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Formic acid i yin’wana ya ti candidates leti tshembisaka swinene eka vuhlayiselo bya nkarhi woleha bya liquid hydrogen. Laha hi humesa nxaxamelo wa ti-ruthenium clamp complexes letintshwa leti nga na fomula yo angarhela [RuHCl(POP)(PPh3)] hi ku tirhisa ti-ligand ta tridentate POP clamp leti xavisiwaka kumbe leti endliweke hi ku olova. Hi tirhise ti complexes leti ku dehydrogenate formic acid ku humelerisa CO2 na H2 ehansi ka swiyimo swo olova, leswinga na reflux hiku tirhisa ionic liquid BMIM OAc (1-butyl-3-methylimidazolium acetate) tani hi solvent. Kusuka eka mavonelo ya nhlayo yale henhla ya ku cinca, catalyst leyi tirhaka swinene i [RuHCl(xantphos)(PPh3)]Ru-1 complex leyi tivekaka eka matsalwa, leyingana nhlayo yale henhla ya ku cinca ka 4525 h-1 eka 90 °C kuringana 10 min. Mpimo wa le ndzhaku ka ku hundzuka a wu ri 74%, naswona ku hundzuriwa ku hetisiwile ku nga si hela tiawara ta 3 (>98%). Hi tlhelo rin’wana, catalyst leyingana matirhelo ya kahle swinene hiku angarhela, novhele [RuHCl(iPr-dbfphos)(PPh3)]Ru-2 complex, yi hlohletela ku hundzuka loku heleleke eka 1 h, leswi endlaka leswaku kuva na mpimo wa ku cinca hinkwako wa 1009 h-1. Ku engetela kwalano, ntirho wa catalytic wutlhele wu voniwa eka mahiselo lawa yanga fika eka 60 °C. Eka xiphemu xa gasi, i CO2 na H2 ntsena leswi voniweke; CO a yi voniwanga. High-resolution mass spectrometry yi kombisile vukona bya N-heterocyclic carbene complexes eka nkatsakanyo wa reaction.
Xiphemu xa makete lexi kulaka xa eneji leyi pfuxetiwaka na ku cinca-cinca ka yona swi endle leswaku ku va na xilaveko xa thekinoloji yo hlayisa eneji ya xiyimo xa tiindasitiri eka swiyenge swa gezi, ku hisa, tiindasitiri na vutleketli1,2. Hydrogen yi tekiwa tani hi yin’wana ya ti rhwari ta eneji leti nga tala swinene3, naswona ti liquid organic hydrogen carriers (LOHCs) sweswinyana ti hundzuke nhlokomhaka ya ndzavisiso, leswi nyikaka xitshembiso xo hlayisa hayidirojeni hi xivumbeko lexi lulamisiwaka hi ku olova handle ka swiphiqo leswi fambelanaka na ntshikelelo kumbe thekinoloji ya cryogenic4. ,5,6. Hikwalaho ka swivumbeko swa tona swa xiviri, vunyingi bya switirhisiwa swa vutleketli leswi nga kona swa petirolo na mafurha man’wana ya mati swi nga tirhisiwa ku fambisa LOHC7,8. Swihlawulekisi swa physical acid (FA) swiendla leswaku yiva candidate leyi tshembisaka eka vuhlayiselo bya hydrogen leyingana ntiko wa hydrogen wa 4.4%9,10. Hambiswiritano, tisisiteme ta catalytic leti kandziyisiweke ta formic acid dehydrogenation hi ntolovelo ti lava ku tirhisiwa ka ti volatile organic solvents, mati kumbe pure formic acid,11,12,13,14 leswinga lavaka kutirhisiwa ka ti solvent vapor separation techniques tofana na condensation, leswinga tisaka swiphiqo eka switirhisiwa swa vatirhisi. switirhisiwa, ndzhwalo wo engetela. Xiphiqo lexi xinga hluriwa hiku tirhisa ti solvents letingana ntshikelelo wa vapor lowu nga nyawuriki, kufana na ti ionic liquids. Khale, ntlawa wa hina wa ntirho wu kombisile leswaku ionic liquid butylmethylimidazolium acetate (BMIM OAc) i solvent leyi faneleke eka nhlamulo leyi hi ku tirhisa fixing complex leyi xavisiwaka Ru-PNP Ru-MACHO type 15. Xikombiso, hi kombisile FA dehydrogenation eka sisiteme ya ku khuluka loku yaka emahlweni hi ku tirhisa BMIM OAc , ku fikelela TON yo tlula 18,000,000 eka 95°C. Hambi leswi maendlelo yan’wana khale yanga fikelela TON yale henhla, yotala ya titshege hi ti volatile organic solvents (kufana na THF kumbe DMF) kumbe swiengeteri leswi tirhisiwaka (kufana na ti bases). Kuhambana na sweswo, ntirho wa hina entiyisweni wu tirhisa ti non-volatile ionic liquids (ILs) naswona kungari na swiengeteri.
Hazari na Bernskoetter va vikile ku susiwa ka hydrogenation ya formic acid (FA) eka 80 °C hiku tirhisa Fe-PNP catalyst eka vukona bya dioxane na LiBF4, leswi fikeleleke nhlayo yo hlamarisa ya turnover (TON) ya kwalomu ka 1,000,00016. Laurenci u tirhise Ru(II)- complex catalyst TPPPTS eka sisiteme ya FA dehydrogenation leyi yaka emahlweni. Ndlela leyi yi endle leswaku kuva na FA dehydrogenation leyi lavaka ku hetiseka laha kungana swiphemu swintsongo swinene swa CO leswi kumiweke eka 80 °C17. Ku yisa emahlweni nsimu leyi, Pidko yi kombisile reversible dehydrogenation ya FA hiku tirhisa Ru-PNP clamp catalysts eka swihlanganisi swa DMF/DBU na DMF/NHex3, ku fikelela mimpimo ya TON ya 310,000 kuya eka 706,500 eka 90 °C18. Hull, Himeda na Fujita va dyondze hi binuclear Ir complex catalyst laha KHCO3 na H2SO4 swi endliweke magandzelo, ku cincana CO2 hydrogenation na FA dehydrogenation. Maendlelo ya vona ya fikelerile ti TONs to tlula 3,500,000 na 308,000 hiku landzelelana eka hydrogenation eka 30°C, CO2/H2 (1:1), 1 bar pressure xikan’we na dehydrogenation exikarhi ka 60 na 90°C19. Sponholz, Junge na Beller va tumbuluxile Mn-PNP complex ya reversible CO2 hydrogenation na FA dehydrogenation eka 90 °C20.
Laha hi tirhise endlelo ra IL, kambe ematshan’wini yo tirhisa ti Ru-PNPs, hi lavisisile ku tirhisiwa ka ti catalysts ta Ru-POP, leswi hi ku tiva ka hina swi nga si kombisiwaka khale eka mhaka leyi.
Hikwalaho ka ku hlanganisiwa ka tona lokunene ka nsimbi-ligand (MLC), ti-amino-PNP clamp complexes leti simekiweke eka miehleketo ya muxaka wa Noyori na mintlawa ya ntirho wa amino ya vumbirhi leyi tirhisanaka 21 (ku fana na Ru-MACHO-BH) hi ntolovelo yi ya yi duma swinene eka matirhelo man’wana ya timolekhuli letitsongo. Swikombiso leswi dumeke swi katsa CO22, hydrogenation ya ti alkenes na carbonyls, transfer hydrogenation23 na acceptorless dehydrogenation ya ti alcohols24. Ku vikiwile leswaku N-methylation ya PNP clamp ligands yinga yimisa hiku hetiseka ntirho wa catalyst25, leswinga hlamuseriwa hi mhaka ya leswaku ti amines ti tirha tani hi swihlovo swa proton, leswinga xilaveko xa nkoka hi nkarhi wa catalytic cycle hiku tirhisa MLC. Hambiswiritano, ntshamiseko lowu hambaneke eka formic acid dehydrogenation wu voniwe sweswinyana hi Beller, laha ti N-methylated Ru-PNP complexes entiyisweni ti kombiseke catalytic dehydrogenation yo antswa ya formic acid ku tlula ti counterparts ta tona leti nga methylated26. Leswi khale ka complex yinga kotiki ku nghenelela eka MLC hiku tirhisa amino unit, leswi swi ringanyeta swinene leswaku MLC, naswona hikokwalaho ka sweswo amino unit, yinga tlanga xiave xa nkoka swinene eka ku cinca kun’wana ka (de)hydrogenation kutlula leswi aswi ehleketiwile khale.
Loko ku pimanyisiwa na ti POP clamps, ti ruthenium complexes ta ti POP clamps ati kamberiwanga ngopfu eka ndzhawu leyi. Ti ligands ta POP hi ndzhavuko ti tirhisiwile ngopfu eka hydroformylation, laha ti tirhaka tani hi ti chelating ligands kutlula xihlawulekisi xa bidentate bite angle ya kwalomu ka 120° eka ti clamping ligands, leti tirhisiweke ku antswisa ku hlawula eka switirhisiwa swa linear na branched27,28,29. Kusukela kwalano, ti Ru-POP complexes ati tirhisiwa ngopfu eka hydrogenation catalysis, kambe swikombiso swa ntirho wa tona eka transfer hydrogenation swivikiwile khale30. Laha hi kombisa leswaku Ru-POP complex i catalyst leyi tirhaka kahle eka dehydrogenation ya formic acid, leswi tiyisisaka ku tshuburiwa ka Beller leswaku amino unit eka classical Ru-PNP amine catalyst ayi na nkoka ngopfu eka reaction leyi.
Dyondzo ya hina yi sungula hi ku hlanganisiwa ka swihlohloteri swimbirhi leswi tolovelekeke leswi nga na fomula yo angarhela [RuHCl(POP)(PPh3)] (Fig. 1a). Ku cinca xivumbeko xa steric na electronic, dibenzo[b,d]furan yi hlawuriwile kusuka eka 4,6-bis(diisopropylphosphino) leyi xavisiwaka (Fig. 1b) 31. Ti catalysts leti dyondziweke eka ntirho lowu ti endliwile hiku tirhisa ndlela yo angarhela leyi tumbuluxiweke hi Whittlesey32, hiku tirhisa [RuHCl(PPh3)3]•toluene33 adduct tani hi precursor. Hlanganisa metal precursor na POP clamp ligand eka THF ehansi ka swiyimo swa strictly anhydrous na anaerobic. Ku cinca cinca loku aku fambisana na ku cinca lokukulu ka muhlovo kusuka eka purple ya ntima kuya eka yotshuka naswona swinyikile xitirhisiwa xo basa endzhaku ka 4 wa tiawara ta reflux kumbe 72 wa tiawara ta reflux eka 40°C. Endzhaku ko susa THF eka vacuum naku hlantswiwa kambirhi hi hexane kumbe diethyl ether, triphenylphosphine yi susiwile kuva yinyika xiendliwa tani hi powder yotshuka eka mbuyelo wale henhla wa nhlayo.
Ku hlanganisiwa ka swivumbeko swa Ru-1 na Ru-2. a) Ndlela yo hlanganisa swilo leswi rharhanganeke. b) Xivumbeko xa xivumbeko lexi hlanganisiweke.
Ru-1 se ya tiviwa ku suka eka matsalwa32, naswona ku ya emahlweni ka vumunhuhati ku kongomisa eka Ru-2. 1H NMR spectrum ya Ru-2 yi tiyisisile xivumbeko xa cis xa athomo ya phosphine eka ligand ya hydride pair. Ploto ya peak dt (Fig. 2a) yi kombisa 2JP-H coupling constants ya 28.6 na 22.0 Hz, leyi nga endzeni ka mpimo lowu languteriweke wa swiviko swa khale32. Eka hydrogen decoupled 31P{1H} spectrum (Fig. 2b), 2JP-P coupling constant ya kwalomu ka 27.6 Hz yi voniwile, leswi tiyisisaka leswaku havumbirhi bya ti clamp ligand phosphines na PPh3 i cis-cis. Ku engetela kwalano, ATR-IR yikombisa xihlawulekisi xa ruthenium-hydrogen stretching band eka 2054 cm-1. Ku ya emahlweni ku hlamuseriwa xivumbeko, Ru-2 complex yi crystallized hi vapor diffusion eka mahiselo ya kamara na khwalithi leyi ringaneleke eka tidyondzo ta X-ray (Fig. 3, Tafula ro Engetela 1). Yi crystallize eka triclinic system ya space group P-1 na cocrystalline benzene unit yin’we hi unit cell. Yi kombisa angle yo anama ya P-Ru-P occlusal ya 153.94°, leyi anameke swinene kutlula 130° occlusal angle ya bidentate DBFphos34. Eka 2.401 na 2.382 Å, ku leha ka Ru-PPOP bond ku lehe swinene kutlula ku leha ka Ru kuya eka PPh3 bond ya 2.232 Å, leswingava mbuyelo wa wide backbone snack angle ya DBFphos leyi vangiwaka hi 5-ring ya yona yale xikarhi. Geometry ya senthara ya nsimbi hi xiviri i octahedral na O-Ru-PPh3 angle ya 179.5°. Nhlanganiso wa H-Ru-Cl awu linear hiku hetiseka, na angle ya kwalomu ka 175° kusuka eka triphenylphosphine ligand. Ti distance ta athomo na ku leha ka bond swi xaxametiwile eka Tafula ra 1.
Xiphemu xa NMR xa Ru-2. a) Ndzhawu ya hydrode ya 1H NMR spectrum leyi kombisaka xikombiso xa Ru-H dt. b) 31 P{ 1 H} NMR spectrum leyi kombisaka swikombiso leswi humaka eka triphenylphosphine (ya wasi) na POP ligand (ya rihlaza).
Xivumbeko xa Ru-2. Ti thermal ellipsoids ti kombisiwa hi 70% wa ku koteka. Leswaku swi va erivaleni, tiatomo ta cocrystalline benzene na hydrogen eka khaboni ti tshikiwile.
Ku kambela vuswikoti bya ti complex ku dehydrogenate formic acid, swiyimo swa reaction swi hlawuriwile laha ehansi ka swona ti complexes ta PNP-clamp leti fambelanaka (xikombiso, Ru-MACHO-BH) a ti tirha swinene15. Ku susiwa ka hayidirojeni ya 0.5 ml (13.25 mmol) ya formic acid hiku tirhisa 0.1 mol% (1000 ppm, 13 μmol) ruthenium complex Ru-1 kumbe Ru-2 hiku tirhisa 1.0 ml (5.35 mmol) ionic liquid (IL) BMIM OAc (xifaniso xa tafula) 2; Xifaniso xa 4);
Ku kuma standard, reaction yisungule ku endliwa hiku tirhisa precursor adduct [RuHCl(PPh3)3]·toluene. Ku cinca cinca loku ku endliwa eka mahiselo kusuka eka 60 kuya eka 90 °C. Kuya hi swivono swo olova leswi voniwaka, complex ayi nga swikoti ku n’oka hiku hetiseka eka IL hambi kuri ku hlanganisiwa nkarhi woleha eka mahiselo ya 90°C, kambe ku n’oka ku humelerile endzhaku ka ku nghenisiwa ka formic acid. Eka 90°C, ku cinca ka 56% (TOF = 3424 h-1) swifikeleriwile eka timinete ta 10 tosungula, naswona kwalomu ka ku cinca ka nhlayo (97%) swifikeleriwile endzhaku ka tiawara tinharhu (entry 1). Ku hunguta mahiselo kuya eka 80 °C swihunguta ku cinca kutlula hafu kuya eka 24% endzhaku ka 10 min (TOF = 1467 h-1, entry 2), leswi yaka emahlweni swihunguta kuya eka 18% na 18% eka 70 °C na 60 °C, hiku landzelelana 6% (entries 3 na 4). Eka swiyimo hinkwaswo, akuri hava nkarhi wa induction lowu kumiweke, leswi kombaka leswaku catalyst yingava yiri tinxaka ta reactive kumbe leswaku ku hundzuriwa ka tinxaka ta reactive swi hatlisa swinene kuva swi voniwa hiku tirhisa data set leyi.
Endzhaku ka ku kamberiwa ka precursor, ti Ru-POP clamp complexes Ru-1 na Ru-2 ti tirhisiwile ehansi ka swiyimo leswi fanaka. Eka 90°C, ku hundzuka lokukulu ku hatle ku voniwa. Ru-1 yifikelerile ku cinca ka 74% eka timinete tosungula ta 10 ta xikambelo (TOFmax = 4525 h-1, entry 5). Ru-2 yi kombisile ntirho wutsongo nyana kambe lowu nga cincekiki, wu hlohletela ku hundzuka ka 60% eka 10 min (TOFmax = 3669 h-1) na ku hundzuka loku heleleke eka 60 min (>99%) (entry 9). Swile rivaleni leswaku Ru-2 yi tlakukile swinene eka nsimbi ya precursor na Ru-1 eka ku hundzuka loku heleleke. Hikokwalaho, loko metal precursor na Ru-1 swiri na mimpimo yofana ya TOFoverall eka ku hetisisiwa ka reaction (330 h-1 na 333 h-1, hiku landzelelana), Ru-2 yina TOFoverall ya 1009 h-1.
Ru-1 na Ru-2 switlhele swiendliwa ku cinca ka mahiselo laha mahiselo yanga hunguteka hakatsongotsongo hiku engeteleriwa ka 10 °C kuya eka nhlayo yale hansi ya 60 °C (Fig. 3). Loko eka 90°C complex yikombe ntirho wa xihatla, kwalomu ka ku hundzuka loku heleleke swihumelerile endzhaku ka awara, kutani eka mahiselo yale hansi ntirho wuhunguteke swinene. Ku hundzuriwa ka Py-1 akuri 14% na 23% endzhaku ka 10 min eka 80°C na 70°C, hiku landzelelana, naswona endzhaku ka 30 min swi tlakuke kuya eka 79% na 73% (entries 6 na 7). Swikambelo leswi haswimbirhi swi kombisile mpimo wa ku hundzuka wa ≥90% eka tiawara timbirhi. Mahanyelo yo fana ya voniwe eka Ru-2 (entries 10 na 11). Lexi tsakisaka, Ru-1 ayi ri na matimba nyana emakumu ka reaction eka 70 °C na TOF hinkwayo ya 315 h-1 loko ku pimanyisiwa na 292 h-1 eka Ru-2 na 299 h-1 eka metal precursor.
Kuhunguteka kun’wana ka mahiselo kuya eka 60 °C swiendle leswaku kungavi na ku cinca loku voniweke eka timinete tosungula ta 30 ta xikambelo. Ru-1 ayi tirhi ngopfu eka mahiselo yale hansi swinene ekusunguleni ka experiment naswona endzhaku ka sweswo yi engetele ntirho, leswi kombaka xilaveko xa nkarhi wa activation laha Ru-1 precatalyst yi hundzuriwaka eka tinxaka leti tirhaka hi catalytically. Hambi leswi leswi swinga kotekaka eka mahiselo hinkwawo, 10 wa timinete ekusunguleni ka xikambelo aswi enelanga ku kuma nkarhi wa activation eka mahiselo yale henhla. Mahanyelo lama fanaka ya kumiwile eka Ru-2. Eka 70 na 60 °C, akuri hava ku cinca loku voniweke eka 10 min yosungula ya xikambelo. I swa nkoka ku xiya leswaku eka swikambelo leswimbirhi, ku tumbuluxiwa ka khaboni monokisayidi a swi voniwanga endzeni ka mpimo wa ku kumiwa ka xitirhisiwa xa hina (<300 ppm), laha H2 na CO2 ku nga swona ntsena swikumiwa leswi voniweke.
Ku pimanisiwa ka mbuyelo wa formic acid dehydrogenation lowu kumiweke khale eka ntlawa lowu wa ntirho, lowu yimelaka xiyimo xa vutshila na ku tirhisa ti Ru-PNP clamp complexes, swi kombisile leswaku Ru-POP clamp leyintshwa leyi endliweke yi na ntirho lowu fanaka na wa PNP counterpart ya yona 15. Loko clamp PNP yi fikelela ti RPMs ta 500-1260 h-1 eka swikambelo swa batch, clamp leyintshwa ya POP yi fikelerile nkoka lowu fanaka wa TOFovertal wa 326 h-1, na mimpimo ya TOFmax ya Ru-1 na 1590 h-1 yi voniwile. hi ku landzelelana, i 1988 h-1 na 1590 h-1. Ru-2 i 1 eka 80 °C, Ru-1 i 4525 h-1 na Ru-1 i 3669 h-1 eka 90 °C, hiku landzelelana.
Ku kamberiwa ka mahiselo ya formic acid dehydrogenation hiku tirhisa Ru-1 na Ru-2 catalysts. Swiyimo: 13 μmol ya xihlohloteri, 0.5 ml (13.25 mmol) ya formic acid, 1.0 ml (5.35 mmol) ya BMIM OAc.
NMR yi tirhisiwa ku twisisa tindlela ta ku angula. Leswi kungana ku hambana lokukulu swinene eka 2JH-P exikarhi ka hydride na phosphine ligands, nhlokomhaka ya ndzavisiso lowu yi le ka nhlohlorhi ya hydride. Eka Ru-1, xivumbeko xa dt lexi tolovelekeke xa yuniti ya hydrogenation xikumeke eka timinete tosungula ta 60 ta dehydrogenation. Hambi leswi kungana ku cinca lokukulu ka downfield kusuka eka −16.29 kuya eka −13.35 ppm, ti coupling constants ta yona na phosphine i 27.2 na 18.4 Hz, hiku landzelelana (Figure 5, Peak A). Leswi swi fambisana na ti phosphines hinkwato tinharhu laha ligand ya hydrogen yinga eka xivumbeko xa cis naswona swiringanyeta leswaku xivumbeko xa ligand xitshamisekile nyana eka IL kuringana kwalomu ka awara yin’we ehansi ka swiyimo leswi antswisiweke swa reaction. Ku cinca lokukulu ka downfield kungava hikokwalaho ka ku herisiwa ka ti chlorinated ligands xikan’we naku vumbiwa ka ti acetyl-formic acid complexes leti fambelanaka, ku vumbiwa ka in situ ka d3-MeCN complex eka NMR tube, kumbe ku vumbiwa ka ti N-heterocycles leti fambelanaka. ku hlamuserile. Xivumbeko xa khabeni (NHC). Hi nkarhi wa dehydrogenation reaction, matimba ya xikombiso lexi ya ye emahlweni ya hunguteka, naswona endzhaku ka 180 wa timinete xikombiso lexi a xi nga ha voniwi. Ematshan’weni ya sweswo, ku tshuburiwe swikombiso swimbirhi leswintshwa. Xosungula xikombisa xivumbeko xa dd lexi nga erivaleni lexi humelelaka eka -6.4 ppm (peak B). Doublet yina coupling constant leyikulu ya kwalomu ka 130.4 Hz, leswi kombaka leswaku yin’wana ya ti phosphine units yi fambile loko yi pimanisiwa na hydrogen. Leswi swinga vula leswaku POP clamp yi lulamisiwile nakambe kuva κ2-P,P configuration. Ku vonaka ka complex leyi endzhaku ka nkarhi eka catalysis swinga kombisa leswaku muxaka lowu wu yisa eka tindlela ta deactivation hiku famba ka nkarhi, leswi endlaka catalyst sink. Hi tlhelo rin’wana, ku cinca ka tikhemikhali ta le hansi ku ringanyeta leswaku yi nga va muxaka wa dihydrogenous15. Nhlohlorhi ya vumbirhi leyintshwa yi kumeka eka -17.5 ppm. Hambi leswi fold ya yona yinga tivekiki, hi tshemba leswaku i triplet leyingana coupling constant leyintsongo ya 17.3 Hz, leswi kombaka leswaku hydrogen ligand yi boha ntsena eka phosphine ligand ya POP clamp, leswi tlhelaka swikomba ku humesiwa ka triphenylphosphine (peak C). Yinga siviwa hi ligand yin’wana, kufana na ntlawa wa acetyl kumbe NHC leyi vumbiweke in situ kusuka eka ionic liquid. Dissociation ya PPh3 yitlhela yi kombisiwa hi singlet yo tiya eka -5.9 ppm. eka 31P{1H} spectrum ya Ru-1 endzhaku ka 180 wa timinete eka 90 °C (vona vuxokoxoko byo engetela).
Ndzhawu ya hydrogen ya 1H NMR spectrum ya Ru-1 hi nkarhi wa dehydrogenation ya formic acid. Swiyimo swa nhlamulo: 0.5 ml ya formic acid, 1.0 ml ya BMIM OAc, 13.0 μmol ya catalyst, 90 °C. NMR yi tekiwile kusuka eka MeCN-d 3 , 500 μl ya deuterated solvent, kwalomu ka 10 μl ya nkatsakanyo wa reaction.
Ku ya emahlweni ku tiyisisa vukona bya tinxaka leti tirhaka eka sisiteme ya catalytic, nxopaxopo wa high resolution mass spectrometry (HRMS) wa Ru-1 wu endliwile endzhaku ka ku cheriwa ka formic acid kuringana 10 min eka 90 °C. Leswi swikomba vukona bya tinxaka leti pfumalaka chlorine ligand precatalyst eka nkatsakanyo wa reaction. xikan’we na ti-NHC complex timbirhi, swivumbeko leswi ehleketiwaka swa swona swi kombisiwile eka Xifaniso xa 6. Xiphemu xa HRMS lexi fambelanaka xi nga voniwa eka Xifaniso xo Engetela xa 7.
Hiku ya hi data leyi, hi ringanyeta endlelo ra intrasphere reaction leri fanaka na leri ringanyetiweke hi Beller, laha ti N-methylated PNP clamps ti catalyze reaction leyi fanaka. Swikambelo leswi engetelekeke leswi nga katsiwiki mati ya ionic a swi kombisanga ntirho wihi na wihi, hikwalaho ku nghenelela ka yona hi ku kongoma ku vonaka ku laveka. Hi ehleketa leswaku ku tirhisiwa ka Ru-1 na Ru-2 ku humelela hi ku hambanisiwa ka chloride loku landzeriwaka hi ku engeteriwa ka NHC loku nga kotekaka na ku hambanisiwa ka triphenylphosphine (Xikimi 1a). Ku tirhisiwa loku eka tinxaka hinkwato swivoniwe khale hiku tirhisa HRMS. IL-acetate i Bronsted base yo tiya ku tlula formic acid naswona yi nga deprotonate swinene leyi yo hetelela35. Hi ehleketa leswaku hi nkarhi wa xirhendzevutani xa catalytic (Xikimi 1b), tinxaka leti tirhaka ta A leti nga na NHC kumbe PPh3 ti hlanganisiwa hi ku tirhisa formate ku vumba muxaka wa B. Ku lulamisiwa nakambe ka complex leyi ku ya eka C eku heteleleni swi endla leswaku ku humesiwa CO2 na trans-dihydrogen complex D Ku protonation loku landzelaka ka acid ku va dihydro complex na acetic acid leyi vumbiweke khale ku vumba dihydro complex E is kufana na goza ra nkoka leri ringanyetiweke hi Beller hiku tirhisa N-methylated PNP clamp homologues. Ku engetela kwalano, analogue ya complex EL = PPh3 khale yi endliwile hi stoichiometric reaction hiku tirhisa Ru-1 eka xibakabaka xa hydrogen endzhaku ko humesiwa ka chloride na sodium salt. Ku susiwa ka hydrogen xikan’we naku hlanganisiwa ka formate swinyika A naswona swihetisisa xirhendzevutani.
Endlelo ra intrasphere reaction ya formic acid dehydrogenation hiku tirhisa fixing complex Ru-POP Ru-1 ya ringanyetiwa.
Xivumbeko lexintshwa xa [RuHCl(iPr-dbfphos)(PPh3)] xi endliwile. Complex leyi yi tiveka hi NMR, ATRIR, EA na X-ray diffraction analysis ya ti crystals tin’we. Hi tlhela hi vika ku tirhisiwa ko sungula loku humelelaka ka ti Ru-POP pincer complexes eka dehydrogenation ya formic acid eka CO2 na H2. Hambi leswi metal precursor yifikeleleke ntirho lowu fanaka (kufikela eka 3424 h-1), complex yifikelele nhlayo yale henhla ya turnover frequency kuya fika eka 4525 h-1 eka 90 °C. Ku tlula kwalaho, eka 90 °C, complex leyintshwa [RuHCl(iPr-dbfphos)(PPh3)] yifikelerile nkarhi hinkwawo wa ku haha ​​(1009 h-1) ku hetisisa formic acid dehydrogenation, leswinga e henhla swinene kutlula ya metal precursor (330 h-1). na xivumbeko lexi vikiweke khale [RuHCl(xantphos)(PPh3)] (333 h-1). Ehansi ka swiyimo leswi fanaka, vuswikoti bya catalytic byi ringanisiwa na bya Ru-PNP clamp complex. Data ya HRMS yikomba vukona bya carbene complex eka nkatsakanyo wa reaction, hambi leswi yinga yitsongo. Sweswi hi le ku dyondzeni ka vuyelo bya catalytic bya ti carbene complexes.
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