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Aside formique ni imwe mu nzira zishobora gutuma umuntu ashobora kubika igihe kirekire amazi y’ihydrogène. Aha turashira ahabona urutonde rw’ibihimba bishasha vy’ivyuma vy’uruthenium bifise ubuhinga rusangi [RuHCl(POP)(PPh3)] dukoresheje ivyuma vy’ivyuma vy’ivyuma vy’ivyuma vy’ivyuma vy’ivyuma vy’ivyuma vy’ivyuma vy’ivyuma vy’ivyuma vy’ivyuma vy’ivyuma vy’ivyuma vy’ivyuma. Twarakoresheje ivyo bihimba kugira ngo dushiremwo aside formique kugira ngo tuvemwo CO2 na H2 mu bihe vy’ubugwaneza, bitagiramwo ivyuka biva mu mazi, dukoresheje amazi y’iyon BMIM OAc (1-butyl-3-methylimidazolium acetate) nk’ikintu gishobora gukuraho amazi. Uravye ku bijanye n’incuro nyinshi z’uguhinduka, ikintu gikora neza cane ni [RuHCl(xantphos)(PPh3)]Ru-1 kizwi mu bitabu, gifise incuro nyinshi z’uguhinduka 4525 h-1 ku 90 °C mu minota 10. Igipimo c’inyuma y’uguhinduka cari 74%, kandi uguhinduka kwarangiye mu masaha 3 (>98%). Ku rundi ruhande, igikoresho gikora neza kuruta ibindi vyose, igitabu [RuHCl(iPr-dbfphos)(PPh3)]Ru-2, kiratera imbere uguhinduka kwuzuye mu masaha 1, bikaba bituma haba igipimo c’uguhinduka kw’amasaha 1009-1. Ikindi, igikorwa c’ugutuma ibintu bigenda neza na co nyene carabonetse ku bushuhe bushika kuri 60 °C. Mu rwego rwa gazi, CO2 na H2 gusa ni vyo vyabonetse; CO ntiyabonetse. Ivyuma vy’ubuhinga bwa none vyerekanye ko hariho ibihimba vy’umubiri bita N-heterocyclic carbene mu vyo bivanga.
Ukwiyongera kw'isoko ry'inguvu zishobora gusubirwamwo n'uguhinduka kwazo vyatumye habaho ugusaba ubuhinga bwo kubika inguvu ku rugero rw'inganda mu nzego z'inguvu, ubushuhe, inganda n'ivy'ugutwara abantu n'ibintu1,2. Ihidrojeni ifatwa nk’imwe mu nzira zitwara inguvu nyinshi cane3, kandi ihidrojeni y’amazi (LOHCs) iherutse kuba ikintu nyamukuru c’ubushakashatsi, itanga umuhango wo kubika ihidrojeni mu buryo bworoshe gutunganirizwa ata ngorane zijanye n’ubuhinga bwo gutera umukazo canke ubuhinga bwo gukoresha umuyagankuba4. ,5,6. Kubera imiterere yavyo, ibikorwa remezo vyinshi vy’ugutwara abantu n’ibintu biriho vy’amavuta ya peteroli n’ibindi bikoresho bishobora gukoreshwa mu gutwara LOHC7,8. Ivyo aside formique (FA) ikora bituma iba nziza cane mu kubika ihydrogène ifise uburemere bwa hydrogène bwa 4.4%9,10. Ariko rero, uburyo bwasohowe bwo gutuma aside formique idakora neza, busanzwe busaba gukoresha ibikoresho bishobora guhinduka, amazi canke aside formique isukuye,11,12,13,14 bishobora gusaba gukoresha ubuhinga bwo gutandukanya umwotsi w’ibinyabuzima nk’ugutera amazi, bishobora gutuma haba ingorane mu gukoresha. ibikorwa, umuzigo w’inyongera. Ico kibazo gishobora gutorwa hakoreshejwe ibintu bifise umuvuduko mutoyi w’umwotsi, nk’amazi y’iyon. Mbere y’aho, umugwi wacu w’abakozi werekanye ko amazi y’iyon butylmethylimidazolium acetate (BMIM OAc) ari ikintu ciza co gutorera umuti muri iyo nzira hakoreshejwe ubuhinga bwo gukosora buboneka mu maduka Ru-PNP Ru-MACHO ubwoko 15. TONI zirenga 18.000.000 ku bushuhe bwa 95°C. Naho uburyo bumwe bumwe bwari bwarashitse ku TON nyinshi, benshi barizigiye ibinyabuzima bishobora guhinduka (nk’ivyo bita THF canke DMF) canke ivyongera bikoreshwa (nk’ivyo bita base). Mu buryo butandukanye n’ubwo, igikorwa cacu mu vy’ukuri gikoresha amazi y’iyon adashobora guhinduka (ILs) kandi nta kintu co kwongerako.
Hazari na Bernskoetter bavuze ko aside formique (FA) yahindutse amazi ku bushuhe bwa 80 °C hakoreshejwe ikintu gitera Fe-PNP iyo hari dioxane na LiBF4, bikaba vyatumye habaho umubare w’ibicuruzwa (TON) utangaje w’ibice nka 1.000.00016. Laurenci yakoresheje igikoresho gikomeye ca Ru(II)- TPPPTS mu buryo buhoraho bwo gukuraho amazi mu mazi. Ubwo buryo bwatumye FA hafi yuzuye gukuraho amazi n’ibice bike cane vya CO vyabonetse ku 80 °C17. Kugira ngo uwo muce utere imbere, Pidko yerekanye ukuntu FA ishobora gusubira inyuma hakoreshejwe ibikoresho bifasha mu gutuma amazi agira Ru-PNP mu bivange vya DMF/DBU na DMF/NHex3, bishika ku gaciro ka TON kuva kuri 310.000 gushika kuri 706.500 ku bushuhe bwa 90 °C18. Hull, Himeda na Fujita barize igikoresho gitera umuriro c’imigera ibiri (Ir complex catalyst) aho KHCO3 na H2SO4 vyatangwa nk’ikimazi, bihinduranya uguhindura CO2 n’ugukuraho FA. Uburyo bwabo bwashitse kuri TONs zirenga 3.500.000 na 308.000 ku bijanye no guhindura amazi ku bushuhe bwa 30°C, CO2/H2 (1:1), umuvuduko wa 1 bar no ku bijanye no guhindura amazi hagati ya 60 na 90°C19. Sponholz, Junge na Beller bakoze ubuhinga bwa Mn-PNP bwo guhindura CO2 n’uguhindura FA ku 90 °C20.
Aha twakoresheje uburyo bwa IL, ariko aho gukoresha Ru-PNPs, twasuzumye ikoreshwa ry’ibitera Ru-POP, ivyo ku bumenyi bwacu ntivyari bwagaragajwe mbere muri ivyo.
Kubera ko zikorana neza cane n’ivyuma (MLC), ivyuma bifatanya amino-PNP bishingiye ku vyiyumviro vy’ubwoko bwa Noyori bifise imigwi y’ibikorwa vy’imitsi 21 (nka Ru-MACHO-BH) muri rusangi biriko birarushiriza kumenyekana mu bikorwa bimwebimwe vy’ibihimba bitobito. Ingero zizwi cane ni CO22, uguhindura alkenes na carbonyls zihinduka amazi, guhindura amazi23 n’ugukuraho amazi y’inzoga24. Vyaravuzwe ko N-methylation ya PNP clamp ligands ishobora guhagarika burundu igikorwa c’ivyuma25, ivyo bikaba bishobora gusigurwa n’uko amamine akora nk’inkomoko y’amaprotoni, ivyo bikaba ari ikintu gihambaye gikenewe mu gihe c’ingendo y’ivyuma hakoreshejwe MLC. Ariko rero, ikintu gihushanye n’ico mu gukuraho amazi mu aside ya formique carabonetse vuba cane na Beller, aho ibihimba vya Ru-PNP bifise N-methylated mu vy’ukuri vyerekana ko aside ya formique ishobora gukuraho amazi kuruta ibindi bitagira methylated26. Kubera ko iyo nzira ya kera idashobora kugira uruhara muri MLC biciye ku gice c’amine, ivyo birerekana cane ko MLC, n’igice c’amine, gishobora kugira uruhara rutoyi cane mu mpinduka zimwe zimwe z’ugukuraho amazi nk’uko vyari vyiyumviriwe mbere.
Ugereranije n’ibikoresho vy’ugufata POP, ivyuma vy’uruthenium vy’ibikoresho vy’ugufata POP ntivyari bwarize bihagije muri ivyo. POP ligands zakoreshejwe cane cane mu hydroformylation, aho zikora nk'ivyuma vy'amazi aho gukora nk'ivyuma vy'amaminwa bifise ubushobozi bwo kurya 120° ku bikoresho vy'ugufatanya, vyakoreshejwe mu guhitamwo neza ibintu vy'umurongo n'ivy'amashami27,28,29. Kuva ico gihe, ibihimba vya Ru-POP ntivyakoreshejwe cane mu gutuma ivyuma bihinduka, ariko ingero z’ibikorwa vyavyo mu guhindura ivyuma vyaravuzwe mbere30. Aha twerekana ko umugwi wa Ru-POP ari ikintu ciza co gutuma aside formique igira amazi, ivyo bikaba vyemeza ivyo Beller yabonye ko igice c’amine kiri mu gice c’amine ca Ru-PNP ca kera kidahambaye cane muri iyo nzira.
Ico cigwa cacu gitangura n’ugukoranya ibintu bibiri bimenyerewe bifise ubuhinga rusangi [RuHCl(POP)(PPh3)] (Ishusho 1a). Kugira ngo hahindurwe imiterere y’ibihimba vy’umubiri n’ivy’ubuhinga bwa none, dibenzo[b,d]furan yatowe mu bihimba vy’umubiri bishobora kugurishwa (Ishusho 1b) 31. ikintu c’imbere. Vanga ivyuma bibanza n’ivyuma bifata POP mu THF mu bihe bitagira amazi n’ibihe bitagira umwuka. Ivyo vyari biherekejwe n’uguhinduka kw’ibara rikomeye kuva ku rangi ry’umuhondo ryirabura gushika ku muhondo kandi vyatanga igicuruzwa gisukuye inyuma y’amasaha 4 y’ugusubira inyuma canke amasaha 72 y’ugusubira inyuma ku 40°C. Amaze gukuraho THF mu busa no kwozwa incuro zibiri n’ivyuma bita hexane canke diethyl ether, triphenylphosphine yarakuweho kugira ngo igicuruzwa kibe nk’ifu y’umuhondo mu mwimbu munini.
Ivyiyumviro vy’ibihimba vy’umubiri bita Ru-1 na Ru-2. a) Uburyo bwo gukoranya ibintu bikomeye. b) Imiterere y’ivyo bihimba vy’umubiri vyakozwe.
Ru-1 irasanzwe izwi mu bitabu32, kandi ibindi bimenyetso vyibanda kuri Ru-2. 1H NMR spectrum ya Ru-2 yemeje ko cis y’atome ya phosphine iri mu gice c’umubiri c’umubiri. Igishushanyo c’isonga rya dt (Ishusho 2a) kigaragaza ibiharuro vy’ugufatanya 2JP-H vy’ibiharuro 28,6 na 22,0 Hz, biri mu rugero rwiteze rwa raporo za kera32. Mu nzira y’iyi hydrogène 31P{1H} (Ishusho 2b), habonetse igipimo c’ihuriro ca 2JP-P c’ibara ry’ibara ry’ibara ry’ibara ry’ibara ry’ibara ry’ibara ry’ibara ry’ibara ry’ibara ry’ibara ry’ibara ry’ibara ry’ibara ry’ibara ry’ibara ry’ibara. Ikindi, ATR-IR yerekana umurongo w’ugukura kw’ivyuma vy’iyidrojeni ku 2054 cm-1. Kugira ngo haboneke ibindi bisobanuro vy’imiterere, igice ca Ru-2 carahindutse ikibiriti biciye mu gukwiragira kw’umwotsi mu bushuhe bwo mu cumba gifise uburyo buhagije bwo gukora inyigisho z’imishwarara ya X (Ishusho 3, Imbonerahamwe y’inyongera 1). Igira ikibiriti mu buryo bw’ibice bitatu vy’umugwi w’ikirere P-1 n’igice kimwe ca benzene cocrystalline ku gice c’ingingo. Igaragaza umwanya munini w’ugufunga P-Ru-P w’ibice 153,94°, ukaba ari munini cane kuruta umwanya w’ugufunga w’ibice 130° w’igikoko citwa DBFphos34. Ku 2.401 na 2.382 Å, uburebure bw’umugozi wa Ru-PPOP burareha cane kurusha uburebure bw’umugozi wa Ru na PPh3 bwa 2.232 Å, ivyo bishobora kuba ari ingaruka y’umwanya wagutse w’umugongo wa DBFphos uterwa n’uruzitiro rwayo rwa 5 rwo hagati. Igishushanyo c’ivyuma hagati ni ahanini gifise amahembe umunani gifise mfuruka ya O-Ru-PPh3 y’ibice 179,5°. Ihuriro rya H-Ru-Cl ntirihuye n’umurongo wose, rifise imfuruka y’ibilometero nka 175° uvuye ku gice c’umubiri citwa triphenylphosphine. Urugendo rw'atome n'uburebure bw'imigenderanire biri ku rutonde rw'Imbonerahamwe 1.
NMR y'umuco wa Ru-2. a) Akarere k’ihydride k’umurongo wa 1H NMR kerekana ikimenyetso ca Ru-H dt. b) 31 P{ 1 H} NMR spectrum yerekana ibimenyetso biva kuri trifenylphosphine (ubururu) n’umugera wa POP (icatsi kibisi).
Imiterere ya Ru-2. Ivyiyumviro vy’ubushuhe vyerekanwa n’ibishoboka 70%. Kugira ngo bimenyekane neza, atome za benzene n’iz’ihydrogène ziri ku karboni zarakuwemwo.
Kugira ngo hasuzumwe ubushobozi bw’ivyo bihimba bwo gukuraho aside formique, hatoranywe uburyo bwo gukora aho ivyo bihimba bihuye n’ivyo bihimba vya PNP-clamp (nk’akarorero, Ru-MACHO-BH) vyari bikora cane15. Gukuraho amazi mu ml 0,5 (13,25 mmol) y’aside formique hakoreshejwe 0,1 mol% (1000 ppm, 13 μmol) y’umugera wa ruthenium Ru-1 canke Ru-2 hakoreshejwe militiro 1,0 (5,35 mmol) y’amazi y’iyon (IL) BMIM OAc (imbonerahamwe-2) Igishushanyo ca 4);
Kugira ngo umuntu aronke urugero, iyo nzira yabanje gukorwa hakoreshejwe umuti w’imbere [RuHCl(PPh3)3]·toluene. Ivyo bikorwa bibera ku bushuhe buva kuri 60 gushika kuri 90 °C. Dushingiye ku vyo umuntu abona vyoroshe, iyo ntungamubiri ntiyashobora gusenyuka burundu muri IL mbere n’aho yoba yavyurwa igihe kirekire ku bushuhe bwa 90°C, ariko gusenyuka kwabaye inyuma y’aho hashizwemwo aside formique. Ku 90°C, uguhinduka kwa 56% (TOF = 3424 h-1) kwashitsweko mu minota 10 ya mbere, kandi uguhinduka hafi kw’ingero (97%) kwashitsweko inyuma y’amasaha atatu (injiza 1). Kugabanya ubushuhe kugera kuri 80 °C bigabanya uguhinduka n’ibice birenga ica kabiri kugera kuri 24% inyuma y’iminota 10 (TOF = 1467 h-1, ingingo ya 2), bikagabanya kandi kugera kuri 18% na 18% ku 70 °C na 60 °C, hakurikijwe 6% (ingingo ya 3 na 4). Mu bihe vyose, nta gihe c’induction cabonetse, bikaba vyerekana ko igituma bishobora kuba ari ubwoko bushobora gusubiza canke ko uguhinduka kw’ubwoko bushobora gusubiza vyihuta cane ku buryo bidashobora kumenyekana hakoreshejwe iyi nkuru.
Inyuma y’isuzuma ry’imbere, ivyuma vy’imbere vy’i Ru-POP Ru-1 na Ru-2 vyakoreshejwe mu buryo bumwe. Ku 90°C, ubwo nyene haca haboneka uguhinduka kwinshi. Ru-1 yashitse ku guhinduka 74% mu minota 10 ya mbere y’igerageza (TOFmax = 4525 h-1, injiza ya 5). Ru-2 yerekanye igikorwa gitoyi ariko gikomeye cane, itera imbere uguhinduka 60% mu minota 10 (TOFmax = 3669 h-1) n’uguhinduka kwuzuye mu minota 60 (>99%) (inyandiko 9). Biragaragara ko Ru-2 iruta cane ivyuma vy’imbere na Ru-1 iyo ihindutse bimwe bishitse. Ku bw’ivyo, naho ivyuma bibanza na Ru-1 bifise agaciro ka TOFoverall gasa n’ako igihe igikorwa kirangiye (330 h-1 na 333 h-1, hakurikijwe), Ru-2 ifise TOFoverall ya 1009 h-1.
Ru-1 na Ru-2 vyaciye bihindurwa ubushuhe aho ubushuhe bwagabanywa buhoro buhoro mu 10 °C gushika ku 60 °C (Ishusho 3). Iyo ku bushuhe bwa 90°C iyo nzira yerekana igikorwa ubwo nyene, uguhinduka hafi kwose kwabaye mu masaha makeyi, hanyuma ku bushuhe buke igikorwa kigabanuka cane. Ihinduka rya Py-1 ryari 14% na 23% inyuma y’iminota 10 ku 80°C na 70°C, hakurikijwe, inyuma y’iminota 30 ryaraduze rishika kuri 79% na 73% (ivyinjijwe 6 na 7). Ivyo bigeragezo vyose vyerekanye ko abantu bahinduka ≥90% mu masaha abiri. Inyifato nk’iyo nyene yarabonetse kuri Ru-2 (injiza 10 na 11). Ikintu gitangaje ni uko Ru-1 yari ihambaye gatoyi ku mpera y’ivyo bisubizo ku 70 °C n’umubare wose w’amasaha 315 h-1 ugereranyije na 292 h-1 ku Ru-2 na 299 h-1 ku vyuma vy’imbere.
Ugusubira kugabanya ubushuhe gushika ku 60 °C kwatumye ata guhinduka kwabonetse mu minota 30 ya mbere y’igerageza. Ru-1 yari idakora cane ku bushuhe bwo hasi cane mu ntango y’igerageza hanyuma mu nyuma irarushiriza gukora, ivyo bikaba vyerekana ko bisaba igihe co gukora aho igikoresho ca Ru-1 gihinduka ubwoko bukora neza. Naho ivyo bishoboka ku bushuhe bwose, iminota 10 mu ntango y’igerageza ntiyari ihagije kugira ngo umuntu amenye igihe co gukora ku bushuhe bwinshi. Inyifato nk’iyo nyene yarabonetse kuri Ru-2. Ku 70 na 60 °C, nta guhinduka kwabonetse mu minota 10 ya mbere y’igerageza. Ni ngombwa kumenya ko muri izo ngeragezwa zompi, uguhingura monoxide de carbone kutabonetse mu rugero rwo kumenya rw’igikoresho cacu (<300 ppm), H2 na CO2 ari vyo vyonyene vyabonetse.
Igereranyo ry’ibisubizo vy’ugukuraho amazi y’aside formique vyabonetse mbere muri iri tsinda ry’akazi, bigereranya ubuhinga bwa none kandi bikoresha ibikoresho vy’ugufata Ru-PNP, vyerekanye ko igikoresho gishasha ca Ru-POP gifise igikorwa gisa n’ica mugenzi waco wa PNP 15. Mu gihe igikoresho ca PNP-12 cashitse kuri hPMs1. igikoresho gishasha ca POP carashitse ku gaciro ka TOFovertal ka 326 h-1, kandi agaciro ka TOFmax ka Ru-1 na 1590 h-1 karabonetse. uko bikurikirana, ni 1988 h-1 n’1590 h-1. Ru-2 ni 1 ku 80 °C, Ru-1 ni 4525 h-1 na Ru-1 ni 3669 h-1 ku 90 °C, uko bikurikirana.
Igenzura ry’ubushuhe bw’ugukuraho amazi mu aside formique hakoreshejwe ibikoresho bitera umuriro Ru-1 na Ru-2. Ivyangombwa: 13 μmol y’ivyo gutera imbere, 0,5 ml (13,25 mmol) y’aside formique, 1,0 ml (5,35 mmol) ya BMIM OAc.
NMR ikoreshwa mu gutahura uburyo ibintu bikora. Kubera ko hariho itandukaniro rikomeye cane muri 2JH-P hagati y’ibihimba vy’umubiri vy’amazi n’ivy’amazi, ikintu nyamukuru iki cigwa kivuga ni isonga ry’amazi. Ku bijanye na Ru-1, uburyo busanzwe bwa dt bw’igice c’ivyuma vy’amazi bwabonetse mu minota 60 ya mbere y’ugukuraho amazi. Naho hariho uguhinduka gukomeye kw’ibarabara kuva kuri −16,29 gushika kuri −13,35 ppm, ibihe vy’ugufatanya kwayo na phosphine ni 27,2 na 18,4 Hz, hakurikijwe (Ishusho 5, Isonga A). Ivyo bihuye n’ivyo bihimba vyose bitatu vy’umubiri (phosphines) aho umugera w’iyidrojeni uri mu rwego rwa cis kandi bikaba vyerekana ko umugera w’iyidrojeni uhagaze neza mu rwego rwa IL mu kiringo c’isaha imwe mu gihe umuntu ariko arakora neza. Ivyo bishobora kuba biterwa n’ugukuraho ivyuma bifise klorine be n’uguhingura ivyuma bihuye n’ivyo bita aside acetyl-formique, uguhingura ivyuma bihuye n’ivyo bita d3-MeCN mu nzira ya NMR, canke uguhingura ivyuma bihuye n’ivyo bita N-heterocycles. yarasobanuye. Ivyuma vy’ikaribeni (NHC) bikomeye. Mu gihe c’ugukuraho amazi, uburemere bw’ico kimenyetso bwabandanije kugabanuka, haciye iminota 180 ico kimenyetso nticasubiye kugaragara. Ahubwo, haravumbuwe ibimenyetso bibiri bishasha. Irya mbere ryerekana urugero rwa dd rutomoye rushika kuri -6,4 ppm (isonga B). Ico gice c’umubiri gifise igipimo kinini c’ugufatanya c’amasaha nka 130,4 Hz, ivyo bikaba vyerekana ko kimwe mu bice vya phosphine cagiye kijanye n’ivyo bihimba vy’umubiri. Ivyo bishobora gusobanura ko igikoresho ca POP gisubira gutunganirizwa mu buryo bwa κ2-P,P. Kuboneka kw’ico gice gikomeye mu gihe c’ugutera imbere bishobora kwerekana ko ubwo bwoko bujana mu nzira z’uguhagarara uko igihe kigenda kirarenga, bigatuma habaho igikoresho co gutera imbere. Ku rundi ruhande, uguhinduka kw’imiti guke kwerekana ko yoba ari ubwoko bw’ibinyabuzima bifise amazi abiri15. Isonga rishasha rya kabiri riri ku -17,5 ppm. Naho igitigiri caco kitazwi, twizera ko ari igice c’ubutatu gifise umurongo mutoyi w’ugufatanya w’ibice 17,3 Hz, ivyo bikaba vyerekana ko igihimba c’iyidrojeni gifatanya gusa n’igihimba c’iyi phosphine c’igihimba ca POP, ivyo bikaba vyerekana kandi ko triphenylphosphine irekurwa (isonga C). Ishobora gusubirizwa n’iyindi ligand, nk’umugwi wa acetyl canke NHC ivutse in situ ivuye mu mazi y’iyon. Ugusenyuka kwa PPh3 kugaragazwa kandi n’igice gikomeye c’umubiri ku -5,9 ppm. mu 31P{1H} spectrum ya Ru-1 inyuma y’iminota 180 ku 90 °C (raba ibindi bisobanuro).
1H NMR spectrum ya Ru-1 mu gihe c’ugukuraho amazi y’aside formique. Ivyo gukoresha: 0,5 ml ya aside formique, 1,0 ml ya BMIM OAc, 13,0 μmol y’ivyo gutera, 90 °C. NMR yafashwe muri MeCN-d 3 , 500 μl y’umunyuro w’ivyuma, hafi 10 μl y’umunyuro w’ivyuma.
Kugira ngo haboneke ko hariho ubwoko bukora mu buryo bw’ugutuma ibintu bigenda neza, hakozwe isesengura ry’uburemere bw’ibintu (HRMS) rya Ru-1 inyuma yo guterwa aside formique iminota 10 ku bushuhe bwa 90 °C. Ivyo vyerekana ko hariho ubwoko butagira igihimba c’umubiri citwa chlorine ligand precatalyst mu mvange y’ivyo bihimba. hamwe n'ibibanza bibiri vya NHC, imiterere yavyo yerekanwa ku gishushanyo ca 6. Ivyo bishobora kubonwa ku gishushanyo ca 7 c'inyongera.
Hashingiwe kuri ayo makuru, dusaba uburyo bwo gusubiza mu mubiri busa n’ubwo Beller yashizeho, aho ama clamps ya PNP afise N-methylated atera iyo nzira nyene. Ibindi bigeragezo bitarimwo amazi y’iyon ntivyerekanye igikorwa na kimwe, ni co gituma ukugira uruhara kwayo ata guca ku ruhande bisa n’ibikenewe. Twiyumvira ko ugukora kwa Ru-1 na Ru-2 bishika biciye mu gusenyuka kwa kloride hakurikijwe kwongerwako NHC bishoboka n’ugusenyuka kwa triphenylphosphine (Igishushanyo 1a). Ukwo gukora mu bwoko bwose kwari kwabonetse mbere hakoreshejwe ubuhinga bwa HRMS. IL-acetate ni umusemburo ukomeye cane wa Bronsted kurusha aside formique kandi ushobora gukuraho cane iyo nyuma35. Twiyumvira ko mu gihe c’ingendo y’ugutuma ibintu bigenda neza (Ikigereranyo 1b), ubwoko bukora A bufise NHC canke PPh3 buhuzwa biciye ku mafomati kugira ngo bube ubwoko B. aside kugira ngo ikore dihydro complex E isa n’intambwe nyamukuru yashikirijwe na Beller akoresheje ibihimba vy’umubiri bifatanya n’ibindi bihimba vy’umubiri bifise N-methylated PNP. Ikindi, ikigereranyo c’ikirungo EL = PPh3 cari carakozwe mbere n’ubuhinga bwa stoikiometrike hakoreshejwe Ru-1 mu kirere c’iyidrojeni inyuma yo gukura kloride n’umunyu wa sodiyumu. Gukuraho ihydrogène no guhuza formate bitanga A kandi bikarangiza uruziga.
Uburyo bwo gukorana n’ibindi bihimba vy’umubiri bikoreshwa mu gukuraho amazi mu mubiri hakoreshejwe umuti Ru-POP Ru-1 burashikirizwa.
Igitera gishasha [RuHCl(iPr-dbfphos)(PPh3)] carakozwe. Ico kibanza carangwa n’ugusesangura NMR, ATRIR, EA n’ugusesangura kw’imishwarara ya X y’ibice bimwe bimwe vy’amabuye y’agaciro. Turatanga raporo kandi y’ugukoresha kwa mbere kw’ibikoresho vy’ugupima Ru-POP mu guhindura aside formique ngo ibe CO2 na H2. Naho igikoresho c’imbere c’icuma cashitse ku gikorwa nk’ico (gushika ku masaha 3424 h-1), ico gikoresho gikomeye carashitse ku ncuro nyinshi cane z’uguhinduka gushika ku masaha 4525 h-1 ku bushuhe bwa 90 °C. Ikindi kandi, ku bushuhe bwa 90 °C, iyo ntungamubiri nshasha [RuHCl(iPr-dbfphos)(PPh3)] yarashitse ku gihe cose co guguruka (1009 h-1) kugira ngo irangize gukuraho amazi mu mfuruka z’aside formique, ivyo bikaba ari vyinshi cane kuruta ivy’ivyuma vy’imbere mu mubiri (330 h-1). n’ivyo bihimba vy’umubiri vyari vyaravuzwe mbere [RuHCl(xantphos)(PPh3)] (333 h-1). Mu bihe nk’ivyo, ubushobozi bw’ivyuma bitera umuriro buragereranywa n’ubw’ivyuma bifatanya Ru-PNP. Amakuru ya HRMS yerekana ko hariho ikintu gikomeye citwa carbene mu mvange y’ivyo bihimba, naho nyene ari mu rugero rutoyi. Ubu turiko turiga ingaruka z’ibintu bitera umuriro biva ku bihimba vy’umubiri bita carbene.
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