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Asidi ya Formic ninzila imwi iikonzya kugwasya kubamba hydrogen kwachiindi chilamfu. Aawa tutondezya zibeela zipya zya ruthenium clamp complexes zili afomula [RuHCl(POP)(PPh3)] kubelesya zintu zijanika mumakwebo naakuti zitakatazyi kupanga xanthos-type tridentate POP clamp ligands. Twakabelesya zintu eezyi kugwisya maanzi mu asidi ya fomiki kuti tupange CO2 a H2 muchiimo chiteteete, kakunyina kujokoloka kubelesya maanzi aa BMIM OAc (1-butyl-3-methylimidazolium acetate) mbuli musamu. Kuzwa mukulanga kwachiindi chilamfu chakusanduka, chintu chibeleka loko ni [RuHCl(xantphos)(PPh3)]Ru-1 complex iizyibidwe mumabbuku, eeyo iijisi chiindi chilamfu chakusanduka cha 4525 h-1 a 90 °C kwamaminiti aali kkumi. Mweelwe wabantu bakasanduka musule wakali 74%, mpawo kusanduka kwakamanizyigwa mumahola otatwe (>98%). Kulubazu lumwi, chintu chichita obotu loko, [RuHCl(iPr-dbfphos)(PPh3)]Ru-2 complex, chisumpula kusanduka koonse mukati ka 1 h, mpawo eezi zipa kuti kube kusanduka koonse kwa 1009 h-1. Mukuyungizya, kubeleka kwa catalytic kwakabonwa akupya kusika ku 60 °C. Muchiimo cha gasi, CO2 a H2 luzutu zyakabonwa; CO tiiyakajanwa pe. Kupima kwakuboneka kabotu kwakatondeezya kubako kwa N-heterocyclic carbene complexes mumusanganisyo wakusanduka.
Kukomena kwamusika wamanguzu aakonzya kubelesegwa lubo akusanduka kwawo kwapa kuti kube kuyandika kwaminchina yakubamba manguzu mumafakitali mumbazu zyamagesi, zyakupya, zyamakkampani azyakweenzya1,2. I-hydrogen ilabonwa kuti ninzila imwi iitola manguzu3, mpawo hydrogen carriers yamaanzi (LOHCs) lino-lino yakaba chintu chiyandikana mukuvwuntauzya, kupa chisyomezyo chakuyobola haayidirojeni munzila nguba-uba kakunyina mapenzi aajanika mukubelesya nzila zyakubelesya manguzu naa nzila zyakutontola4. ,5,6. Akaambo kabube bwazyo, bunji bwazibelesyo zyakweenzya ziliwo zyamafuta aamafuta aambi zilakonzya kubelesegwa kweenzya LOHC7,8. Bube bwa asidi yafoomu (FA) bupa kuti ibe chintu chibotu chakuyobweda haayidirojeni abulemu bwa haayidirojeni bwa 4.4%9,10. Nokuba boobo, nzila zyakasimbwa zyakugwasya kugwisya maanzi mumubili zya fomic acid kanjikanji ziyanda kubelesya zintu zikonzya kuzungaana, maanzi naa formic acid iisalala,11,12,13,14 eezyo zinga zyapa kuti kube kubelesya nzila zyakugwisya busi bwa solvent mbuli condensation, eezyo zinga zyaleta mapenzi mukubelesya basikuula. zibelesyo, mukuli uuyungizyidwe. Penzi eeli lilakonzya kuzundwa akubelesya zintu zijisi busi butayandiki kapati, mbuli maanzi aajisi ionic. Chiindi, kabunga kesu kakatondezya kuti ionic liquid butylmethylimidazolium acetate (BMIM OAc) nchintu chikonzya kunyonganya muchiimo eechi kubelesya nzila iijanwa mumakwebo ya Ru-PNP Ru-MACHO type 15. Mbuli chitondeezyo, twakatondezya FA dehydrogenation munzila iitamani kubelesya BMIMA, OAc kwiinda mu TON 18,000,000 a 95°C. Nikuba kuti zimwi nzila zyakasika a TON mpati, zyiingi zyakali kusyoma zintu zikonzya kuzungaana (mbuli THF naa DMF) naa zintu ziyungizyidwe (mbuli ma base). Mukwiimpana, mulimu wesu ubelesya maanzi aatazungaani (ILs) kakunyina zintu ziyungizyidwe.
Hazari a Bernskoetter bakaamba kugwisya maanzi mu asidi (FA) a 80 °C kubelesya Fe-PNP catalyst kakuli dioxane a LiBF4, mpawo bakajana mweelwe mupati wa turnover (TON) uubalilwa ku 1,000,00016. Laurenci wakabelesya Ru(II)- complex catalyst TPPPTS munzila iizumanana ya FA dehydrogenation system. Eeyi nzila yakapa kuti FA igwisye maanzi mumubili yoonse kakunyina buyo CO yakajanwa a 80 °C17. Kuyungizya kuya kunembo mumulimo ooyu, Pidko wakatondezya kugwisya maanzi mu FA kabelesya Ru-PNP clamp catalysts mu DMF/DBU antoomwe a DMF/NHex₃ misanganisyo, kusika ku TON values ​​ya 310,000 kusika ku 706,500 a 90 °C18. Hull, Himeda a Fujita bakaiya nzila ya Ir complex catalyst oomo KHCO3 a H2SO4 mozyakali kutuulwa, kabacincanya CO2 hydrogenation a FA dehydrogenation. Nzila zyabo zyakasika ku TONs zya 3,500,000 a 308,000 kweendelana a hydrogenation a 30°C, CO2/H2 (1:1), 1 bar pressure antoomwe a dehydrogenation aakati ka 60 a 90°C19. Sponholz, Junge a Beller bakapanga nzila ya Mn-PNP yakugwisya CO2 a FA a 90 °C20.
Aawa twakabelesya nzila ya IL, pesi muciindi cakubelesya Ru-PNPs, twakalanga-langa kubelesya Ru-POP catalysts, eezyo kweelana aluzibo lwesu tiizyakali kutondezyegwa kale mumakani aaya.
Akaambo kakujatana kwabo kubotu kwa metal-ligand (MLC), amino-PNP clamp complexes zyeendelana a Noyori-type concepts antoomwe a interacting secondary amino functional groups 21 (mbuli Ru-MACHO-BH) kanjikanji zilikuyaa kuzyibwa kapati mumilimo imwi yama molecule masyoonto. Zikozyanyo zizibidwe zibikkilizya CO22, kusanzya ma alkenes ama carbonyls, kusandula ma haidrojeni23 antoomwe akugwisigwa kwamaanzi mumubili24. Kwakaambwa kuti N-methylation ya PNP clamp ligands ilakonzya kulesya mulimo wa catalyst25, eecho chikonzya kupandululwa nkaambo kakuti ma amines abelekela mbuli ma proton, eecho nchintu chiyandikana loko muchiindi cha catalytic cycle kubelesya MLC. Nokuba boobo, nzila iimpene yakugwisigwa kwa asidi ya foomu yakabonwa ino-ino a Beller, ooko N-methylated Ru-PNP complexes nkwaakatondezya kugwisigwa kwa asidi kwa foomu kwiinda eezyo zitakwe methylated26. Mbwaanga chikozyano chakaindi tachikonzyi kutola lubazu mu MLC kwiinda mu amino unit, eezi zitondezya kuti MLC, aboobo amino unit, ilakonzya kuchita mulimu uutayandiki kapati mukusanduka kumwi kwa (de)hydrogenation kwiinda mbokwakali kuyeeyelwa chiindi.
Kweezyanisya a POP clamps, ruthenium complexes zya POP clamps tiizyakavwuntauzyigwa kabotu muchibaka eechi. Ma ligands aa POP akali kubelesegwa kapati mu hydroformylation, ooko nkwaakali kubeleka mbuli chelating ligands kutali bidentate bite angle iili afwaafwi kusika ku 120° mukujata ma ligands, alo akabelesegwa kugwasya kusala kabotu kwa zintu zili mumulongo azya mitabi27,28,29. Kuzwa aawo, Ru-POP complexes tiizyakali kubelesegwa pe mukupa kuti kube hydrogenation, asi zikozyanyo zyakubeleka kwawo mu transfer hydrogenation zyakaambwa kale30. Aawa tutondezya kuti Ru-POP complex nchintu chigwasya loko mukugusya busani bwa formic acid, ikusinizya kujana kwa Beller kuti amino unit mu Ru-PNP amine catalyst yakaindi taiyandiki pe muchiimo eechi.
Chiiyo chesu chitalikila akupanga zintu zibili zipa kuti kube kuchita zintu munzila iigaminide [RuHCl(POP)(PPh3)] (Fig. 1a). Kuchincha bupange bwa steric a electronic, dibenzo[b,d]furan yakasalwa kuzwa ku 4,6-bis(diisopropylphosphino) (Mufanikisyo 1b) 31. Zibelesyo zyakavwuntauzyigwa mumulimo ooyu zyakabambwa kubelesya nzila yabuleya yakabambwa a Whittlesey32, akubelesya [RuHCl(PP3]h333] mbuli musamu wakuyungizya ntalisyo. Swanizya nsimbi zyakusaanguna antoomwe a POP clamp ligand mu THF mubukkale butakwe maanzi akubula muuya. Kuchincha ooku kwakachitwa akusanduka kwamubala kuzwa kusalala pyu kuya kumubala wasalala pyu mpawo kwakapa chintu chisalala nikwakainda mawoola one aakujokela musule naakuti mawoola aali makumi musanu aabili aabili aakujokela musule a 40°C. Musule akugwisya THF mumuwo mpawo akusanzya tubili a hexane naa diethyl ether, triphenylphosphine yakagwisigwa kuti ipe chintu eecho mbuli fulaulu uusalala mumweelwe mupati.
Kupanga Ru-1 antoomwe a Ru-2. a) Nzila yakupanga zintu zikatazya kumvwisisisya. b) Bupange bwazintu zyakabambwa.
Ru-1 ilizyibidwe kale kuzwa mumabbuku32, mpawo bupanduluzi bumbi bubikkila maanu kuli Ru-2. I 1H NMR spectrum ya Ru-2 yakasinizya bupange bwa cis bwa atomu ya phosphine mu ligand ya hydride pair. Chitondeezyo cha dt (Fig. 2a) chitondeezya 2JP-H kweendelana kwa 28.6 antoomwe a 22.0 Hz, eezyo zili mukati kazyeezyo zyakali kulangilwa mumalipooti aakaindi32. Muchiimo cha hydrogen decoupled 31P{1H} spectrum (Fig. 2b), 2JP-P coupling constant ya 27.6 Hz yakabonwa, kusinizya kuti zyoonse zyobile clamp ligand phosphines antoomwe a PPh3 zili cis-cis. Mukuyungizya, ATR-IR itondezya bbandi lyakutandabika lya ruthenium-hydrogen a 2054 cm-1. Kuti tuyungizye kumvwisisisya bupange, Ru-2 complex yakasanduka kwiinda mukumwaika kwamuwo muchiimo chakutontola chakaanda abubotu buzulide muziiyo zya X-ray (Fig. 3, Supplementary Table 1). Ilasanduka munzila ya triclinic ya kabunga ka P-1 antoomwe a cocrystalline benzene yuniti yomwe ku yuniti ya selo. Itondezya P-Ru-P occlusal angle mpati ya 153.94°, eeyo mpati kwiinda 130° occlusal angle ya bidentate DBFphos34. A 2.401 a 2.382 Å, bulamfu bwachilongwe cha Ru-PPOP bulalampa kwiinda bulamfu bwachilongwe cha Ru to PPh3 bwa 2.232 Å, eecho chikonzya kuba akaambo kakuti DBFphos ilaa 5-ring. Bupange bwaakati kabutale buli akati-akati bwa octahedral a O-Ru-PPh3 angle ya 179.5°. Kuswaangana kwa H-Ru-Cl takuli kwamulongo pe, ambali aa 175° kuzwa ku triphenylphosphine ligand. Misinzo ya atomu abulamfwu bwakujatana zililembedwe mu Table 1.
NMR spectrum ya Ru-2. a) Busena bwa Hydride bwa 1H NMR spectrum butondezya Ru-H dt signal. b) 31 P{ 1 H} NMR spectrum itondezya zitondezyo kuzwa ku triphenylphosphine (mubala wa lubululu) a POP ligand (mubala wa sokwe).
Bupange bwa Ru-2. Ma ellipsoid aapya atondezyegwa a 70% yakulangilwa. Kuti chimvwisisisye, ma atomu aa cocrystalline benzene a hydrogen aali aa kaboni akagwisigwa.
Kulingula manguzu aama complexes aakugwisya muya mumubili, bukkale bwakusanduka bwakasalwa oomo PNP-clamp complexes (nkokuti, Ru-MACHO-BH) mozyakali kubeleka loko15. Kugwisya maanzi mu 0.5 ml (13.25 mmol) asidi yafoomu kubelesya 0.1 mol% (1000 ppm, 13 μmol) ruthenium complex Ru-1 naa Ru-2 kubelesya 1.0 ml (5.35 mmol) ionic liquid (IL) BMIM OAc (tebulu 2); Cifwanikiso 4);
Kuti tujane mweelwe, kusanduka kwakasaanguna kuchitwa kubelesya musamu wakusaanguna [RuHCl(PPh3)3]·toluene. Kuchincha ooku kuchitwa aawo mpokupya kuzwa ku 60 kusika ku 90 °C. Kweelana akulangisisya, chintu eechi tiichakali kukonzya kunyoneka mu IL nikuba kuti chakali kuzungaanisigwa kwachiindi chilamfu a 90°C, pesi kunyonyooka kwakachitika nikwakabikkwa asidi ya formic. A 90°C, kusanduka kwa 56% (TOF = 3424 h-1) kwakachitwa mumaminiti aali kkumi aakusaanguna, mpawo kusanduka kwa mweelwe (97%) kwakachitwa musule lyamawoola otatwe (kunjila 1). Kuselezya kupya kusika ku 80 °C kuchesya kusanduka kwiinda haafu kusika ku 24% musule lya 10 min (TOF = 1467 h-1, kunjila 2), akuyungizya kuchesya kusika ku 18% a 18% a 70 °C a 60 °C, kweendelana 6% (kunjila 3 a 4). Muzyiimo zyoonse, taakwe chiindi chakutalisya chakajanika, kutondeezya kuti chintu chikonzya kuchita zintu chikonzya kuba chintu chikonzya kuchita zintu naakuti kusanduka kwazintu zikonzya kuchincha nchintu chifwambaana loko kuti chikonzye kujanwa kubelesya data eeyi.
Musule akulangisisya kwakusaanguna, Ru-POP clamp complexes Ru-1 antoomwe a Ru-2 zyakabelesegwa mubukkale bukozyenye. A 90°C, kusanduka kupati kwakabonwa ndilyona. Ru-1 yakajana kusanduka kwa 74% mumaminiti aali kkumi aakusaanguna aamusunko (TOFmax = 4525 h-1, entry 5). Ru-2 yakatondezya mulimo muniini pesi uuzumanana, wakasumpula 60% yakusanduka mukati ka 10 min (TOFmax = 3669 h-1) akusanduka koonse mukati ka 60 min (>99%) (entry 9). Nchintu chilikabotu kuti Ru-2 ulisumpukide kwiinda nsimbi zyakasaanguna a Ru-1 mukusanduka koonse. Aboobo, nikuba kuti nsimbi zyakusaanguna a Ru-1 zilijisi TOFoverall iikozyenye kumamanino aakuchita (330 h-1 a 333 h-1, kweendelana), Ru-2 ilijisi TOFoverall ya 1009 h-1.
Ru-1 a Ru-2 mpawo bakabikkwa mukusanduka kwakupya ooko kupya nkokwakacheya asyoonto-asyoonto muzibeela zya 10 °C kusika ku 60 °C (Fig. 3). Kuti a 90°C chikozyano chakatondezya kubeleka chakufwambaana, kusanduka koonse kwakachitika mukati kawoola lyomwe, mpawo aawo mpaakali kupya loko kubeleka kwakaceya loko. Kusanduka kwa Py-1 kwakali 14% a 23% musule lya 10 min a 80°C a 70°C, kweendelana, mpawo musule lya 30 min kwakatanta kusika ku 79% a 73% (malembe 6 a 7). Zyoonse zyobile zyakusunka zyakatondezya mweelwe wakusanduka wa ≥90% mukati kamawoola obile. Kulilemeka kukozyenye kwakabonwa kuli Ru-2 (malembe 10 a 11). Chakugambya, Ru-1 wakali mupati mbichaani kumamanino aa 70 °C a TOF yoonse ya 315 h-1 kweelanisigwa a 292 h-1 ya Ru-2 antoomwe a 299 h-1 ya metal precursor.
Kuyungizya kuseluka kwakupya kusika ku 60 °C kwakapa kuti kutabi kusanduka kwakabonwa mumaminiti aakusaanguna aali 30 aakusola. Ru-1 teensi yakali kubeleka pe aawo mpaakali kupya kapati kumatalikilo aakusola mpawo yakayungizya kubeleka, kutondezya kuti kuyandika chiindi chakubeleka aawo Ru-1 precatalyst niyasandulwa kuba zintu zibeleka. Nikuba kuti eezi zilakonzeka kutempelecha zyoonse, maminiti aali kkumi kumatalikilo aakusola tiizyakali kuzula pe kuti tuzyibe chiindi chakubeleka mutempelecha mpati. Kulilemeka kukozyenye kwakajanika kuli Ru-2. Ku 70 a 60 °C, taakwe kusanduka kwakabonwa mumaminiti aali kkumi aakusaanguna aamusunko. Nchintu chipati kuzyiba kuti mumasunko oonse obile, kupanga kaboni monokisayidi tiikwakabonwa mukati kachiimo chesu chakubelesya (<300 ppm), a H2 a CO2 nzizyo zilikke zyakabonwa.
Kweezyanisya zyazwa mukugwisya mafuta mumubili zyakajanwa musule mukabunga aaka, kutondezya bukkale bwamazubaano akubelesya Ru-PNP clamp complexes, kwakatondezya kuti Ru-POP clamp mpya yakapangwa ilaa mulimo uukozyenye a PNP counterpart 15. Aawo clamp PNP yakajana RPMs ya 50-160-160 h mumulongo mupya wakusola POP clamp yakajana mweelwe uukozyenye wa TOFovertal wa 326 h-1, mpawo mweelwe wa TOFmax wa Ru-1 a 1590 h-1 wakabonwa. kweendelana, zili 1988 h-1 antoomwe a 1590 h-1. Ru-2 ngu 1 a 80 °C, Ru-1 ngu 4525 h-1 mpawo Ru-1 ngu 3669 h-1 a 90 °C, kweendelana.
Kulangisisya kupya kwa asidi ya foomu kubelesya Ru-1 antoomwe a Ru-2. Ziimo: 13 µmol catalyst, 0.5 ml (13.25 mmol) formic acid, 1.0 ml (5.35 mmol) BMIM OAc.
NMR ilabelesyegwa kumvwisisisya nzila zyakusanduka. Mbwaanga kuli kwiimpana kupati mu 2JH-P aakati ka hydride a phosphine ligands, chiiyo eechi chibikkilwa maanu kapati ku hydride peak. Kuli Ru-1, nzila iizyibidwe ya dt ya yuniti ya hydrogenation yakajanwa mumaminiti aakusaanguna aali 60 aakugwisigwa hydrogenation. Nikuba kuti kuli kusanduka kupati kuzwa ku −16.29 kusika ku −13.35 ppm, kweendelana kwayo a phosphine kuli 27.2 a 18.4 Hz, kweendelana (Chitondeezyo 5, Nkomwe A). Eezi zileendelana ama phosphines woonse otatwe oomo hydrogen ligand moili muchiimo cha cis mpawo chitondeezya kuti bubambe bwa ligand buli kabotu mu IL kwawoola lyomwe muchiimo chili kabotu. Kusanduka kupati kwaansi kulakonzya kuba akaambo kakugwisigwa kwa chlorinated ligands akupanga ma acetyl-formic acid complexes, kupanga kwa d3-MeCN complex mu NMR tube, naa kupanga kwa N-heterocycles kweendelana. wakapandulula. Carbene (NHC) complex. Muchiindi chakugwisya maanzi mumubili, nguzu zyachitondezyo eechi zyakazumanana kuseluka, mpawo musule lyamaminiti aali 180 chitondeezyo tiichakachili kubonwa pe. Muciindi, zitondezyo zipya zyobile zyakajanika. Chakusanguna chitondezya dd pattern iisalala iichitika a -6.4 ppm (peak B). I doublet ilijisi kujatana kupati kwa 130.4 Hz, kutondeezya kuti chimwi chazibeela zya phosphine chakayinka kweendelanya a haayidirojeni. Eezi zilakonzya kwaamba kuti POP clamp yakabambululwa kuba κ2-P,P. Kuboneka kwachintu eechi kumamanino aakusanduka kulakonzya kutondeezya kuti musyobo ooyu usololela kukulesya kubeleka kwachiindi chilamfu, mpawo apanga busena bwakusofwaazya. Kulubazu lumwi, kusanduka kwamakemikalu kusyoonto kutondeezya kuti inga kacili musyobo uutakwe maanzi15. Nkomwe yabili mpya ili a -17.5 ppm. Nikuba kuti kuvwunga kwayo takuzibinkene pe, tusyoma kuti ncibeela chatatu chili a 17.3 Hz, kutondeezya kuti hydrogen ligand ilajata buyo ku phosphine ligand ya POP clamp, alimwi kutondeezya kuzwa kwa triphenylphosphine (peak C). ilakonzya kunjililwa busena achimwi chintu, mbuli kabunga ka acetyl naakuti NHC yakapangwa mubusena oobo kuzwa ku ionic liquid. Kuzanduka kwa PPh3 kwatondezyegwa a singlet mpati a -5.9 ppm. mu 31P{1H} spectrum ya Ru-1 musule lyamaminiti aali 180 a 90 °C (langa aambi makani).
Busena bwa Hydride bwa 1H NMR spectrum ya Ru-1 muchiindi chakugwisya maanzi mu asidi ya foomu. Ziimo zyakusanduka: 0.5 ml ya asidi yafoomu, 1.0 ml ya BMIM OAc, 13.0 μmol chakugwasya, 90 °C. NMR yakagwisigwa kuzwa ku MeCN-d 3, 500 μl ya deuterated solvent, aali 10 μl ya reaction mixture.
Kuyungizya kusinizya kubako kwamisyobo iibeleka munzila ya catalytic system, high resolution mass spectrometry (HRMS) analysis ya Ru-1 yakachitwa nikwakamana kunjizigwa fomic acid kwamaminiti aali kkumi a 90 °C. Eezi zitondezya kubako kwamisyobo iitakwe chlorine ligand precatalyst mumusanganisyo wakusanduka. antoomwe azibeela zyobile zya NHC, zibeela zyazyo zitondezyedwe muchifanikisyo 6. I HRMS spectrum ilakonzya kubonwa muchifanikisyo chakuyungizya 7.
Kwiinda mu data eeyi, twasala nzila yakusanduka mukati kanyika iikozyenye ayeeyo yakaambwa a Beller, oomo N-methylated PNP clamps moichita kuti kube kusanduka kukozyenye. Kusola kumwi kutabikkilizyi maanzi aajisi ion tiikwakatondezya mulimo pe, aboobo kujatikizyigwa kwawo kulibonya kuti kuyandika. Tuyeeya kuti kubeleka kwa Ru-1 a Ru-2 kulachitika kwiinda mukugwisigwa kwa chloride kutobelwa akuyungizigwa kwa NHC akugwisigwa kwa triphenylphosphine (Scheme 1a). Ooku kubeleka mumisyobo yoonse kwakabonwa kale kubelesya HRMS. IL-acetate nchintu chiyumu kwiinda asidi yafoomu mpawo ilakonzya kugwisya mapulotoni35. Tuyeeyela kuti muchiindi chakucinca (Scheme 1b), misyobo iibeleka A iijisi NHC naa PPh3 ilaswaangana kwiinda mu formate kuti ipange musyobo B. Kubamba alimwi cibeela eeci kuba C kumamanino kupa kuti CO2 izwe alimwi a trans-dihydrogen complex D. kupanga dihydro complex E nchintu chili mbuli ntaamu mpati yakaambwa a Beller kubelesya N-methylated PNP clamp homologues. Mukuyungizya, chintu chili mbuli EL = PPh3 chakabambwa kale kwiinda mukubelesya Ru-1 mumulengalenga wa hydrogen nikwakagwisigwa chloride amunyo wa sodium. Kugwisigwa kwa haayidirojeni akujatanisya kwa formate kupa A mpawo kumanizya zyintu zyoonse.
Nzila yakusanduka kwa intrasphere ya formic acid dehydrogenation kubelesya fixing complex Ru-POP Ru-1 ilayeeyelwa.
Chintu chipya [RuHCl(iPr-dbfphos)(PPh3)] chakapangwa. Busena oobu bwakazyibwa a NMR, ATRIR, EA antoomwe a X-ray diffraction analysis yama crystals. Alimwi twaambilizya kuzwidilila kutaanzi kwakubelesya Ru-POP pincer complexes mukugusya mafuta aa formic acid kuya ku CO2 a H2. Nikuba kuti chintu chakusaanguna chakachita mulimu uukozyenye (kusikila ku 3424 h-1), chikozyano eechi chakasika achiindi chilamfu chakusanduka kusika ku 4525 h-1 a 90 °C. Kwiindawo, a 90 °C, chintu chipya [RuHCl(iPr-dbfphos)(PPh3)] chakajana chiindi choonse chakuuluka (1009 h-1) kuti chimanizye kugwisya maanzi mumubili, eecho nchipati kwiinda chakusanguna (330 h-1). antoomwe a complex yakaambwa musule [RuHCl(xantphos)(PPh3)] (333 h-1). Mubukkale bukozyenye, kubeleka kabotu kwa catalytic kulakonzya kweezyanisyigwa a Ru-PNP clamp complex. Data ya HRMS itondezya kubako kwa carbene complex mumusanganisyo wakusanduka, nikuba kuti mubunji buniini. Aciindi cino tuli mukwiiya zyintu zipa kuti zintu zibe kabotu zya carbene complexes.
Data yoonse yakajanwa naakuti yakavwuntauzyigwa muchiiyo eechi ilibikkilizyidwe muchibalo eechi [amafayela aagwasyilizya].
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