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Formic acid n’emwe aha miringo erikuha amatsiko g’okubiika amaizi g’amaizi kumara obwire buraingwa. Aha nituha omubaro gw‘ebintu bisya eby‘okuteeraho ruthenium ebiine enkora y‘omutaano [RuHCl(POP)(PPh3)] turikukoresa ebikwato by‘okuteeraho POP eby‘omuringo gwa xanthos ebirikushangwa omu katare nari ebirikukorwa omu muringo gworobi. Twakozesa ebirungo ebi kukyendeeza amaizi g’omubazi gwa formic asidi kubaasa kureetaho CO2 na H2 omu mbeera ezitarimu kugaruka enyima turikukoresa amaizi g’ayoni BMIM OAc (1-butyl-3-methylimidazolium acetate) nk’ekirungo. Okurugirira aha kureeba emirundi y’okuhindura okurikukirayo, ekirikureetaho okuhinduka okurikukirayo n’ekirungo kya [RuHCl(xantphos)(PPh3)]Ru-1 ekimanyirwe omu bihandiiko, ekiine emirundi y’okuhindura okurikukirayo 4525 h-1 ahari 90 °C kumara edakiika 10. Omubaro gw‘okuhindura bwanyima gukaba guri 74%, kandi okuhindura kukahwa omu shaaha 3 (>98%). Aha rubaju orundi, ekirikureetaho okuhinduka okurikukirayo oburungi omu bwijwire, ekihandiiko [RuHCl(iPr-dbfphos)(PPh3)]Ru-2 complex, nikitunguura okuhindura okuhikire omu shaaha 1, ekirikureetaho omubaro gw’okuhindura omu bwijwire ogwa 1009 h-1. Okwongyera ahari ekyo, emirimo y’okureetaho ebiriisa (catalytic activity) nayo ekareebeka aha bwire bw’obutagatsi oburikuhika ahari 60 °C. Omu nkora ya gaasi, CO2 na H2 byonka nibyo byareebekire; CO terikushangwa. Okupima obuhango bw’ebintu ebyabaire nibikora gye munonga kukooreka ngu hariho ebirungo bya N-heterocyclic carbene omu ntaburwa y’okugarukamu.
Okweyongyera kw’akatare k’amaani agarikugarukaho n’okuhinduka kwago kureeteire okwetenga kwa tekinologiya y’okubiika amaani aha rurengo rw’amakorero omu by’amashanyarazi, eby’okwotsya, eby’amakorero n’eby’entambura1,2. Haidrojeni neetwarwa nk’emwe aha nshonga ezirikutwara amaani maingi3, kandi ebirikutwara amaizi g’ebihangirwe (LOHCs) ebiherize kuhinduka ekigyendererwa ky’okucondooza, ebirikuha okuraganisa kw’okubiika haidrojeni omu muringo gworobi ogurikukorwaho hatariho bizibu ebirikukwatagana n’okukoresa pressurization nari cryogenic technologies4. ,5,6. Ahabw’ebintu byazo eby’omubiri, bingi aha by’entambura ebiriho eby’amajuta g’emotoka n’ebindi ebiri omu maizi nibibaasa kukoresibwa kutwara LOHC7,8. Ebintu by’omubiri bya formic acid (FA) nibigihindura ekintu ekirikuha amatsiko omu kubiika amaizi g’omubiri n’oburemeezi bwa 4.4%9,10. Kwonka, enkora z‘okushohoza ezihandiikirwe ez‘okukyendeeza aha maizi g‘omubiri (catalytic acid dehydrogenation) omu muringo gw‘omutaano nizetenga okukoresa ebirungo by‘ebihangirwe ebirikuhinduka, amaizi nari pure formic acid,11,12,13,14 ebirikubaasa kwetengyesa okukoresa obukoryo bw‘okutaanisa omuyaga gw‘ebirungo nk‘okuteerana, ekirikubaasa kureetera oburemeezi omu kukozesa. ebishabirwe, omugugu ogwongyeirweho. Ekizibu eki nikibaasa kusingurwa orikukoresa ebirungo ebiine omuyaga ogutarikwetegyerezibwa, nk’amaizi g’ayoni. Enyima, ekibiina kyaitu ky‘okukora kikooreka ngu amaizi g‘omubiri agarikwetwa butylmethylimidazolium acetate (BMIM OAc) n‘ekintu ekihikire omu nkora egi barikukoresa omubazi gw‘okuhamya ogurikushangwa omu katare Ru-PNP Ru-MACHO omuringo 15. Nk‘eky‘okureeberaho, tukooreka FA erikugumizamu n‘okusheeshasheesha kw‘amaizi omu nkora y‘okusheeshasheesha kwa FA a TON y’ebintu ebirikurenga 18,000,000 ahari 95°C. N‘obu enkora ezimwe ziraabe zaabaire zitungire TON y‘ahaiguru enyima, nyingi zikaba nizeesiga ebirungo by‘ebihangirwe ebirikuhindukahinduka (nka THF nari DMF) nari ebirungo ebirikukoresibwa (nk‘ebirungo by‘okutandikiraho). Okutaana n’ekyo, omurimo gwaitu buzima nigukoresa amaizi agatarikuhinduka (ILs) kandi hatariho ebirikwongera.
Hazari na Bernskoetter bakagamba aha kusheeshasheesha kw’amaizi g’omubiri (FA) ahari 80 °C barikukoresa ekirungo kya Fe-PNP omu kubaho kwa dioxane na LiBF4, bakatunga omubaro gw’okuhindura (TON) ogurikushemeza ogurikwingana 1,000,00016. Laurenci akakozesa Ru(II)- ekigumire ekirikureetaho TPPPTS omu nkora y‘okugumizamu n‘okukyendeeza amaizi ga FA. Omuringo ogu gukarugamu okusheeshasheesha kwa FA haihi okuhikire n’obucweka bukye munonga bwa CO obushangirwe ahari 80 °C17. Okutunguura omurimo ogu, Pidko akooreka okugaruka enyima kw’okukyendeeza amaizi ga FA arikukoresa ebikwato bya Ru-PNP clamp omu ntaburwa za DMF/DBU na DMF/NHex3, akahikiiriza emihendo ya TON eya 310,000 kuhika 706,500 ahari 90 °C18. Hull, Himeda na Fujita bakacondooza aha nkora ya Ir complex ey’ebicweka bibiri omu KHCO3 na H2SO4 ebyabaire nibiheebwayo nk’ekitambo, barikuhindura CO2 okuhindura amaizi n’okuhindura amaizi ga FA. Enkora zaabo zikatunga TONs ezirikurenga 3,500,000 na 308,000 ahabw’okuhindura amaizi aha 30°C, CO2/H2 (1:1), 1 bar pressure n’okuhindura amaizi ahagati ya 60 na 90°C19. Sponholz, Junge na Beller bakakora ekicweka kya Mn-PNP eky’okugaruzaho CO2 n’okukyendeeza FA aha 90 °C20.
Aha tukakozesa enkora ya IL, kwonka omu mwanya gw‘okukoresa Ru-PNPs, tukacondooza aha kukozesa ebikwato bya Ru-POP, ebi nk‘oku turikumanya bitakagambirweho enyima omu nshonga egi.
Ahabw‘okuteerana kwabo okurungi munonga kw‘ekyoma n‘ebikwato (MLC), amino-PNP clamp complexes ezirikwegamira aha miteekateekyere y‘omuringo gwa Noyori n‘ebicweka by‘emirimo bya amino eby‘akabiri ebirikukoragana 21 (nka Ru-MACHO-BH) okutwarira hamwe nibyeyongyera kukundwa omu mirimo emwe y‘ebicweka bikye. Eby’okureeberaho ebirikumanywa munonga harimu CO22, okuhindura amaizi ga alkenes na carbonyls, okuhindura amaizi g’okuhingisa23 n’okuhindura amaizi g’eby’okunywa ebitarikwikirizibwa24. Kigambirwe ngu N-methylation ya PNP clamp ligands neebaasa kwemereza kimwe omurimo gw’okureetaho25, ekirikubaasa kushoboororwa ahabw’okugira ngu amines nizikora nk’enshonga za purotoni, ekiri ekyetengo kikuru omu bwire bw’okuhindura ebiri omu nkora orikukoresa MLC. Kwonka, omuze ogurikuhakanisa omu kusheeshasheesha kwa formic acid gukareebeka juba na Beller, ahu N-methylated Ru-PNP complexes buzima zaayorekire okusheeshasheesha kurungi kw’okusheeshasheesha kwa formic acid kukira bagyenzi baabo abatari methylated26. Ahabw‘okugira ngu ekicweka ky‘okubanza tikirikubaasa kwejumba omu MLC kurabira omu kicweka kya amino, eki nikimanyisa munonga ngu MLC, n‘ahabw‘ekyo ekicweka kya amino, nikibaasa kukora omurimo mukye omu mpinduka ezimwe eza (de)hydrogenation kukira oku kyabaire nikiteekateekwaho enyima.
Okugyeragyeranisa n‘ebikwato bya POP, ebikwato bya ruthenium eby‘ebikwato bya POP tibikakyebeirwe gye omu mwanya ogu. POP ligands omu buhangwa zikoresiibwe munonga omu hydroformylation, ahu zirikukora nka chelating ligands omu mwanya gw’okukoresa bidentate bite angle erikwingana 120° ahabw’okukwatira ligands, ezibaire zikoresiibwe kutunguura okutoorana kw’ebintu ebiri omu murongooti n’ebiine amataagi27,28,29. Kuruga obwo, Ru-POP complexes tizirikukoresibwa munonga omu kuhindura amaizi, kwonka eby’okureeberaho by’emirimo yaabyo omu kuhindura amaizi bikaba byagambirweho enyima30. Aha nitworeka ngu Ru-POP complex n’ekintu ekirikukora gye omu kusheeshasheesha kwa formic acid, ekirikuhamya okuzoora kwa Beller ngu ekicweka kya amino omu kirungo kya Ru-PNP amine eky’omurembe tikiine mugasho omu nkora egi.
Okwega kwaitu nikutandika n‘okuteerana ebirungo bibiri eby‘omutaano ebiine enkora y‘omugasho [RuHCl(POP)(PPh3)] (Fig. 1a). Okuhindura omu nkora ya steric n’ey’ebyoma, dibenzo[b,d]furan ekatooranwa kuruga omu 4,6-bis(diisopropylphosphino) erikushangwa omu katare (ekishushani 1b) 31. Ebirikureetaho okuhinduka kw’ebintu ebyashomwa omu murimo ogu bikakorwa barikukoresa omuringo gw’omutaano ogwakozirwe Whittlesey32, n’okukoresa [PP]3uct3uct. ekirikubanza. Tabura ekyoma ekirikubanza na POP clamp ligand omu THF omu mbeera z‘okubura amaizi n‘okubura omuyaga. Okugarukamu kukaba kuriho n’empindahinduka y’erangi y’amaani kuruga aha rangi erikutukura kuza aha rangi ya kyenju kandi ekaha ekirugiremu ekishemeire bwanyima y’eshaaha 4 z’okugaruka omu nkora nari eshaaha 72 z’okugaruka omu nkora ahari 40°C. Bwanyima y’okuihaho THF omu mwanya ogutarimu kintu kyona n’okunaaba emirundi ebiri na hexane nari diethyl ether, triphenylphosphine ekaihwaho kuha ekirugiremu nk’esaano y’erangi ya kyenju omu kutunga ebiriisa bingi.
Okuteerana kw’ebicweka bya Ru-1 na Ru-2. a) Omuringo gw’okuteerana ebigambo ebigumire. b) Omubumbi w’ekicweka ekikozirwe omu nkora.
Ru-1 ekaba yaaheza kumanywa kuruga omu bihandiiko32, kandi okushoboorora okurikukiraho nikuta omutima ahari Ru-2. 1H NMR spectrum ya Ru-2 ekahamya enkora ya cis ey’atomu ya phosphine omu ligand y’omubaro gw’amaizi. Puloti ya dt y‘ahaiguru (Fig. 2a) neeyoreka ebicweka by‘okuteerana 2JP-H ebya 28.6 na 22.0 Hz, ebiri omu nkora erikuteekateekwaho omu ripoota ezabandize32. Omu nkora y‘okuteerana kwa haidrojeni 31P{1H} (ekishushani 2b), okuteerana kwa 2JP-P okutarimu kuhinduka okwa 27.6 Hz kukareebeka, ekirikuhamya ngu bombi phosphines z‘okuteerana kw‘ekikwato ky‘okuteerana na PPh3 ni cis-cis. Okwongyera ahari ekyo, ATR-IR neeyoreka obumanyiso bw’okutambatambura kwa ruthenium-hydrogen ahari 2054 cm-1. Ahabw’okushoboorora okurikukiraho aha nkora, ekicweka kya Ru-2 kikaba kiri ekibiriiti ahabw’okujanjaara kw’omuyaga aha bwire bw’obutagatsi bw’omu kishengye n’omutindo ogurikumara okucondooza kwa X-ray (Fig. 3, Supplementary Table 1). Nikihinduka ekibiriiti omu nkora ya triclinic ey’ekibiina ky’omu mwanya P-1 n’ekicweka kimwe kya cocrystalline benzene ahari buri kicweka ky’obutafaari. Nikyoreka enkokora mpango ya P-Ru-P ey’okukinga eya 153.94°, erikukira munonga enkokora y’okukinga eya 130° ey’ebihangirwe bidentate DBFphos34. Aha 2.401 na 2.382 Å, oburaingwa bw‘omukago gwa Ru-PPOP nibukira munonga oburaingwa bw‘omukago gwa Ru kuhika PPh3 ogwa 2.232 Å, ekirikubaasa kuba nikiruga omu nkora mpango y‘omugongo gwa DBFphos erikureetwaho 5-ring yaayo eya rwagati. Geometry y’ekyoma ahagati y’ekyoma n’eky’omugasho munonga ey’ebicweka munaana n’enkokora ya O-Ru-PPh3 eya 179.5°. Okuteerana kwa H-Ru-Cl tikuri omu nkora yoona, n’enkokora erikwingana 175° kuruga aha nkora ya triphenylphosphine. Oburaingwa bwa atomu n’oburaingwa bw’enkoragana biri omu runyiriri 1.
NMR ekishushani kya Ru-2. a) Ekicweka kya Hydride eky’omubaro gwa 1H NMR ekirikworeka akamanyiso ka Ru-H dt. b) 31 P{ 1 H} NMR spectrum erikworeka obumanyiso kuruga omu nkora ya POP (bururu) n‘enkora ya POP (kinyasi).
Enkora ya Ru-2. Ebishushani by’okwotsya nibyorekwa n’okubaasa kubaho kwa 70%. Ahabw’okushoborokyerwa gye, atomu za benzene na haidrojeni eziri aha kaboni zikarugaho.
Okushwijuma obushoboorozi bw‘ebizibu by‘okukyendeeza amaizi omu mubiri gwa formic acid, embeera z‘okugarukamu zikatooranwa ahansi y‘ebizibu bya PNP-clamp ebirikuhikaana (nk‘eky‘okureeberaho, Ru-MACHO-BH) ebyabaire nibikora munonga15. Okukyendeeza aha maizi g‘omubiri (IL) BMIM OAc (ekipande-2) Ekishushani 4);
Okutunga omutindo, okugarukamu kukabanza kwakorwa barikukoresa ekirungo ky’okubanza [RuHCl(PPh3)3]·toluene. Okugarukamu oku nikukorwa aha bwire bw’obutagatsi kuruga ahari 60 kuhika ahari 90 °C. Okurugirira aha kureeba okwanguhi okurikureebwa, ekizibu eki kikaba kitarikubaasa kusheesheka kimwe omu IL n’obu kyakuba nikisheesheka kumara obwire buraingwa aha bwire bw’obutagatsi bwa 90°C, kwonka okusheesheka kukabaho bwanyima y’okutaho formic acid. Aha 90°C, okuhindura kwa 56% (TOF = 3424 h-1) kukahikirizibwa omu dakiika 10 z‘okubanza, kandi haihi okuhindura kw‘omubaro (97%) kukahikirizibwa bwanyima y‘eshaaha ishatu (okutaaha 1). Okukyendeeza aha bwire bw‘obwire kuhika ahari 80 °C nikikyendeeza aha kuhinduka n‘ebicweka ebirikurenga aha kicweka kuhika ahari 24% bwanyima y‘edakiika 10 (TOF = 1467 h-1, enyuguta 2), kwongyera kukyendeeza aha 18% na 18% ahari 70 °C na 60 °C, buri kimwe 6% (enyuguta 3 na 4). Omu mbeera zoona, tihaine obwire bw‘okutandika (induction period) obwashangirwe, ekirikumanyisa ngu ekirikureetaho okuhinduka nikibaasa kuba kiri ebika by‘ebintu ebirikukora nari ngu okuhindura ebika by‘ebintu ebirikukora nikurahuka munonga kubaasa kumanyirwaho orikukoresa ekibiina ky‘amakuru eki.
Bwanyima y‘okushwijuma ebirikubanza, ebikwato bya Ru-POP clamp complexes Ru-1 na Ru-2 bikakoresibwa omu mbeera zimwe. Aha 90°C, okuhinduka kw’ahaiguru kukareebeka ahonaaho. Ru-1 ekatunga okuhinduka kwa 74% omu dakiika 10 z‘okubanza z‘okugyezesa (TOFmax = 4525 h-1, okutaaha 5). Ru-2 ekooreka emirimo mikye kwonka etarikuhinduka, erikutunguura okuhindura 60% omu dakiika 10 (TOFmax = 3669 h-1) n‘okuhindura okuhikire omu dakiika 60 (>99%) (okutaaha 9). Nikimanyisa ngu Ru-2 neekira munonga ekyoma ekirikubanza na Ru-1 omu kuhinduka okuhikire. Nahabwekyo, obwo ekyoma ekirikubanza na Ru-1 biine emihendo ya TOFoverall erikushushana aha kuhendera kw’okugarukamu (330 h-1 na 333 h-1, buri kimwe), Ru-2 eine TOFoverall ya 1009 h-1.
Ru-1 na Ru-2 bwanyima bakahindurwa obutagatsi obu obutagatsi bwakyendeera mpora mpora omu kweyongyera kwa 10 °C kuhika ahari 60 °C (Fig. 3). Ku kiraabe ngu aha 90°C ekizibu kyorekire emirimo y‘ahonaaho, okuhinduka haihi okuhikire kukabaho omu shaaha emwe, reero aha bwire bw‘obwire bw‘ahansi emirimo ekagwa munonga. Okuhinduka kwa Py-1 kukaba kuri 14% na 23% bwanyima y‘edakiika 10 ahari 80°C na 70°C, kandi bwanyima y‘edakiika 30 kukaba kweyongyera kuhika ahari 79% na 73% (enyuguta 6 na 7). Okucondooza kwombi kukooreka omubaro gw‘okuhindura ≥90% omu shaaha ibiri. Emicwe nk‘egi ekareebeka ahari Ru-2 (enyuguta 10 na 11). Ekirikushemeza, Ru-1 ekaba neekiraho kakye aha muheru gw’okugarukamu ahari 70 °C n’omubaro gwona ogwa TOF ogwa 315 h-1 kugyeragyeranisa na 292 h-1 ahari Ru-2 na 299 h-1 ahari ekyoma ekirikubanza.
Okwongyera kukyendeera kw’obutagatsi kuhika ahari 60 °C kukareetera ngu tihaine kuhinduka okwareebirwe omu dakiika 30 z’okubanza ez’okugyezesa. Ru-1 ekaba etarikukora munonga aha bwire bw’obwire oburi ahansi munonga aha kutandika kw’okugyezesa kandi bwanyima y’ekyo ekayongyera aha mirimo, ekirikworeka ngu nikyetengyesa obwire bw’okukora obu Ru-1 precatalyst erikuhindurwamu ebika ebirikukora nk’eby’okukora. N‘obu eki kiraabe nikibaasika aha bwire bw‘obwire bwona, edakiika 10 aha kutandika kw‘okugyezesa zikaba zitarikumara kubaasa kumanya obwire bw‘okukora aha bwire bw‘obwire bw‘ahaiguru. Emicwe nk’egyo ekashangwa ahari Ru-2. Aha 70 na 60 °C, tihaine kuhinduka okwareebirwe omu dakiika 10 z’okubanza ez’okugyezesa. Ni kikuru kumanya ngu omu kucondooza kwombi, okuhangwa kwa carbon monoxide tikwareebirwe omu kikomo ky‘okukyebera eky‘ekikwato kyaitu (<300 ppm), H2 na CO2 nizo zonka ezaareebirwe.
Okugyeragyeranisa ebyarugamu omu kukyebera amaizi g‘omubiri (formic acid dehydrogenation) ebyatungirwe enyima omu guruupu y‘okukora egi, ebirikujwekyera embeera y‘omurembe kandi birikukoresa ebikwato bya Ru-PNP clamp complexes, byorekire ngu ekikwato kya Ru-POP ekisya ekikozirwe kiine emirimo erikushushana n‘eya PNP 15. Obu ekikwato kya ba PNP-02 kitungire hPMs1. ekikwato kisya kya POP kikatunga omuhendo gwa TOFovertal ogurikushushana ogwa 326 h-1, kandi omuhendo gwa TOFmax ogwa Ru-1 na 1590 h-1 gukakyeberwa. nk’oku biri, ni 1988 h-1 na 1590 h-1. Ru-2 ni 1 ahari 80 °C, Ru-1 ni 4525 h-1 kandi Ru-1 ni 3669 h-1 ahari 90 °C, nk’oku biri.
Okukyebera obutagatsi bw’okukyendeeza amaizi omu nkora ya formic acid orikukoresa ebikwato bya Ru-1 na Ru-2. Embeera: 13 μmol y‘ekirungo ky‘okureetaho, miriyoni 0.5 (mmol 13.25) y‘omubazi gw‘okukyebera, miriyoni 1.0 (mmol 5.35) ya BMIM OAc.
NMR neekoresibwa kwetegyereza emiringo y‘okugarukamu. Ahabw‘okugira ngu hariho entaaniso mpango munonga omu 2JH-P ahagati y‘ebicweka bya hydride na phosphine ligands, ekigyendererwa ky‘okwega oku kiri aha mutwe gwa hydride. Aha Ru-1, omuringo gwa dt ogw‘omutaano gw‘ekicweka ky‘okuha amaizi gukashangwa omu dakiika 60 z‘okubanza z‘okuha amaizi. N‘obu haraabe hariho okuhinduka kw‘amaani kuruga aha −16.29 kuhika ahari −13.35 ppm, ebirikugumaho eby‘okuteerana kwayo na phosphine ni 27.2 na 18.4 Hz, buri kimwe (ekishushani 5, Enshonga A). Eki nikikwatagana na phosphines zoona ishatu ezi hydrogen ligand eri omu nkora ya cis kandi nikimanyisa ngu enkora ya ligand neegumaho omu IL kumara nk‘eshaaha emwe ahansi y‘embeera z‘okugarukamu ezihikire. Okuhinduka kw’amaani okw’ahansi nikubaasa kuba nikureetwaho okumaraho ebikwato ebirimu klorini n’okukora ebikwato ebirikuhikaana na acetyl-formic acid complexes, okukora in situ ekirungo kya d3-MeCN omu ntuumo ya NMR, nari okukora ebikwato bya N-heterocycles ebirikuhikaana. akashoboorora. Ekizibu kya karibeni (NHC). Omu bwire bw’okukora kw’okukyendeeza amaizi, amaani g’akamanyiso aka gakagumizamu nigakyendeera, kandi bwanyima y’edakiika 180 akamanyiso kakaba katakireebeka. Kureka, bakazoora obumanyiso bubiri busya. Eky‘okubanza nikyoreka enkora ya dd erikureebwa gye erikubaho ahari -6.4 ppm (enshonga B). Ekicweka kya kabiri kiine ekicweka kihango ky’okuteerana ekirikugumaho nka 130.4 Hz, ekirikworeka ngu kimwe aha bicweka bya phosphine kikatambura kugyeragyeranisa na haidrojeni. Eki nikibaasa kumanyisa ngu ekikwato kya POP nikigaruka kitebeekanisibwa omu nkora ya κ2-P,P. Okureebeka kw’ekizibu eki bwanyima y’okukyerererwa omu kuhindura ebiri omu nkora nikibaasa kworeka ngu ekika eki nikireetaho emihanda y’okuremwa kukora omu bwire, ekirikureetaho ekizibu ky’okuhindura ebiri omu nkora. Aha rubaju orundi, okuhinduka kw’eby’obuhangwa okukye nikworeka ngu nikibaasa kuba kiri ekika ky’amaizi g’ebinyonyi bibiri15. Enshonga ensya eya kabiri eri aha -17.5 ppm. N‘obu omubiri gwayo guraabe gutarikumanywa, nitwikiriza ngu n‘ekicweka kishatu ekiine akacweka kakye k‘okuteerana aka 17.3 Hz, ekirikworeka ngu ekicweka ky‘amaizi nikikwatanisa n‘ekicweka kya phosphine kyonka eky‘ekikwato kya POP, ekirikworeka n‘okurekura kwa triphenylphosphine (enshonga C). Nikibaasa kuhindurwa ekindi kirungo, nk’ekibiina kya acetyl nari NHC erikubaho omu mwanya kuruga omu maizi g’ayoni. Okutaana kwa PPh3 nikugaruka kworekwa singlet y’amaani ahari -5.9 ppm. omu 31P{1H} spectrum ya Ru-1 bwanyima y’edakiika 180 ahari 90 °C (reeba ebindi).
Ekicweka kya hydride ekya 1H NMR spectrum ya Ru-1 omu bwire bw’okusheeshasheesha kwa asidi ya formic. Embeera z‘okugarukamu: miriyoni 0.5 z‘asidi ya formiki, miriyoni 1.0 ya BMIM OAc, 13.0 μmol y‘ekirungo ky‘okureetaho, 90 °C. NMR ekatwarwa kuruga omu MeCN-d 3 , 500 μl y’ekirungo ekirimu deuterated, enkumi 10 μl z’ekirungo ky’okugarukamu.
Okwongera kuhamya okubaho kw’ebika ebirikukora omu nkora y’okureetaho okuhinduka, okucondooza kwa Ru-1 okwa high resolution mass spectrometry (HRMS) kukakorwa bwanyima y’okuteebwamu formic acid kumara edakiika 10 ahari 90 °C. Eki nikimanyisa okubaho kw’ebika ebitariho ekirungo kya chlorine ligand precatalyst omu ntaburwa y’okugarukamu. hamwe n‘ebicweka bibiri bya NHC, ebitebeekanisiibwe byabyo nibyorekwa omu kishushani 6. Eby‘okureeberaho bya HRMS ebirikuhikaana nibibaasa kureebwa omu kishushani ky‘okwongyeraho 7.
Okurugirira aha makuru aga, nituteekateeka aha nkora y‘okugarukamu ey‘omunda y‘ensi erikushushana n‘eyateirweho Beller, omu N-methylated PNP clamps zirikureetaho okugarukamu kumwe. Ebindi bigyezo ebitarimu amaizi g’ayoni tibyorekire omurimo gwona, n’ahabw’ekyo okwejumba kwayo okuhikire nikureebeka nk’okurikwetengyesa. Nituteekateeka ngu okukora kwa Ru-1 na Ru-2 nikubaho kurabira omu kusheesheka kwa kloride kukuratirwaho okwongyeraho NHC okurikubaasa kubaho n‘okusheesheka kwa triphenylphosphine (Ekishushani 1a). Okukora oku omu miringo yoona kukaba kureebekire enyimaho barikukoresa HRMS. IL-acetate n’ekirungo kya Bronsted eky’amaani kukira formic acid kandi nikibaasa kusheenya munonga eky’aha muheru35. Nituteekateeka ngu omu bwire bw‘omuringo gw‘okuhindura (Scheme 1b), ebika ebirikukora A ebiine NHC nari PPh3 nibikwatanisibwa kurabira omu formate kuhanga ebika B. Okugaruka kutebeekanisa ekizibu eki kuza omu C aha muheru nikirugamu okurekura CO2 n‘ekizibu kya trans-dihydrogen D Okukurataho a protonation ya dixd asidi kubaasa kuhanga dihydro complex E neeshushana n‘eidaara rikuru eri Beller yaateireho arikukoresa ebikwato by‘okuteeraho PNP ebiine N-methylated. Okwongyera ahari ekyo, analogue y’ekintu ekigumire EL = PPh3 ekaba ekozirwe enyimaho omu nkora ya stoichiometric reaction barikukoresa Ru-1 omu mwanya gw’amaizi bwanyima y’okushohoza kloride n’omunyugunyu gwa sodium. Okwihaho haidrojeni n‘okuteerana kwa formate nikiha A kandi nikihezaho omuzingo.
Enkora y‘okugarukamu kw‘omunda y‘omubiri ey‘okukyendeeza amaizi g‘omubiri (formic acid) orikukoresa ekirungo ky‘okuhamya Ru-POP Ru-1 neeteekateekwaho.
Ekirungo kisya [RuHCl(iPr-dbfphos)(PPh3)] kikozirwe. Ekizibu eki kikaba nikimanyirwa aha kucondooza kwa NMR, ATRIR, EA hamwe na X-ray okurikukoresibwa okutaana kw’ebishushani by’ebicupuri bimwe. Nituha n’okuha ripooti y’okubanza ey’obusinguzi bw’okukoresa ebikwato bya Ru-POP pincer complexes omu kuhindura amaizi g’omubiri gwa formic acid kuba CO2 na H2. N’obu ekyoma ekirikubanza kyatunga omurimo nigwo gumwe (okuhika ahari 3424 h-1), ekizibu eki kikahika aha nkora y’okuhindura ebirikwingana 4525 h-1 ahari 90 °C. Ekindi, ahari 90 °C, ekizibu ekisya [RuHCl(iPr-dbfphos)(PPh3)] kikatunga obwire bwona obw’okuguruka (1009 h-1) kuhezaho okusheeshasheesha kwa formic acid, okuri ahaiguru munonga kukira okw’ekyoma ekirikubanza (330 h-1). n‘ekizibu ekyagambirweho enyima [RuHCl(xantphos)(PPh3)] (333 h-1). Omu mbeera nk‘ezo, obushoboorozi bw‘okureetaho okuhinduka nibugyeragyeranisibwa n‘obwa Ru-PNP clamp complex. Ebihandiiko bya HRMS nibyoreka okubaho kw’ekirungo kya carbene omu ntaburwa y’okugarukamu, n’obu kiraabe kiri omu bwingi bukye. Obwahati turiyo nitushoma aha bikwatiraine n’ebintu ebirikukora nk’ebirungo bya carbene.
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