33874dde-ef80-4155-8a7c-dbe7488cdc7e2020-06-24T09:32:18.318894SUCCESS33874dde-ef80-4155-8a7c-dbe7488cdc7e.htmlTable 1 Crystallographic data for 1–4, 8, 9 and ppt0296.2T/K1296.2T/K2296.2T/K3296.2T/K4296.2T/K8296.2T/Kppt296.2T/K9296.2T/K14CuC10H8Cl2N2S2Formula1Cu2C20H16Cl4N4S4Formula2CuC10H8Br2N2S2Formula3CuC10H8ClN2S2Formula4CuC10H8BrN2SFormula8C10H8N2SFormulapptCuC11H10Cl2N2S2Formula9CuC18H15F6N4PS3Formula14354.76M1709.52M2443.66M3319.31M4331.70M8188.25Mppt368.79M9592.03M14TrigonalCrystal system1TriclinicCrystal system2MonoclinicCrystal system3MonoclinicCrystal system4TriclinicCrystal system8MonoclinicCrystal systempptMonoclinicCrystal system9MonoclinicCrystal system14P31 (no. 144)Space group1P1̄ (no. 2)Space group2C2/c (no. 15)Space group3P21/n (no. 14)Space group4P1̄ (no. 2)Space group8P21 (no. 4)Space grouppptP21/n (no. 14)Space group9P21/a (no. 14)Space group148.3704(9)a/Å17.530(1)a/Å213.241(2)a/Å37.933(3)a/Å47.655(1)a/Å86.655(1)a/Åppt12.476(1)a/Å914.414(2)a/Å148.3704(9)b/Å18.2269(9)b/Å27.499(1)b/Å315.061(2)b/Å48.821(1)b/Å86.641(2)b/Åppt8.4932(9)b/Å910.132(2)b/Å1416.774(2)c/Å111.618(1)c/Å214.093(1)c/Å310.383(2)c/Å49.4081(9)c/Å810.4614(7)c/Åppt13.1982(8)c/Å915.605(2)c/Å1490α/°187.87(1)α/°290α/°390α/°472.237(9)α/°890α/°ppt90α/°990α/°1490β/°173.02(1)β/°2102.203(9)β/°3112.43(2)β/°472.262(9)β/°890.288(8)β/°ppt99.004(6)β/°991.534(4)β/°14120γ/°171.86(1)γ/°290γ/°390γ/°467.494(10)γ/°890γ/°ppt90γ/°990γ/°141017.8(2)U/Å31653.0(2)U/Å321367.7(3)U/Å331146.6(4)U/Å34546.0(1)U/Å38456.3(1)U/Å3ppt1381.3(2)U/Å392278.4(6)U/Å3143Z12Z21Z34Z42Z82Zppt4Z94Z148.586μ(Mo-Kα)/mm−112.376μ(Mo-Kα)/mm−127.740μ(Mo-Kα)/mm−132.470μ(Mo-Kα)/mm−145.825μ(Mo-Kα)/mm−180.303μ(Mo-Kα)/mm−1ppt2.250μ(Mo-Kα)/mm−191.368μ(Mo-Kα)/mm−114531.00F(000)1354.00F(000)2852.00F(000)3640.00F(000)4324.00F(000)8196.00F(000)ppt740.00F(000)91188.00F(000)142352Data collected14059Data collected22233Data collected33686Data collected43374Data collected83104Data collectedppt4461Data collected922495Data collected142016 (0.018)Unique data (Rint)13812 (0.007)Unique data (Rint)22004 (0.018)Unique data (Rint)33338 (0.018)Unique data (Rint)43184 (0.007)Unique data (Rint)82663 (0.016)Unique data (Rint)ppt4027 (0.032)Unique data (Rint)95117 (0.040)Unique data (Rint)142003Observed data [I > 2σ(I)]13310Observed data [I > 2σ(I)]21555Observed data [I > 2σ(I)]32440Observed data [I > 2σ(I)]42587Observed data [I > 2σ(I)]82433Observed data [I > 2σ(I)]ppt2588Observed data [I > 2σ(I)]93700Observed data [I > 2σ(I)]140.0306Final R1 [I > 2σ(I)]10.0244Final R1 [I > 2σ(I)]20.0290Final R1 [I > 2σ(I)]30.0312Final R1 [I > 2σ(I)]40.0303Final R1 [I > 2σ(I)]80.0286Final R1 [I > 2σ(I)]ppt0.0396Final R1 [I > 2σ(I)]90.0415Final R1 [I > 2σ(I)]140.0857wR210.0631wR220.0700wR230.0687wR240.0737wR280.0828wR2ppt0.0978wR290.1054wR214Compound12348ppt914T/K296.2296.2296.2296.2296.2296.2296.2296.2FormulaCuC10H8Cl2N2S2Cu2C20H16Cl4N4S4CuC10H8Br2N2S2CuC10H8ClN2S2CuC10H8BrN2SC10H8N2SCuC11H10Cl2N2S2CuC18H15F6N4PS3M354.76709.52443.66319.31331.70188.25368.79592.03Crystal systemTrigonalTriclinicMonoclinicMonoclinicTriclinicMonoclinicMonoclinicMonoclinicSpace groupP31 (no. 144)P1̄ (no. 2)C2/c (no. 15)P21/n (no. 14)P1̄ (no. 2)P21 (no. 4)P21/n (no. 14)P21/a (no. 14)a/Å8.3704(9)7.530(1)13.241(2)7.933(3)7.655(1)6.655(1)12.476(1)14.414(2)b/Å8.3704(9)8.2269(9)7.499(1)15.061(2)8.821(1)6.641(2)8.4932(9)10.132(2)c/Å16.774(2)11.618(1)14.093(1)10.383(2)9.4081(9)10.4614(7)13.1982(8)15.605(2)α/°9087.87(1)909072.237(9)909090β/°9073.02(1)102.203(9)112.43(2)72.262(9)90.288(8)99.004(6)91.534(4)γ/°12071.86(1)909067.494(10)909090U/Å31017.8(2)653.0(2)1367.7(3)1146.6(4)546.0(1)456.3(1)1381.3(2)2278.4(6)Z32142244μ(Mo-Kα)/mm−18.5862.3767.7402.4705.8250.3032.2501.368F(000)531.00354.00852.00640.00324.00196.00740.001188.00Data collected235240592233368633743104446122495Unique data (Rint)2016 (0.018)3812 (0.007)2004 (0.018)3338 (0.018)3184 (0.007)2663 (0.016)4027 (0.032)5117 (0.040)Observed data [I > 2σ(I)]20033310155524402587243325883700Final R1 [I > 2σ(I)]0.03060.02440.02900.03120.03030.02860.03960.0415wR20.08570.06310.07000.06870.07370.08280.09780.1054Table 2 Electrochemical data for [Cu(TPTM)(CH3CN)]PF6 and [CuBr(TPTM)][Cu(TPTM)(CH3CN)][Cu(TPTM)(CH3CN)]E/V (Epa − Epc)−0.174 (0.089), 0.65 (0.100)CH2Cl2E/V (Epa − Epc)−0.327 (0.064), 0.654 (pc)CH3CNE/V (Epa − Epc)NoValueE/V (Epa − Epc)[CuBr(TPTM)][CuBr(TPTM)]E/V (Epa − Epc)−0.691 (pa), 0.462 (0.063)CH2Cl2E/V (Epa − Epc)−0.359 (0.065), 0.512 (0.084)CH3CNE/V (Epa − Epc)E/V (Epa − Epc)[Cu(TPTM)(CH3CN)][Cu(TPTM)(CH3CN)]CH2Cl2−0.174 (0.089), 0.65 (0.100)CH3CN−0.327 (0.064), 0.654 (pc)[CuBr(TPTM)][CuBr(TPTM)]CH2Cl2−0.691 (pa), 0.462 (0.063)CH3CN−0.359 (0.065), 0.512 (0.084)Table 3 S–S Bond distances (Å) and C–S–S–C torsion angles (°) for Cu(II) complexes 1–30S–SS–S2S–SS–S32.024(1)2.031(2)22.059(2)2.031(2)32.047(1)2NoValue3C–S–S–CC–S–S–C2C–S–S–CC–S–S–C371.1(2)71.1(2)2108.9(2)71.1(2)3123S–SS–SS–S2.031(2)2.024(1)2.059(2)2.047(1)C–S–S–CC–S–S–CC–S–S–C71.1(2)71.1(2)108.9(2)81.3(2)http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210420m/b210420m-s1.gifhttp://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210420m/b210420m-s2.gifhttp://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210420m/b210420m-s3.gifhttp://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210420m/b210420m-s4.gifhttp://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210420m/b210420m-s5.gifLigand abbreviations: 3-mpds = 2,2′-bis(3-methylpyridyl)disulfide; 6-mpds = 2,2′-bis(6-methylpyridyl)disulfide (6-mpds); 6,3-mppt = 6-methyl-1-[2-(3-methyl)pyridyl]pyridinium-2-thiolate.http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210420m/b210420m-f1.gifCD spectra of resolved 6,3-mppt in 2-propanol.http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210420m/b210420m-s6.gifhttp://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210420m/b210420m-f2.gifCyclic voltammetry of [Cu(CH3CN)(TPTM)]PF6 (thin line) and [CuBr(TPTM)] (thick line) in (a) CH2Cl2 and (b) CH3CN.http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210420m/b210420m-f3.gifAbsorption spectra of 14 in an electrolysis cell: (a) in CH2Cl2 before electrolysis (b) after electrolysis and measured in situ.http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210420m/b210420m-f4.gifFrozen glass ESR spectrum of [Cu(CH3CN)(TPTM)]PF6 in CH3CN ∶ CH2Cl2 ∶ C3H7CN = 1 ∶ 1 ∶ 1.http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210420m/b210420m-f5.gifORTEP drawing of 1 with a view along the 31 axis in the P31 space group (upper) and a stereoscopic view of the helicate. Part of the pyridine rings are removed for clarity.http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210420m/b210420m-f6.gifORTEP drawing of 2, shown as a dimer.http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210420m/b210420m-f7.gifORTEP drawing of [CuBr2(dpds)] (3).http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210420m/b210420m-f8.gifORTEP drawing of 8 along with a schematic representation.http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210420m/b210420m-f9.gifORTEP drawing of ppt.http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210420m/b210420m-f10.gifORTEP drawing of 9.http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210420m/b210420m-f11.gifORTEP drawing of 14.CuC10H8Cl2N2S2[CuCl2(μ-dpds)2]n1CHClSNCusystemAutoTableParserTrigonalCuC10H8Cl2N2S2[CuCl2(μ-dpds)2]n1Crystal systemP31CuC10H8Cl2N2S2[CuCl2(μ-dpds)2]n1Space groupFalseCuC10H8Cl2N2S2[CuCl2(μ-dpds)2]n1Crystal system531.0CuC10H8Cl2N2S2[CuCl2(μ-dpds)2]n1531.00F(000)Kelvin^(1.0)296.2CuC10H8Cl2N2S2[CuCl2(μ-dpds)2]n1K296.2T354.76CuC10H8Cl2N2S2[CuCl2(μ-dpds)2]n1354.76MCu2C20H16Cl4N4S4[CuCl2(dpds)]22CHClSNCusystemAutoTableParserTriclinicCu2C20H16Cl4N4S4[CuCl2(dpds)]22Crystal systemP1̄Cu2C20H16Cl4N4S4[CuCl2(dpds)]22Space groupFalseCu2C20H16Cl4N4S4[CuCl2(dpds)]22Crystal system354.0Cu2C20H16Cl4N4S4[CuCl2(dpds)]22354.00F(000)Kelvin^(1.0)296.2Cu2C20H16Cl4N4S4[CuCl2(dpds)]22K296.2T709.52Cu2C20H16Cl4N4S4[CuCl2(dpds)]22709.52M,CuC10H8Br2N2S2complex3CHBrSNCusystemAutoTableParserMonoclinic,CuC10H8Br2N2S2complex3Crystal systemC2/c,CuC10H8Br2N2S2complex3Space groupFalse,CuC10H8Br2N2S2complex3Crystal system852.0,CuC10H8Br2N2S2complex3852.00F(000)Kelvin^(1.0)296.2,CuC10H8Br2N2S2complex3K296.2T443.66,CuC10H8Br2N2S2complex3443.66MCuC10H8ClN2S2[CuI(μ-Cl)(μ-dpds)]n4CIHClSNCusystemAutoTableParserMonoclinicCuC10H8ClN2S2[CuI(μ-Cl)(μ-dpds)]n4Crystal systemP21/nCuC10H8ClN2S2[CuI(μ-Cl)(μ-dpds)]n4Space groupFalseCuC10H8ClN2S2[CuI(μ-Cl)(μ-dpds)]n4Crystal system640.0CuC10H8ClN2S2[CuI(μ-Cl)(μ-dpds)]n4640.00F(000)Kelvin^(1.0)296.2CuC10H8ClN2S2[CuI(μ-Cl)(μ-dpds)]n4K296.2T319.31CuC10H8ClN2S2[CuI(μ-Cl)(μ-dpds)]n4319.31MCuC10H8BrN2S[Cu(ppt)Br]n8CHBrSNCusystemAutoTableParserTriclinicCuC10H8BrN2S[Cu(ppt)Br]n8Crystal systemP1̄CuC10H8BrN2S[Cu(ppt)Br]n8Space groupFalseCuC10H8BrN2S[Cu(ppt)Br]n8Crystal system324.0CuC10H8BrN2S[Cu(ppt)Br]n8324.00F(000)Kelvin^(1.0)296.2CuC10H8BrN2S[Cu(ppt)Br]n8K296.2T331.7CuC10H8BrN2S[Cu(ppt)Br]n8331.70MIR1systemAutoTableParserMonoclinicIR1Crystal systemP21IR1Space groupFalseIR1Crystal system196.0IR1196.00F(000)Kelvin^(1.0)296.2IR1K296.2T188.25IR1188.25MCuC11H10Cl2N2S2[CuCl2(BPTM)]n9CHClSNCuPBsystemAutoTableParserMonoclinicCuC11H10Cl2N2S2[CuCl2(BPTM)]n9Crystal systemP21/nCuC11H10Cl2N2S2[CuCl2(BPTM)]n9Space groupFalseCuC11H10Cl2N2S2[CuCl2(BPTM)]n9Crystal system740.0CuC11H10Cl2N2S2[CuCl2(BPTM)]n9740.00F(000)Kelvin^(1.0)296.2CuC11H10Cl2N2S2[CuCl2(BPTM)]n9K296.2T368.79CuC11H10Cl2N2S2[CuCl2(BPTM)]n9368.79MCuC18H15F6N4PS3[Cu(TPTM)(CH3CN)]PF614CFHSNCuPsystemAutoTableParserMonoclinicCuC18H15F6N4PS3[Cu(TPTM)(CH3CN)]PF614Crystal systemP21/aCuC18H15F6N4PS3[Cu(TPTM)(CH3CN)]PF614Space groupFalseCuC18H15F6N4PS3[Cu(TPTM)(CH3CN)]PF614Crystal system1188.0CuC18H15F6N4PS3[Cu(TPTM)(CH3CN)]PF6141188.00F(000)Kelvin^(1.0)296.2CuC18H15F6N4PS3[Cu(TPTM)(CH3CN)]PF614K296.2T592.03CuC18H15F6N4PS3[Cu(TPTM)(CH3CN)]PF614592.03MIR1Space groupAutoTableParserMonoclinicIR1Crystal systemP21IR1Space groupFalseIR1Space group196.0IR1196.00F(000)188.25IR1188.25M10.1039/b210420mpyridineCu(II)sulfur[Cu(μ-Br){1-(2-pyridyl)pyridinium-2-thiolate}]ncoppermethanolCuClMeOHpotassium cyanideyellow precipitateBrHCu[CuCl2(μ-dpds)]n2,2′-bis(6-methylpyridyl)disulfideCuCl2(μ-dpds)KOHdpdssulfurpptCu–Cbromide5-methylpyridine-2-thiolate6-methyl-1-[2-(3-methyl)pyridyl]pyridinium-2-thiolateCH2Cl2sulfurN2-dpdsCu(I)[Cu(μ-Cl)(μ-dpds)]nchloride1Hyellow precipitate2-propanolH2,2′-dipyridyldisulfide[Cu(μ-Cl)(μ-ppt)]nN1-(2-pyridyl)pyridinium-2-thiolatecopper[Cu(ppt)Cl]n[Cu(TPTM)(CH3CN)]PF66-mpds6-mpdsCHCu(II)[Cu(TPTM)(CH3CN)]PF6(dpds)CuCl(μ-Cl)2CuCl(dpds)NHBPTM13Cpyridine-2-thiolCuX(tmpa)[Cu(TPTM)(CH3CN)]PF6[Cu(TPTM)(CH3CN)]PF6CuBr2CuBr(TPTM)tolueneppt1-(2-Pyridyl)pyridinium-2-thiolate2-propanolC–S–S–CCuCl2Nbis(pyridyl-2-thio)methaneNCH2Cl2HN–CHsilicaCu–SCe(NH3)2(NO3)4Cu(II)CH2Cl2H[Cu(ppt)Br]nHsulfonatemethanoldpdsdpdsKOHtmpa = tris(pyridylmethyl)amineCHTPTMCuBr(TPTM)Cu(II)/Cu(III)C11H10N2S2C–S–S–CCu(II)–C(sp3)NCH2CDCl3NpyridiniumCH2Cl23-nitrobenzyl alcoholCuIICl2·2H2OCH2Cl2–CH3CNcopper(II)CuCl2·2H2OpyridinenitrogenchloridesCuCl2dpdsacetonitrilecopper(II)chloride[Cu(CH3CN)4]PF6CuIIBr2(dpds)[CuCl2(dpds)]2copper(I)Cu(II)Cu–Clbis(pyridylthio)methaneCu–Br[Cu(CH3CN)(TPTM)]2+Cu–NCuCuCl2·2H2OsulfurCuBr(TPTM)tris(2-pyridylthio)methaneKCNtolueneCuBr2C–S–S–CCuCHCH2CH3Cu(II)S–Ssilicamethanolmethanoldpds1-(2-pyridine)pyridiniumthiolate6-methyl-1-[2-(3-methyl)pyridyl]pyridinium-2-thiolatepyridineCu(I)BPTMCuCl2bromidesScopper(I)pyridine-2-thiolCu(III)Cu(II)dpdsHHNHHCu(II)pptpyridineCu(I)CHBr3acetonitrileS–SCuCl2ethersJEOLCudichloromethanedpdsbis(pyridyl-2-thio)methaneCl13CcopperCu(I)CuBr26-mpdsHtribromomethaneCu(μ-X)(μ-ppt)[CuCl2(μ-dpds)2]n3-mpdsnitrogenCuBr(TPTM)methanol[CuCl2(μ-dpds)2]2systems.Pyridine-2-thiolCu(I)Cu(II)BPTMCu–N(py)Ndpds3-mpdsCDCl3chlorideJEOL[Cu(TPTM)(CH3CN)]0/+/2+dpdsC11H10Cl2CuN2S2methanolpyridinecopper[Cu(CH3CN)(TPTM)]PF6HC10H8N2SCuClpyridineHBr(1)–Cu–N(1)Cu(1)methanol2,2′-bis(3-methylpyridine)disulfidegraphitedpdsCu(II)/Cu(III)CH2Cl2Ndpdspptdisulfide S–S2Hmethanol2-dpdsdichloromethaneCHIRALCEL ODdisulfideCH2Cl2–CH3CN1H1HsulfurCH2Cl2Cu(II)potassium cyanideCH2Cl2HpptCH2Cl2CuS–S[CuCl2(dpds)]2tolueneargonCuBr2HchlorideCu(I)CuBrHHtranspyridine NBr(1)–Cu–N(1)*CuBr2(dpds)dpds[Cu(TPTM)(CH3CN)]PF66-mpds6-mpdspyridinenitrogenBPTMHcoppercopper2,2′-dipyridyldisulfideCH2Cl2–CH3CNdpds1,2-propanediolcarbonCHpyridylCl(2)BPTMdpds[CuCl2(μ-dpds)2]ndichloromethane[Cu(μ-Br)(μ-dpds)]nmethanol1-(2-pyridyl)pyridinium-2-thiolate1-(2-pyridyl)pyridinium-2-thiolateacetonitrileCu(II)CuX(tmpa)acetonitrileCHsulfurCe(NH3)2(NO3)4C10H8N7SCuBrCuBracetonitrilediethyl etherCuCl2Cldpdssilica gelCu(II)Hsulfur2HCHdpdstolueneCDCl3CDCl3Br–Cu–Br[Cu(μ-Br)(μ-dpds)]nCu–CpyridinenitrogenacetonitrileHCuClbromide1H-6-methylpyridine-2-thionemethanolmethanoloxygenchloridedpdshydrogenmethanolS–ScarbonpptCu–BrAg/AgClTPTMH13C{1H}3-mpdspptC16H13N3S3Silica-gelHCu(II)Ncopper[Cu(Br)2(μ-BPTM)]npyridine-2-thiolateCu(I)[Cu(μ-Cl)(μ-dpds)]nchloridegraphiteCu–SHdichloromethaneHTPTMargoncoppercopperCu(I) halides13CCuCuBr2CH2Cl22-propanol1HCu(III)oxygen5mpytNhalidecopper complextolueneCH2Cl2C10H8N2S2CuBr2pyridylnitrogenC20H16Br4Cu4N4S4·3CH2Cl2dpdspotassium cyanideCH3Cu–Cloxygen2-bromo-3-methylpyridineBr(1)–Cu–Br(1)*C12H12N2S·0.1H2O-blue[CuBr(ppt)]nTPTMHacetonitrileH1Hbis(2-pyridylthio)methaneCu(II)Cu(I)/Cu(II)dpdschloridedpdscopperS–S–C–N[Cu(TPTM)(CH3CN)]+[Cu(CH3CN)(TPTM)]PF6pptCu(III)CuBr2diethyl etherCuN-confused porphyrinsCu(μ-1-(2-pyridine)pyridiniumthiolato)(μ-Cl)bromideoxygenoxygenligandsbis(2-pyridylthio)methanebromidesmethanolCu(II)–C(sp3)[Cu(TPTM)(CH3CN)]PF61-(2-pyridyl)pyridinium-2-thiolateCuIICl2copper(I)Cusulfurcopperpyridine-2-thiolatedpdsdpdsdpdsCH3CNoxygentoluenemethanolpyridine thiolatemethanolCu(II)TPTMHCH2Cl2HpptCuX(pmap)1-(2-pyridyl)pyridinium-2-thiolbis(pyridyl-2-thio)methaneCu(I)Cl(1)Cu(I)/Cu(II)CuCl2·2H2OTPTMcopperCH2Cl2CH32-dpdstris(2-pyridylthio)methaneNpyridinesulfurpyridine-2-thiolTPTMH1-(2-pyridyl)pyridinium-2-thiolCu(II)[Cu(μ-Br)(μ-dpds)]n6acetonitrileCu(II)–C(sp3)2,2′-dipyridyldisulfideCuBr2(dpds)[CuCl2(μ-dpds)2]nNSulfurCDCl3Pt(5-mpyt)2Pt[CuCl2(BPTM)]npyridinedpds6-mpds6,3-mpptCuCl2CH3CNCuBr(dpds)CDCl3copperCHCHCH2Cl2–CH3CNCHCuBr(TPTM)Cu–BrNC12H12N2S·0.1H2Omagnesium sulfate anhydride[Cu(μ-Br)(μ-ppt)]nmethanol1-(2-pyridyl)pyridinium-2-thiolatepyridine-2-thiolatesulfurcarbonCH2Cl2CuBr2argon2-propanolmethanol[Cu(μ-Br)(μ-dpds)]n2,2′-bis(3-methylpyridyl)disulfideNH[Cu(μ-Br)(μ-dpds)]nCHNdpdsC10H8N2S2CuBrCuBr(TPTM)Cu2I4(BPTM)2MercurymethanolCuCl2·2H2OCH2Cl2pytTPTMHdisulfideCHCuCl2dichloromethaneCu(II)Cu(II)Cu(II)2,2′-bis(6-methylpyridyl)disulfide[Cu4Br4(dpds)2]nCH2Cl2HBPTMmethanolCuCuBr(TPTM)BPTMBPTMCl−CuHHsulfursulfurCH3CNcopper[CuX(TPTM)]0dpdspyridylnitrogenS–SKOHCu(μ-X)(μ-ppt)1Hpyridine-2-thiolBPTM2-dpdsCopper2,2′-bis(3-methylpyridyl)disulfide[Cu(μ-Br)(dpds)]2[Cu(CH3CN)(TPTM)]PF6[Cu(μ-Br)(dpds)]2acetonitrile nitrogen[Cu(TPTM)(CH3CN)]PF6[CuCl2(μ-dpds)2]nbis(2-pyridylthio)methane13CnitrogendpdsC18H15CuF6N4PS3ligandTris(2-pyridylthio)methane[Cu(μ-Cl)(μ-ppt)]nbis(3-methyl-2-pyridine)disulfideTPTMH2-dpds2,2′-bis(3-methylpyridyl)disulfideTPTMCHhydrogenCu(μ-Cl)(μ-dpds)CH2Cl2HNNCHdpdsCuBrchloridecarbonacetonitriledpdsCu–N(acetonitrile)HCuBrC16H12BrCuN3S33,3-mpptHHthiolateCH3CNdpds2,2′-bis(6-methylpyridyl)disulfideC–SCusulfursilica[CuI(μ-Cl)(μ-dpds)]n3-mpdsNClHHacetonitrilesilicapptH[Cu(TPTM)(CH3CN)]PF6oxygenHC–S[Cu(CH3CN)4]PF6TPTMHtolueneCu(1)ethanolcopperppthydrogenC10H8N2S2CuCl2sulfur2,2′-dipyridyldisulfidepyridine-2-thiolCu(II)NTris(2-pyridylthio)methane2,2′-bis(6-methylpyridine)disulfidedpdspyridineBPTMCH2Cl2–CH3CN[Cu(NCMe)4]+[Cu(Cl)2(μ-BPTM)]nCuIClcopperCuIBPTMBPTMC20H16Br4Cu4N4S4·2CH2Cl2dpdsCDCl3bis(2-pyridylthio)methane3-mpdsCu(II)HbromideTPTMHCu(II)2-dpdsC22H20Cu4I4N4S4C10H8N2S2CuCl2methanolCHIRALCEL ODCuBrbis[2-(2-pyridyl)ethyl](2-pyridyl)methylamineS–SpyridineC–SCH3disulfideCuCl2Cu(II)–C(sp3)tolueneCH2Cl2HH1HC11H10Br2CuN2S2CuBr2glassy-carbon-diskCuCl2 [CuCl2(BPTM)]nC10H8N2S2CuBrCH3CNmethanol[Cu(μ-Br)(dpds)]22HcopperCuCuBr(TPTM)C–N[Cu(CH3CN)(TPTM)]PF6CuBr2(dpds)pyridinium nitrogenCu(I)CuCl2(dpds)C10H8N2S2CuCldpdsCu(II)KBrNCuBr(TPTM)CHpytdisulfide[CuCl2(μ-dpds)2]nmethanolC⋯C6-methyl-1-[2-(3-methyl)pyridyl]pyridinium-2-thiolatesulfurCu(II)pyridine-2-thiolatesulfurCu–SCuBr2S–SdichloromethaneCu(I)MethanoldpdsTPTMH[CuCl2(μ-dpds)2]n[Cu(TPTM)(CH3CN)]PF6Cl−chlorideNmethanolSulfurcopper100Isamu KinoshitaL. James WrightSachiko KuboKentaro KimuraAkio SakataToshihiro YanoRiichi MiyamotoTakanori NishiokaKiyoshi IsobeIsamu KinoshitaL. James WrightSachiko KuboKentaro KimuraAkio SakataToshihiro YanoRiichi MiyamotoTakanori NishiokaKiyoshi IsobeDalton Transactionshttp://pubs.rsc.org/en/Content/ArticlePDF/2003/DT/B210420Mhttp://pubs.rsc.org/en/Content/ArticleLanding/2003/DT/B210420M20031993Royal Society of Chemistry1713AkioNNPSakataNNP,,ToshihiroNNPToshihiroAkio Sakata2319RiichiNNPMiyamotoNNP,,TakanoriNNPTakanoriRiichi Miyamoto2523includingVBG[CuCl2(μ-dpds)]B-CM[CuCl2(μ-dpds)]including1610betainNN-HYPHcontainingVBGproductNN,,[Cu(μ-1-(2-pyridine)pyridiniumthiolato)(μ-Cl)]B-CM[Cu(μ-1-(2-pyridine)pyridiniumthiolato)(μ-Cl)]betain - containing product2523complexJJ[Cu(CH3CN)(TPTM)]PF6B-CM[Cu(CH3CN)(TPTM)]PF6complex1410hexanuclearJJcomplexNN,,[Cu(μ-pyt)]6NN[Cu(μ-pyt)]6hexanuclear complex62H-shapedJJcellNN(-LRB-ϕNNϕH-shaped cell62H-shapedJJcellNN(-LRB-ϕNNϕH-shaped cell129nmNN(-LRB-εNNεnm3733H-shapedJJcellNN(-LRB-ϕNNϕH-shaped cell3733H-shapedJJcellNN(-LRB-ϕNNϕH-shaped cell2318monochromatedJJCu-KαNNradiationNN(-LRB-λNNλmonochromated Cu-Kα radiation3931RigakuNNPAFC-7SNNPdiffractometerNNusingVBGMo-KαNNradiationNN(-LRB-λNNλRigaku AFC-7S diffractometer using Mo-Kα radiation2419monochromatedJJMo-KαNNradiationNN(-LRB-λNNλmonochromated Mo-Kα radiation127-HYPHcontainingVBGmaterialNN,,[CuI(μ-Cl)(μ-dpds)]nB-CM[CuI(μ-Cl)(μ-dpds)]n- containing material86formulaNN[Cu(μ-Br)(dpds)]2B-CM[Cu(μ-Br)(dpds)]2formula2926congenerNN,,[Cu(μ-Cl)(dpds)]2NN[Cu(μ-Cl)(dpds)]2congener52congenerNN,,[Cu(μ-Cl)(dpds)]2NN[Cu(μ-Cl)(dpds)]2congener62interestingJJproductNN,,[Cu(TPTM)(CH3CN)]PF6B-CM[Cu(TPTM)(CH3CN)]PF6interesting product1814relatedJJcomplexNN,,[CuBr(TPTM)]B-CM[CuBr(TPTM)]related complex128interestingJJelectrochemistryNN(-LRB-TableNNTableinteresting electrochemistry41contrastNN,,[CuBr(TPTM)]B-CM[CuBr(TPTM)]contrast74resultNN,,[CuBr(TPTM)]B-CM[CuBr(TPTM)]result2724formNN,,[CuX(TPTM)]0B-CM[CuX(TPTM)]0form1310nmNN,,εNNεnm2320nmNN,,εNNεnm3633nmNN,,εNNεnm6664anionicJJTPTMB-CMTPTManionic96nmNN,,εNNεnm1916nmNN,,εNNεnm3027nmNN,,εNNεnm1410frozenJJglassNN(-LRB-[Cu(TPTM)(CH3CN)]PF6B-CM[Cu(TPTM)(CH3CN)]PF6frozen glass1814dimericJJcomplexNN,,[Cu(μ-Br)(dpds)]2B-CM[Cu(μ-Br)(dpds)]2dimeric complex1614differentJJBPTMB-CMBPTMdifferent1614complexNN[Cu(TPTM)(CH3CN)]PF6B-CM[Cu(TPTM)(CH3CN)]PF6complex40K.NNPJohnsonNNP,,ORTEPNNPORTEPK. Johnson3228OakNNPRidgeNNP,,TNNNPTNOak Ridge2003-05-152,2′-dipyridyldisulfidedpdsbis(2-pyridylthio)methaneBPTMtris(2-pyridylthio)methaneTPTMHpyridine-2-thiolatepyt5-methylpyridine-2-thiolate5mpyt1-(2-pyridyl)pyridinium-2-thiolatepptbis(2-pyridylthio)methaneBPTM149.44 ( 6-py ) , 136.024-py122.50 ( 3-py ) , 119.715-pyTris(2-pyridylthio)methaneTPTM136.31 ( 4-py ) , 122.203-py6-methyl-1-[2-(3-methyl)pyridyl]pyridinium-2-thiolate6,3-mppt2,2′-bis(3-methylpyridyl)disulfide3-mpds2,2′-bis(6-methylpyridyl)disulfide6-mpds2,2′-dipyridyldisulfidedpds1-(2-pyridyl)pyridinium-2-thiolateppt1-(2-pyridyl)pyridinium-2-thiolateppt2,2′-bis(6-methylpyridine)disulfide6-mpds2,2′-bis(3-methylpyridine)disulfide3-mpds2,2′-bis(3-methylpyridyl)disulfide3-mpds2,2′-bis(6-methylpyridyl)disulfide6-mpds6-methyl-1-[2-(3-methyl)pyridyl]pyridinium-2-thiolate6,3-mppt2,2′-bis(3-methylpyridyl)disulfide3-mpds2,2′-bis(6-methylpyridyl)disulfide6-mpds6-methyl-1-[2-(3-methyl)pyridyl]pyridinium-2-thiolate6,3-mppt2,2′-bis(6-methylpyridyl)disulfide6-mpdsthe new ligandTris(2-pyridylthio)methaneTPTMH2,2′-dipyridyldisulfide2-dpds1-(2-pyridyl)pyridinium-2-thiolatepptbis(2-pyridylthio)methaneBPTM2,2′-dipyridyldisulfidedpdstris(2-pyridylthio)methaneTPTMH