analysis of the compounds. Thermal analysiswas done on a Seiko DT/TGA 320 Thermoanalyzerunder Ar gas (300ml/min) with copper reference andsample pans. The sample of trans-[H(dmso)2][Ru(dmso)2Cl4] (8.252 mg) was heatedfrom 30 – 350 oC at 5 oC/min. The microwavesynthesis was performed using a CEM DiscoverMicrowave Reactor. 1H NMR spectra were obtained ona Bruker Avance 300 NMR spectrophotometer using d-chloroform with TMS as an internal standard.Three methods were employed for the microwavesynthesis of trans-[H(dmso)2][Ru(dmso)2Cl4]:Method A: A 0.15 g (0.57 mmol) sample ofRuCl3.xH2O was dissolved in 0.7 mL DMSO and 0.1mL 37% aqueous HCl, and the mixture was placed inthe microwave reactor and heated to 80 °C for 2 min.A red-orange solution was obtained and after additionof 5 mL acetone and setting for several hours at roomtemperature, red crystals formed. The product wasfiltered, washed with acetone and vacuum dried; yield= 95 %, melting point (mp) = 120 oC.Method B: A 0.10 g (0.38 mmol) sample ofRuCl3.xH2O was placed in the microwave reaction tubewith 2 mL ethanol, and the mixture was heated in themicrowave reactor to 75 °C for 15 min. Then 0.2 mLDMSO and 0.1 mL 37% aqueous HCl was added andthe mixture was heated in the microwave to 75 °C for 3min. The resulting red-orange solution formed redcrystals after addition of acetone and leaving forseveral hours at room temperature. The product wasfiltered, washed with acetone and vacuum dried; yield= 79 %, mp = 120 oC.Method C: The reaction was done by placing the fourreagents, 0.10 g (0.38 mmol) RuCl3.xH2O, 0.2 mLDMSO, 0.1 mL 37% aqueous HCl, and 2 mL ethanoltogether in the reaction tube and the mixture washeated in the microwave reactor to 75 °C for 18 min.After the 18 min reaction time, a red-orange colorformed in the solution. After addition of acetone, andleaving for several hours at room temperature, redcrystals precipitated from solution. The product wasfiltered, washed with acetone and vacuum dried; yield= 67 %, mp = 120 oC.The visible spectrum (Figure 1) and melting pointsof the products from all three microwave methodsmatched the literature values for trans-[H(dmso)2][Ru(dmso)2Cl4] (Alessio et al. 1991).Proton NMR spectra of the products obtained from themicrowave reactions were identical to the NMRspectrum obtained for trans-[H(dmso)2][Ru(dmso)2Cl4]prepared following the methods of Alessio andcoworkers (Alessio et al. 1991).Figure 1. Visible spectra of trans-[H(dmso)2][Ru(dmso)2Cl4]prepared using microwave techniques.Microwave synthesis of trans-(Ph4P)[Ru(dmso)2Cl4],Ph = phenylA 0.15 g (0.57 mmol) sample of RuCl3.xH2O wasdissolved in 0.7 mL DMSO and 2 mL ethanol, and180Journal of the Arkansas Academy of Science, Vol. 63 [2009], Art. 24Published by Arkansas Academy of Science, 2009Microwave Syntheses and Thermal Gravimetric Analysis of trans-Hydrogenbis(dimethylsulfoxide)tetrachlororuthenate(III)Journal of the Arkansas Academy of Science, Vol. 63, 20091810.22 g (0.57 mmol) Ph4PCl (tetraphenylphosphoniumchloride) was added. The mixture was placed in themicrowave reactor and heated to 100 oC for 2 min.Upon reaction completion, an orange precipitateformed. The product was filtered and dried; yield =54 %, mp = 120 oC. The visible spectrum matched thevalues reported in the literature for trans-[H(dmso)2][RuCl4(dmso)2] (Alessio et al. 1991).Microwave Syntheses. Three methods for themicrowave synthesis of the title compound wereinvestigated. The first two microwave methodsmirrored the preparations reported in the literature(Alessio et al. 1991). Microwave Method C variesfrom Method A by the addition of ethanol. Ethanolwas used by Alessio to improve solubility of the RuCl3before reaction with DMSO.The microwave techniques provide a possiblealternate preparative route for the synthesis of trans-[H(dmso)2][Ru(dmso)2Cl4]. Method A (95 % yield)gave a better yield than the literature preparation (80%).Method B showed a comparable yield to that reportedin the literature and Method C had a lower yield thanthe literature (Alessio et al. 1991). In particular,method A provides the best synthetic route for the titlecompound as seen by the increase in yield and thedecrease in reaction times (2 min vs 30 min).Addition of PPh4Cl as a chloride source alsoprovided a counterion for the Ru(dmso)2Cl4- ion.Though lower yields are obtained, trans-PPh4[Ru(dmso)2Cl4] precipitates from solution and caneasily be isolated.Thermal Analysis of trans-[H(dmso)2][Ru(dmso)2Cl4]. The thermaldecomposition of trans-[H(dmso)2][Ru(dmso)2Cl4] canbe seen in Figure 2. With an onset temperature of108.4 oC, the trans-[H(dmso)2][RuCl4(dmso)2]complex decomposes in five steps, starting with theinitial loss of HCl. Subsequent loss of the fourremaining DMSO moieties occurs in a stepwisemanner. Thermal decomposition of trans-[H(dmso)2][Ru(dmso)2Cl4] occurs between 100 and300 oC as the title compound loses mass stepwise untilRuCl3 remains. Understanding the thermal propertiesof trans-[H(dmso)2][Ru(dmso)2Cl4] may lead toimproved syntheses of other Ru(III) complexes(Alessio et al. 1991).Figure 2. Thermal Gravimetric Analysis plot for trans-[H(dmso)2][Ru(dmso)2Cl4]AcknowledgmentsFunding for the TG/DTA provided by the NationalScience Foundation (Grant No. DUE-9351560). Theauthors thank the Arkansas State University and theDepartment of Chemistry and Physics for their supportof this project.Literature CitedAlessio E, G Balducci, M Calligaris, G Costa andWM Attia. 1991. Synthesis, molecular structure,and chemical behavior of hydrogen trans-bis(dimethyl sulfoxide)-tetrachlororuthenate(III)and mer-trichloro-tris(dimethyl sulfoxide)ruthenium(III): the first fully characterizedchloride-dimethyl sulfoxide-ruthenium(III)complexes. Inorganic Chemistry 30(4):609-18.Harvey A, SK Chiu, R Snell, M Draganjac, and EBenjamin. 2009. Microwave synthesis of cis-dichlorotetrakis(dimethylsulfoxide)ruthenium(II).Journal of the Arkansas Academy of Science63:185.181Journal of the Arkansas Academy of Science, Vol. 63 [2009], Art. 24https://scholarworks.uark.edu/jaas/vol63/iss1/24

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Microwave Syntheses and Thermal Gravimetric Analysis of trans-Hydrogen bis(dimethylsulfoxide)tetrachlororuthenate(III)

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