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Aside formike ni imwe mu zitanga icyizere cyo kubika hydrogen y'amazi igihe kirekire. Hano turabagezaho urukurikirane rw'ibice bishya bya ruthenium clamp complexes hamwe na formula rusange [RuHCl(POP)(PPh3)] hakoreshejwe ligands za xanthos-type tridentate POP clamp ligands ziboneka ku isoko cyangwa zoroshye gukora. Twakoresheje izi complexes kugira ngo dukuremo aside formike kugira ngo tubone CO2 na H2 mu bihe byoroshye, bidafite reflux dukoresheje ikinyabutabire cya ionic BMIM OAc (1-butyl-3-methylimidazolium acetate) nk'umusemburo. Ukurikije frequency ntarengwa yo guhindura, catalyst nziza cyane ni [RuHCl(xantphos)(PPh3)]Ru-1 complex izwi mu nyandiko, ifite frequency ntarengwa yo guhindura 4525 h-1 kuri 90 °C mu gihe cy'iminota 10. Igipimo cyo guhindura imiterere nyuma yo guhindura imiterere cyari 74%, kandi guhindura imiterere byarangiye mu masaha 3 (>98%). Ku rundi ruhande, catalyst ifite imikorere myiza muri rusange, inkuru nshya [RuHCl(iPr-dbfphos)(PPh3)]Ru-2 complex, itera impinduka yuzuye mu isaha imwe, bigatuma habaho igipimo rusange cy’ihindagurika rya h-1009. Byongeye kandi, ibikorwa bya catalytic byagaragaye no ku bushyuhe bugera kuri 60 °C. Mu gice cya gaze, CO2 na H2 gusa ni byo byagaragaye; CO2 ntabwo yabonetse. Spectrometry y’uburemere ifite ubushobozi bwo hejuru yagaragaje ko hari complexes za N-heterocyclic carbene mu ruvange rw’ibisubizo.
Isoko ry’ingufu zisubira kwiyongera hamwe n’ihindagurika ryazo byatumye hakenerwa ikoranabuhanga ryo kubika ingufu mu nganda mu nzego z’ingufu, ubushyuhe, inganda n’ubwikorezi1,2. Hydrogen ifatwa nk'imwe mu zitwara ingufu nyinshi3, kandi zitwara hydrogen y’amazi (LOHCs) ziherutse kuba intego y’ubushakashatsi, zitanga icyizere cyo kubika hydrogen mu buryo bworoshye butunganywa nta bibazo bifitanye isano n’umuvuduko cyangwa ikoranabuhanga rituma habaho gushyuha4. ,5,6. Bitewe n’imiterere yazo ifatika, ibikorwa remezo byinshi byo gutwara lisansi n’ibindi bikomoka ku mazi bishobora gukoreshwa mu gutwara LOHC7,8. Imiterere ifatika ya aside formike (FA) ituma iba umukandida mwiza wo kubika hydrogen ifite uburemere bwa hydrogen bwa 4.4%9,10. Ariko, sisitemu za catalytic zasohotse zo gukuraho aside formike ubusanzwe zisaba ikoreshwa ry’ibintu bihumanya ikirere, amazi cyangwa aside formike nziza,11,12,13,14 bishobora gusaba ikoreshwa ry’uburyo bwo gutandukanya umwuka nk’ubushyuhe, bishobora guteza ibibazo mu mikoreshereze y’abaguzi. Iki kibazo gishobora gukemurwa hakoreshejwe imiti ivangavanze ifite umuvuduko muto w’umwuka, nk’ibinyobwa bya ionic. Mbere, itsinda ryacu ryagaragaje ko amazi ya ionic butylmethylimidazolium acetate (BMIM OAc) ari umuti ukwiriye muri iki gikorwa hakoreshejwe uburyo bwo gutunganya ibintu bwa Ru-PNP Ru-MACHO type 15 bugurishwa. Urugero, twerekanye ko FA dehydrogenation muri sisitemu ikomeza gutemba hakoreshejwe BMIM OAc, tugera kuri TON irenga 18.000.000 kuri 95°C. Nubwo hari sisitemu zageze kuri TON nyinshi, nyinshi zishingiye ku miti ivangavanze (nka THF cyangwa DMF) cyangwa inyongeramusaruro zikoreshwa (nk’ibice). Mu buryo bunyuranye, akazi kacu gakoresha amazi ya ionic adahindagurika (ILs) kandi nta nyongeramusaruro zikoreshwa.
Hazari na Bernskoetter batangaje ko aside formic (FA) yakuweho umwuka kuri 80 °C bakoresheje catalyst ya Fe-PNP imbere ya dioxane na LiBF4, bagera ku mubare utangaje w’ihindagurika ry’ikirere (TON) wagera kuri 1.000.00016. Laurenci yakoresheje catalyst ya Ru (II)- complex TPPPTS muri sisitemu yo gukuraho umwuka kuri FA. Ubu buryo bwatumye FA ikurwaho umwuka neza cyane, haboneka ibimenyetso bike bya CO kuri 80 °C17. Kugira ngo bakomeze guteza imbere uru rwego, Pidko yagaragaje uburyo FA ikurwaho umwuka ikoresheje catalyst ya Ru-PNP clamp muri DMF/DBU na DMF/NHex₃ mixes, bagera ku gaciro ka TON kari hagati ya 310.000 na 706.500 kuri 90 °C18. Hull, Himeda na Fujita bigaga kuri catalyst ya binuclear Ir complex aho KHCO3 na H2SO4 byatambwaga, bisimburana kuri hydrogenation ya CO2 na FA ikurwaho umwuka. Sisitemu zabo zageze kuri TON zirenga 3,500,000 na 308,000 mu rwego rwo kongeramo hydrogenation kuri 30°C, CO2/H2 (1:1), umuvuduko wa bar 1 no kongeramo hydrogenation hagati ya 60 na 90°C19. Sponholz, Junge na Beller bakoze complex ya Mn-PNP yo kongeramo hydrogenation ya CO2 na FA kuri 90°C20.
Aha twakoresheje uburyo bwa IL, ariko aho gukoresha Ru-PNPs, twasesenguye ikoreshwa rya Ru-POP catalysts, uko tubizi, ritigeze rigaragazwa mbere muri urwo rwego.
Bitewe n’uburyo bwiza bwo guhuza metal-ligand (MLC), amino-PNP clamp complexes zishingiye ku bitekerezo bya Noyori hamwe n’amatsinda y’imikorere ya amino 21 (nka Ru-MACHO-BH) muri rusange zigenda zikundwa cyane mu mikorere mito ya molekile. Ingero zikunzwe zirimo CO22, hydrogenation ya alkenes na carbonyls, transfer hydrogenation23 no receptor dehydrogenation ya alcohols24. Byatangajwe ko N-methylation ya PNP clamp ligands ishobora guhagarika burundu imikorere ya catalyst25, ibi bikaba bishobora gusobanurwa n’uko amines zikora nk’isoko ya proton, ibi bikaba ari ngombwa cyane mu gihe cya catalytic cycle ikoresha MLC. Ariko, Beller aherutse kubona ko ibinyuranye n’ibyo muri formic acid dehydrogenation, aho N-methylated Ru-PNP complexes byagaragaje catalytic dehydrogenation nziza ya aside formic kurusha izindi zidafite methylation26. Kubera ko urusobe rwa kera rudashobora kwitabira MLC binyuze muri amino unit, ibi bigaragaza cyane ko MLC, bityo na amino unit, ishobora kugira uruhare ruto mu mpinduka zimwe na zimwe (de) hydrogenation kurusha uko byatekerezwaga mbere.
Ugereranije na POP clamps, complexes za ruthenium za POP clamps ntizigeze zisuzumwa bihagije muri uru rwego. POP ligands ubusanzwe zakoreshejwe cyane cyane mu gukwirakwiza hydroformylation, aho zikora nk'inguni ya chelating ligands aho kuba nk'inguni iranga bidentate bite ya hafi 120° yo gufunga ligands, zakoreshejwe mu kunoza uburyo bwo guhitamo ibicuruzwa biri ku murongo n'ibice 27,28,29. Kuva icyo gihe, complexes za Ru-POP ntizakoreshejwe cyane mu gukwirakwiza hydrogenation, ariko ingero z'ibikorwa byazo mu gukwirakwiza hydrogenation zaragaragajwe mbere30. Aha tugaragaza ko complex ya Ru-POP ari catalyst nziza yo gukuraho hydrogenation ya aside formic, byemeza ko Beller yavumbuye ko amino unit muri catalyst ya Ru-PNP amine ya kera idakenewe cyane muri iki gikorwa.
Inyigo yacu itangirana no gukora catalysts ebyiri zisanzwe hamwe na formula rusange [RuHCl(POP)(PPh3)] (Ishusho ya 1a). Kugira ngo duhindure imiterere ya steric na electronic, dibenzo[b,d]furan yatoranijwe muri 4,6-bis(diisopropylphosphino) iboneka ku isoko (Ishusho ya 1b) 31. Catalysts zakorewe muri iki gikorwa zakozwe hakoreshejwe uburyo rusange bwakozwe na Whittlesey32, hakoreshejwe [RuHCl(PPh3)3]•toluene33 adduct nk'inyongera. Vanga precursor y'icyuma na POP clamp ligand muri THF mu bihe bikomeye by'amazi n'iby'umwuka. Igisubizo cyaherekejwe n'impinduka zikomeye z'ibara kuva ku muhengeri wijimye ujya ku muhondo kandi byatanze umusaruro mwiza nyuma y'amasaha 4 ya reflux cyangwa amasaha 72 ya reflux kuri 40°C. Nyuma yo gukuraho THF mu cyuma gisukuye no gukaraba kabiri na hexane cyangwa diethyl ether, triphenylphosphine yakuweho kugira ngo umusaruro ube ifu y'umuhondo mu bwinshi.
Guhuza imiterere ya Ru-1 na Ru-2. a) Uburyo bwo guhuza imiterere. b) Imiterere y'imiterere ya imiterere.
Ru-1 imaze kumenyekana mu nyandiko32, kandi ibindi bisobanuro byibanda kuri Ru-2. 1H NMR spectrum ya Ru-2 yemeje imiterere ya cis ya atome ya fosfini muri ligand ya hydride pair. Igishushanyo cya peak dt (Ishusho ya 2a) kigaragaza 2JP-H coupling constants ya 28.6 na 22.0 Hz, iri mu rugero rwitezwe nk'uko byatangajwe mbere32. Muri hydrogen decoupled 31P{1H} spectrum (Ishusho ya 2b), 2JP-P coupling constant ya hafi 27.6 Hz yagaragaye, yemeza ko clamp ligand fosfini na PPh3 ari cis-cis. Byongeye kandi, ATR-IR igaragaza imiterere ya ruthenium-hydrogen stretching band kuri 2054 cm-1. Kugira ngo hamenyekane neza imiterere y'urusobe rw'ibintu, imiterere ya Ru-2 yahinduwe kristu binyuze mu gukwirakwira kw'umwuka mu bushyuhe bw'icyumba hamwe n'ubwiza buhagije bwo gusesengura X-ray (Ishusho ya 3, Imbonerahamwe y'inyongera ya 1). Ihinduka kristu muri sisitemu ya triclinic y'itsinda rya P-1 hamwe n'igice kimwe cya cocrystalline benzene kuri buri kagari. Igaragaza inguni nini ya P-Ru-P occlusal ya 153.94°, ikaba ari nini cyane kuruta inguni ya 130° occlusal ya bidentate DBFphos34. Kuri 2.401 na 2.382 Å, uburebure bw'umugozi wa Ru-PPOP ni burebure cyane kuruta uburebure bw'umugozi wa Ru na PPh3 bwa 2.232 Å, bishobora kuba biterwa n'inguni nini y'umugongo ya DBFphos iterwa n'impeta yayo yo hagati ya 5. Imiterere y'icyuma hagati muri rusange ni octahedral ifite inguni ya O-Ru-PPh3 ya 179.5°. Ihuzabikorwa rya H-Ru-Cl ntabwo rihagaze neza, rifite inguni ya hafi 175° uvuye kuri ligand ya trifenilifosfini. Intera ya atomike n'uburebure bw'imibanire byanditse mu mbonerahamwe ya 1.
Umubumbe wa NMR wa Ru-2. a) Agace ka Hydride ka 1H NMR spectrum yerekana ikimenyetso cya Ru-H dt. b) 31 P{ 1 H} Umubumbe wa NMR ugaragaza ibimenyetso bivuye kuri trifenilifosfini (ubururu) na POP ligand (icyatsi kibisi).
Imiterere ya Ru-2. Ellipsoids z'ubushyuhe zigaragazwa zifite amahirwe angana na 70%. Kugira ngo bisobanuke neza, atome za benzene na hydrogen za cocrystalline kuri karuboni zarakuwemo.
Kugira ngo hasuzumwe ubushobozi bw'ibice byo mu bwoko bwa complexes bwo gukuraho aside formic, hatoranijwe imiterere y'ibisubizo aho complexes za PNP-clamp (urugero, Ru-MACHO-BH) zijyanye nazo zari zifite imbaraga nyinshi15. Gukuraho aside formic ya 0.5 ml (13.25 mmol) hakoreshejwe 0.1 mol% (1000 ppm, 13 µmol) ya ruthenium complex Ru-1 cyangwa Ru-2 hakoreshejwe 1.0 ml (5.35 mmol) ionic liquid (IL) BMIM OAc (imbonerahamwe-shusho) 2; Ishusho ya 4);
Kugira ngo haboneke igipimo ngenderwaho, igisubizo cyabanje gukorwa hakoreshejwe uburyo bwa precursor adduct [RuHCl(PPh3)3]·toluene. Igisubizo gikorwa ku bushyuhe buri hagati ya 60 na 90 °C. Dukurikije uko bigaragara, complex ntiyashoboraga gushonga burundu muri IL nubwo yavungagurishijwe igihe kirekire ku bushyuhe bwa 90 °C, ariko gushonga byabayeho nyuma yo gushyiramo aside formike. Kuri 90 °C, ihinduka rya 56% (TOF = 3424 h-1) ryagezweho mu minota 10 ya mbere, kandi ihinduka ry’ikigereranyo (97%) ryagezweho nyuma y’amasaha atatu (injira ya 1). Kugabanya ubushyuhe kuri 80 °C bigabanya ihinduka ho hejuru ya kimwe cya kabiri kugeza kuri 24% nyuma y’iminota 10 (TOF = 1467 h-1, injira ya 2), birushaho kugabanuka kuri 18% na 18% kuri 70 °C na 60 °C, uko bikurikirana 6% (injira ya 3 na 4). Muri rusange, nta gihe cyo gutangira cyabonetse, bigaragaza ko catalyst ishobora kuba ubwoko bw’ibinyabuzima bushobora kugaragara cyangwa ko ihinduka ry’ubwoko bw’ibinyabuzima bushobora kugaragara vuba cyane hakoreshejwe iyi mibare.
Nyuma yo gusuzuma ibyabanje, imiterere ya Ru-POP clamp Ru-1 na Ru-2 byakoreshejwe mu buryo bumwe. Kuri 90°C, ihinduka ryinshi ryagaragaye ako kanya. Ru-1 yageze ku ihinduka rya 74% mu minota 10 ya mbere y'igerageza (TOFmax = 4525 h-1, igice cya 5). Ru-2 yagaragaje ibikorwa bike ariko bihoraho, bituma ihinduka rya 60% mu minota 10 (TOFmax = 3669 h-1) n'ihinduka ryuzuye mu minota 60 (> 99%) (igice cya 9). Ni ngombwa kumenya ko Ru-2 iruta cyane metal yabanje na Ru-1 mu ihinduka ryuzuye. Kubwibyo, nubwo metal yabanje na Ru-1 bifite agaciro ka TOForall kamwe mu ihinduka ryuzuye (330 h-1 na 333 h-1, uko bikurikirana), Ru-2 ifite TOForall ya 1009 h-1.
Nyuma yaho, Ru-1 na Ru-2 byagiye bihinduka mu bushyuhe aho ubushyuhe bwagabanutse buhoro buhoro mu nyongera ya 10 °C kugeza nibura kuri 60 °C (Ishusho ya 3). Iyo kuri 90 °C complex yagaragaje ko ihinduka ry’ibintu rihita rikorwa, ihinduka ry’ibintu hafi ya byose ryabaye mu isaha imwe, noneho ku bushyuhe buri hasi ihinduka ry’ibintu ryagabanutse cyane. Ihinduka rya Py-1 ryari 14% na 23% nyuma y’iminota 10 kuri 80 °C na 70 °C, uko bikurikirana, kandi nyuma y’iminota 30 ryiyongereyeho 79% na 73% (inyongera ya 6 na 7). Igerageza ryombi ryagaragaje igipimo cyo guhindura ibintu cya ≥90% mu masaha abiri. Imyitwarire nk’iyo yagaragaye kuri Ru-2 (inyongera ya 10 na 11). Igishimishije ni uko Ru-1 yari ikomeye gato mu mpera y’ihinduka ryakozwe kuri 70 °C hamwe na TOF yose ya 315 h-1 ugereranije na 292 h-1 kuri Ru-2 na 299 h-1 ku cyuma gitangira.
Kugabanuka gukomeye k'ubushyuhe kugera kuri 60 °C byatumye nta guhindura kwagaragaye mu minota 30 ya mbere y'igerageza. Ru-1 ntiyakoraga cyane ku bushyuhe bwo hasi cyane mu ntangiriro y'igerageza, nyuma yaho ibikorwa byiyongera, bigaragaza ko hakenewe igihe cyo gukora aho Ru-1 precatalyst ihinduka ubwoko bukora catalytically. Nubwo ibi bishoboka ku bushyuhe bwose, iminota 10 mu ntangiriro y'igerageza ntabwo yari ihagije kugira ngo hamenyekane igihe cyo gukora ku bushyuhe bwinshi. Imyitwarire nk'iyo yabonetse kuri Ru-2. Kuri 70 na 60 °C, nta guhindura kwagaragaye mu minota 10 ya mbere y'igerageza. Ni ngombwa kumenya ko muri ubwo bushakashatsi bwombi, ikorwa rya monoxide ya karuboni ntiryagaragaye mu rugero ntarengwa rwo gupima igikoresho cyacu (<300 ppm), aho H2 na CO2 ari byo byonyine byagaragaye.
Kugereranya ibisubizo byo gukuraho aside formic byabonetse mbere muri iri tsinda ry’abakozi, bigaragaza iterambere rigezweho kandi hakoreshejwe uburyo bwa Ru-PNP clamp complexes, byagaragaje ko clamp nshya ya Ru-POP ifite imikorere isa n’iya PNP 15. Mu gihe clamp PNP yageze kuri RPM za 500-1260 h-1 mu bushakashatsi bwa batch, clamp nshya ya POP yageze ku gaciro ka TOFovertal ka 326 h-1, kandi agaciro ka TOFmax ka Ru-1 na 1590 h-1 kagaragaye. Uko bikurikirana, ni 1988 h-1 na 1590 h-1. Ru-2 ni 1 kuri 80 °C, Ru-1 ni 4525 h-1 na Ru-1 ni 3669 h-1 kuri 90 °C, uko bikurikirana.
Gupima ubushyuhe bwa aside formike igabanuka hakoreshejwe catalysts za Ru-1 na Ru-2. Ibipimo: catalysts za 13 µmol, aside formike 0.5 ml (13.25 mmol), 1.0 ml (5.35 mmol) BMIM OAc.
NMR ikoreshwa mu gusobanukirwa uburyo bwo gukora reaction. Kubera ko hari itandukaniro rikomeye cyane muri 2JH-P hagati ya hydride na fosphine ligands, ikibandwaho muri ubu bushakashatsi ni ku gice cy’umurambararo wa hydride. Kuri Ru-1, imiterere isanzwe ya dt y’igice cya hydrogenation yabonetse mu minota 60 ya mbere yo gutakaza hydrogenation. Nubwo hari impinduka ikomeye kuva kuri −16.29 kugeza kuri −13.35 ppm, ibipimo byayo byo guhuza na fosphine ni 27.2 na 18.4 Hz, uko bikurikirana (Ishusho ya 5, Peak A). Ibi bihuye na fosphine zose uko ari eshatu aho hydrogen ligand iri mu miterere ya cis kandi bigaragaza ko imiterere ya ligand ihamye muri IL mu gihe cy’isaha imwe mu gihe cy’imikorere myiza. Impinduka ikomeye ishobora guterwa no gukuraho ligande za chlorine no kurema aside acetyl-formic complexes, kurema d3-MeCN complex muri NMR tube, cyangwa kurema N-heterocycles zijyanye nayo. byasobanuwe. Carbene (NHC) complex. Mu gihe cyo kubura hydrogenation, imbaraga z'iki kimenyetso zakomeje kugabanuka, kandi nyuma y'iminota 180 ikimenyetso nticyongeye kugaragara. Ahubwo, ibimenyetso bibiri bishya byavumbuwe. Icya mbere kigaragaza ishusho isobanutse ya dd igaragara kuri -6.4 ppm (peak B). Doublet ifite coupling constant nini ya 130.4 Hz, bigaragaza ko imwe mu matsinda ya fosfini yimutse ugereranije na hydrogen. Ibi bishobora gusobanura ko POP clamp isubirwamo mu buryo bwa κ2-P,P. Kugaragara kw'iki kimenyetso nyuma ya catalysis bishobora kwerekana ko ubu bwoko butuma inzira zo guhagarika gukora uko igihe kigenda, bigatuma habaho catalyst sink. Ku rundi ruhande, impinduka nkeya y’imiti igaragaza ko ishobora kuba ubwoko butandukanye bwa hydrogen15. Isonga rya kabiri rishya riri kuri -17.5 ppm. Nubwo ipfundo ryayo ritazwi, twizera ko ari triplet ifite coupling constant nto ya 17.3 Hz, bigaragaza ko hydrogen ligand ifatana gusa na fosphine ligand ya POP clamp, kandi bigaragaza ko triphenylphosphine (peak C). Ishobora gusimburwa n'indi ligand, nk'itsinda rya acetyl cyangwa NHC yakozwe muri situ iturutse kuri ayoni. Gutandukana kwa PPh3 bigaragazwa kandi na singlet ikomeye kuri -5.9 ppm. muri 31P{1H} spectrum ya Ru-1 nyuma y'iminota 180 kuri 90 °C (reba andi makuru).
Agace ka Hydride ka 1H NMR spectrum ya Ru-1 mu gihe aside formic igabanuka. Imiterere y'ibisubizo: 0.5 ml aside formic, 1.0 ml BMIM OAc, 13.0 µmol catalyst, 90 °C. NMR yakuwe muri MeCN-d 3, 500 μl ya deuterated solvent, hafi 10 μl y'uruvange rw'ibisubizo.
Kugira ngo byemezwe neza ko hari ubwoko bw’ibinyabuzima bukora muri sisitemu ya katalegisi, hakozwe isesengura rya HRMS rya Ru-1 nyuma yo guterwa aside formike mu minota 10 kuri 90 °C. Ibi bigaragaza ko hari ubwoko budafite chlorine ligand precatalyst mu mvange y’ibisubizo. hamwe n’ibice bibiri bya NHC, imiterere yabyo igaragara ku Ishusho ya 6. Imiterere ya HRMS ijyanye nayo igaragara ku Ishusho y’inyongera ya 7.
Dushingiye kuri aya makuru, dutanga uburyo bwo gukora interasphere nk'ubwatanzwe na Beller, aho N-methylated PNP clamps itera imbaraga iyo reaction imwe. Igerageza ryinyongera ritarimo ibinyobwa bya ionic ntabwo ryagaragaje igikorwa icyo ari cyo cyose, bityo uruhare rwabyo rugaragara nk'aho ari ngombwa. Dutekereza ko gukora kwa Ru-1 na Ru-2 bibaho binyuze mu kwitandukanya kwa chloride bigakurikirwa no kongeramo NHC no kwitandukanya kwa triphenylphosphine (Scheme 1a). Uku gukora mu moko yose byagaragaye mbere hakoreshejwe HRMS. IL-acetate ni ishingiro rikomeye rya Bronsted kurusha aside formic kandi ishobora gukuraho prototone cyane ya nyuma35. Dutekereza ko mu gihe cy’izunguruka rya catalytic (Igishushanyo cya 1b), ubwoko bukora bwa A bufite NHC cyangwa PPh3 buhuzwa binyuze mu ibumba kugira ngo bukore ubwoko bwa B. Guhindura iyi complex kuri C amaherezo bivamo irekurwa rya CO2 na trans-dihydrogen complex D. Gutera aside muri dihydro complex hamwe na aside asetiki yakozwe mbere kugira ngo ikore dihydro complex E bisa n'intambwe y'ingenzi yatanzwe na Beller akoresheje N-methylated PNP clamp homologues. Byongeye kandi, analogue ya complex EL = PPh3 yabanje gukorwa hakoreshejwe reaction ya stoichiometric ikoresheje Ru-1 mu kirere cya hydrogen nyuma yo gukuramo chloride hamwe n'umunyu wa sodium. Gukuraho hydrogen no guhuza formate bitanga A kandi birangiza cycle.
Uburyo bwo gukora imikorere y’ingirabuzimafatizo mu gihe cy’igabanuka ry’aside formike hakoreshejwe uburyo bwo kuyitunganya bwa Ru-POP Ru-1 buratangwa.
Hakozwe imiterere mishya [RuHCl(iPr-dbfphos)(PPh3)]. Iyi complex yagaragajwe n'isesengura rya NMR, ATRIR, EA na X-ray diffraction ya kristu imwe. Turatangaza kandi ko ikoreshwa rya mbere rya Ru-POP pincer complexes ryagenze neza mu gukuraho aside formic kuri CO2 na H2. Nubwo icyuma cyabanje gukora ibintu bisa (kugeza kuri 3424 h-1), complex yageze ku nshuro ntarengwa yo kuzenguruka kugeza kuri 4525 h-1 kuri 90 °C. Byongeye kandi, kuri 90 °C, complex nshya [RuHCl(iPr-dbfphos)(PPh3)] yageze ku gihe cyose cyo kuguruka (1009 h-1) kugira ngo yuzuze gukuraho aside formic, iri hejuru cyane kurusha icyuma cyabanje (330 h-1). hamwe n'icyavuzwe mbere [RuHCl(xantphos)(PPh3)] (333 h-1). Mu bihe nk'ibi, ubushobozi bwa catalytic bugereranywa n'ubw'uburyo bwa Ru-PNP clamp complex. Amakuru ya HRMS agaragaza ko hari complex ya carbene mu ruvange rw'ibisubizo, nubwo ari buke. Ubu turimo kwiga ingaruka za catalytic za carbene complexes.
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