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Formic acid ndeimwe yemhando dzinonyanya kuvimbisa kuchengetedza hydrogen yemvura kwenguva refu. Pano tinoratidza runyoro rwemhando itsva dzeruthenium clamp complexes dzine fomura yakajairika [RuHCl(POP)(PPh3)] tichishandisa xanthos-type tridentate POP clamp ligands dzinowanikwa kutengeswa kana kuti dziri nyore kugadzira. Takashandisa ma complexes aya kubvisa hydrogenate formic acid kuti igadzire CO2 neH2 pasi pemamiriro akapfava, asina reflux tichishandisa ionic liquid BMIM OAc (1-butyl-3-methylimidazolium acetate) se solvent. Kubva pakuona kwehuwandu hwemaximum turnover frequency, catalyst inoshanda zvikuru i [RuHCl(xantphos)(PPh3)]Ru-1 complex inozivikanwa mumabhuku, ine maximum turnover frequency ye4525 h-1 pa90 °C kwemaminitsi gumi. Chiyero che post-conversion chaive 74%, uye conversion yakapedzwa mukati memaawa matatu (>98%). Kune rumwe rutivi, catalyst ine kushanda kwakanakisisa, itsva [RuHCl(iPr-dbfphos)(PPh3)]Ru-2 complex, inokurudzira kushanduka kwakazara mukati meawa imwe chete, zvichikonzera huwandu hwekuchinjana kwe1009 h-1. Pamusoro pezvo, catalytic activity yakaonekwawo patembiricha inosvika 60 °C. Muchikamu chegasi, CO2 neH2 chete ndizvo zvakaonekwa; CO2 haina kuonekwa. High-resolution mass spectrometry yakaratidza kuvapo kweN-heterocyclic carbene complexes mumusanganiswa we reaction.
Kukura kwemusika wesimba rinodzokororwa uye kusiyana kwaro kwakaita kuti pave nekudiwa kwetekinoroji dzekuchengetedza simba dzemaindasitiri muzvikamu zvemagetsi, zvekupisa, zvemaindasitiri uye zvekufambisa1,2. Hydrogen inoonekwa seimwe yemagetsi anotakura simba akawanda3, uye liquid organic hydrogen carriers (LOHCs) ichangobva kuve chinangwa chekutsvagisa, ichipa vimbiso yekuchengetedza hydrogen muchimiro chiri nyore kushandisa pasina matambudziko ane chekuita nekumanikidzwa kana tekinoroji ye cryogenic4. ,5,6. Nekuda kwehunhu hwavo hwepanyama, zvivakwa zvakawanda zvekufambisa zviripo zvepeturu nemamwe mafuta emvura zvinogona kushandiswa kutakura LOHC7,8. Hunhu hwepanyama hwe formic acid (FA) hunoita kuti ive mukana wekuchengetedza hydrogen ine huremu hwehydrogen hwe4.4%9,10. Zvisinei, masisitimu e catalytic akaburitswa e formic acid dehydrogenation anowanzo da kushandiswa kwe volatile organic solvents, mvura kana pure formic acid,11,12,13,14 izvo zvinogona kuda kushandiswa kwe solvent vapor separation techniques dzakadai se condensation, izvo zvinogona kutungamira kumatambudziko mukushandiswa kwevatengi. maapplication, mutoro wekuwedzera. Dambudziko iri rinogona kugadziriswa nekushandisa zvinonyungudutsa zvine simba shoma remhepo, zvakaita se ionic liquids. Kare, boka redu rekushanda rakaratidza kuti ionic liquid butylmethylimidazolium acetate (BMIM OAc) ndiyo solvent yakakodzera mukuita uku tichishandisa Ru-PNP Ru-MACHO type 15 inowanikwa mukutengeserana. Semuenzaniso, takaratidza FA dehydrogenation mu continuous flow system tichishandisa BMIM OAc, tichiwana TON inopfuura 18,000,000 pa95°C. Kunyangwe mamwe masisitimu akambowana TON yakakwira, mazhinji aivimba nezvinyungudutsa zve organic (senge THF kana DMF) kana zvimwe zvinoshandiswa (senge mabhesi). Kusiyana neizvi, basa redu rinoshandisa non-volatile ionic liquids (ILs) uye hapana zvimwe zvinowedzerwa.
Hazari naBernskoetter vakataura nezvekubviswa kwehydrogen kweformic acid (FA) pa80 °C vachishandisa Fe-PNP catalyst pamberi pe dioxane neLiBF4, zvichiwana nhamba inoshamisa yekuchinjana (TON) inosvika 1,000,00016. Laurenci akashandisa Ru(II)- complex catalyst TPPPTS muchirongwa chekubvisa hydrogenation cheFA chinoenderera mberi. Nzira iyi yakaguma nekubviswa kwehydrogenation kweFA kwakazara nezviratidzo zvishoma zveCO zvakaonekwa pa80 °C17. Kuti afambise mberi basa iri, Pidko akaratidza kuderedzwa kwehydrogenation kweFA achishandisa Ru-PNP clamp catalysts muDMF/DBU uye DMF/NHex₃ mixtures, achiwana TON values ​​​​dze310,000 kusvika 706,500 pa90 °C18. Hull, Himeda naFujita vakadzidza binuclear Ir complex catalyst umo KHCO3 neH2SO4 zvakabayirwa, zvichichinjana CO2 hydrogenation uye FA dehydrogenation. Masisitimu avo akawana maTON anopfuura 3,500,000 uye 308,000 zvichiteerana kuti awane hydrogenation pa30°C, CO2/H2 (1:1), 1 bar pressure uye kuti awane hydrogenation pakati pe60 ne90°C19. Sponholz, Junge naBeller vakagadzira Mn-PNP complex ye CO2 hydrogenation inodzoserwa uye FA dehydrogenation pa90°C20.
Pano takashandisa nzira yeIL, asi pachinzvimbo chekushandisa Ru-PNPs, takaongorora kushandiswa kweRu-POP catalysts, izvo zvatisati tamboona zvichiratidzwa panyaya iyi.
Nekuda kwekubatana kwavo kwakanaka kwesimbi-ligand (MLC), ma amino-PNP clamp complexes akavakirwa paNoyori-type concepts nemapoka echipiri eamino anoshanda 21 (akadai seRu-MACHO-BH) ari kuramba achinyanya kufarirwa mune mamwe mamorekuru madiki. Mienzaniso yakakurumbira inosanganisira CO22, hydrogenation yealkenes nemacarbonyls, transfer hydrogenation23 uye acceptorless dehydrogenation yealcohols24. Zvakataurwa kuti N-methylation yePNP clamp ligands inogona kumisa zvachose catalyst activity25, izvo zvinogona kutsanangurwa nekuti amines anoshanda semaproton sources, inova chinhu chakakosha panguva ye catalytic cycle uchishandisa MLC. Zvisinei, mafambiro akasiyana mu formic acid dehydrogenation akaonekwa munguva pfupi yapfuura naBeller, uko N-methylated Ru-PNP complexes yakaratidza zviri nani catalytic dehydrogenation ye formic acid kupfuura unmethylated counterparts26. Sezvo complex yekare isingakwanise kutora chikamu muMLC kuburikidza neamino unit, izvi zvinoratidza zvakasimba kuti MLC, uye nokudaro amino unit, inogona kutamba basa risinganyanyi kukosha mune mamwe mashanduko (de)hydrogenation kupfuura zvaifungidzirwa kare.
Zvichienzaniswa nePOP clamps, ruthenium complexes dzePOP clamps hadzina kudzidzwa zvakakwana munzvimbo iyi. POP ligands dzagara dzichishandiswa zvakanyanya pakuita hydroformylation, uko dzinoshanda se chelating ligands pane kuita se bidentate bite angle inosvika 120° ye clamping ligands, iyo yakashandiswa kugadzirisa sarudzo yezvigadzirwa zve linear uye branched27,28,29. Kubva ipapo, Ru-POP complexes hadzina kushandiswa zvakanyanya mu hydrogenation catalysis, asi mienzaniso yekushanda kwadzo mu transfer hydrogenation yakambotaurwa30. Pano tinoratidza kuti Ru-POP complex i catalyst inoshanda ye dehydrogenation ye formic acid, zvichisimbisa kuwanikwa kwaBeller kuti amino unit mu classical Ru-PNP amine catalyst haina kukosha zvakanyanya mukuita uku.
Chidzidzo chedu chinotanga nekugadzirwa kwema catalysts maviri akajairika nefomura yakajairika [RuHCl(POP)(PPh3)] (Mufananidzo 1a). Kuti tigadzirise chimiro chesteric ne electronic, dibenzo[b,d]furan yakasarudzwa kubva ku4,6-bis(diisopropylphosphino) inowanikwa mukutengeserana (Mufananidzo 1b) 31. Ma catalysts akadzidzwa mubasa iri akagadzirwa achishandisa nzira yakajairika yakagadzirwa naWhittlesey32, nekushandisa [RuHCl(PPh3)3]•toluene33 adduct se precursor. Sanganisa metal precursor nePOP clamp ligand muTHF pasi pemamiriro emvura uye anaerobic. Kuita kwacho kwakaperekedzwa nekuchinja kukuru kweruvara kubva pa dark purple kuenda kune yero uye kwakapa chigadzirwa chakachena mushure memaawa mana e reflux kana maawa makumi manomwe nemaviri e reflux pa40°C. Mushure mekubvisa THF mu vacuo uye kuisuka kaviri ne hexane kana diethyl ether, triphenylphosphine yakabviswa kuti chigadzirwa chacho chive upfu hweyero hwakakura.
Kugadzirwa kweRu-1 neRu-2 complexes. a) Nzira yekugadzira complexes. b) Maumbirwo ecomplex yakagadzirwa.
Ru-1 yatove kuzivikanwa kubva mumabhuku32, uye mamwe matsananguriro anotarisa paRu-2. Iyo 1H NMR spectrum yeRu-2 yakasimbisa chimiro checis cheatomu yephosphine mu ligand ye hydride pair. Iyo peak dt plot (Mufananidzo 2a) inoratidza 2JP-H coupling constants ye28.6 ne22.0 Hz, iri mukati mehuwandu hwaitarisirwa kubva mumishumo yapfuura32. Mu hydrogen decoupled 31P{1H} spectrum (Mufananidzo 2b), 2JP-P coupling constant yeinenge 27.6 Hz yakaonekwa, ichisimbisa kuti clamp ligand phosphines nePPh3 zvese zviri cis-cis. Pamusoro pezvo, ATR-IR inoratidza hunhu hwe ruthenium-hydrogen stretching band pa2054 cm-1. Kuti zvinyatsojekeswa, Ru-2 complex yakasanganiswa nekupararira kwemhepo patembiricha yemumba ine hunhu hwakakwana pakudzidza X-ray (Mufananidzo 3, Tafura Yekuwedzera 1). Inobatanidza mu triclinic system yeboka renzvimbo P-1 ne cocrystalline benzene unit imwe neimwe pasero reyuniti. Inoratidza angle yakakura yeP-Ru-P occlusal ye153.94°, iyo yakafara zvakanyanya kupfuura angle ye130° occlusal ye bidentate DBFphos34. Pa2.401 na2.382 Å, kureba kwebonde reRu-PPOP kwakareba zvakanyanya kupfuura kureba kwebonde reRu kusvika kuPPh3 ye2.232 Å, izvo zvinogona kunge zviri mugumisiro wekona yakakura yesnack yemusana yeDBFphos inokonzerwa ne 5-ring yayo yepakati. Geometry yepakati pesimbi inonyanya kuve octahedral ine angle yeO-Ru-PPh3 ye179.5°. Kubatana kweH-Ru-Cl hakuna kurongeka zvakakwana, nekona yeinenge 175° kubva ku triphenylphosphine ligand. Madaro eatomu nehurefu hwemabhondi zvakanyorwa muTafura 1.
NMR spectrum yeRu-2. a) Nzvimbo yeHydride ye1H NMR spectrum inoratidza chiratidzo cheRu-H dt. b) 31 P{ 1 H} NMR spectrum inoratidza zviratidzo kubva kutriphenylphosphine (bhuruu) uye POP ligand (girini).
Maumbirwo eRu-2. Ma ellipsoid ekupisa anoratidzwa nemukana we70%. Kuti zvive pachena, maatomu e cocrystalline benzene ne hydrogen ari pakabhoni haana kujeka.
Kuti vaongorore kugona kwemacomplexes kubvisa hydrogen kuformic acid, mamiriro ekuita akasarudzwa pasi payo apo maPNP-clamp complexes anoenderana (semuenzaniso, Ru-MACHO-BH) aishanda zvakanyanya15. Kubviswa kwehydrogen kwe0.5 ml (13.25 mmol) formic acid uchishandisa 0.1 mol% (1000 ppm, 13 µmol) ruthenium complex Ru-1 kana Ru-2 uchishandisa 1.0 ml (5.35 mmol) ionic liquid (IL) BMIM OAc (tafura-mufananidzo) 2; Mufananidzo 4);
Kuti uwane mwero, chiitiko ichi chakatanga kuitwa uchishandisa precursor adduct [RuHCl(PPh3)3]·toluene. Chiitiko ichi chinoitwa patembiricha iri pakati pe60 ne90 °C. Zvichienderana nekutarisa kuri nyore, complex iyi haigone kunyungudutswa zvachose muIL kunyangwe nekukurunga kwenguva refu patembiricha ye90°C, asi kunyungudika kwakaitika mushure mekuiswa kweformic acid. Pa90°C, shanduko ye56% (TOF = 3424 h-1) yakawanikwa mukati memaminitsi gumi ekutanga, uye shanduko inosvika quantitative (97%) yakawanikwa mushure memaawa matatu (kupinda 1). Kuderedza tembiricha kusvika 80 °C kunoderedza shanduko neinopfuura hafu kusvika 24% mushure memaminitsi gumi (TOF = 1467 h-1, kupinda 2), zvichiwedzera kuideredza kusvika 18% ne18% pa70 °C ne60 °C, zvichiteerana 6% (kupinda 3 ne4). Muzviitiko zvese, hapana nguva yekupinza yakawanikwa, zvichiratidza kuti catalyst inogona kunge iri mhando dzemhuka dzinoita reactive kana kuti kushandurwa kwemhando dzemhuka dzinoita reactive kunokurumidza kuonekwa uchishandisa data iri.
Mushure mekuongororwa kwepakutanga, Ru-POP clamp complexes Ru-1 naRu-2 zvakashandiswa pasi pemamiriro akafanana. Pa90°C, kutendeuka kwakanyanya kwakaonekwa pakarepo. Ru-1 yakawana kutendeuka kwe74% mukati memaminitsi gumi ekutanga ekuyedza (TOFmax = 4525 h-1, kupinda 5). Ru-2 yakaratidza kushanda kushoma asi kwakasimba, ichikurudzira kutendeuka kwe60% mukati memaminitsi gumi (TOFmax = 3669 h-1) uye kutendeuka kwakazara mukati memaminitsi makumi matanhatu (>99%) (kupinda 9). Zvakakosha kuziva kuti Ru-2 iri nani zvakanyanya pane precursor metal naRu-1 pakuchinja kwakazara. Naizvozvo, nepo metal precursor naRu-1 vaine TOFoverall values ​​​​dzakafanana pakupedzwa kwe reaction (330 h-1 na333 h-1, zvichiteerana), Ru-2 ine TOFoverall ye1009 h-1.
Ru-1 naRu-2 zvakabva zvachinja tembiricha umo tembiricha yakaderedzwa zvishoma nezvishoma mukuwedzera kwe10 °C kusvika padiki pa60 °C (Mufananidzo 3). Kana pa90°C complex yakaratidza kushanda nekukurumidza, kuchinja kwacho kwakaitika mukati meawa imwe chete, saka pakupisa kwakaderera chiitiko chacho chakadzikira zvakanyanya. Kuchinja kwePy-1 kwaive 14% ne23% mushure memaminitsi gumi pa80°C ne70°C, zvichiteerana, uye mushure memaminitsi makumi matatu kwakawedzera kusvika 79% ne73% (zvinyorwa 6 ne7). Kuedza kwese kwakaratidza mwero wekushanduka we ≥90% mukati memaawa maviri. Maitiro akafanana akaonekwa paRu-2 (zvinyorwa 10 ne11). Zvinofadza kuti, Ru-1 yaive nesimba zvishoma pakupera kwekuita pa70 °C neTOF yese ye315 h-1 zvichienzaniswa ne292 h-1 yeRu-2 ne299 h-1 yesimbi yekutanga.
Kudzikira kwekupisa kusvika pa60 °C kwakaita kuti pasave nekushanduka kwakaonekwa mukati memaminitsi makumi matatu ekutanga ekuyedza. Ru-1 yakanga isingashande zvakanyanya pakupisa kwakaderera pakutanga kwekuyedza uye yakazowedzera kushanda, zvichiratidza kudiwa kwenguva yekushanda apo Ru-1 precatalyst inoshandurwa kuita mhando dzinoshanda. Kunyangwe izvi zvichikwanisika pakupisa kwese, maminetsi gumi pakutanga kwekuyedza akanga asina kukwana kuona nguva yekushanda pakupisa kwakakwira. Maitiro akafanana akawanikwa paRu-2. Pa70 ne60 °C, hapana kushanduka kwakaonekwa mukati memaminitsi gumi ekutanga ekuyedza. Zvakakosha kuziva kuti mukuyedza kwese, kuumbwa kwecarbon monoxide hakuna kuonekwa mukati memuganhu wekuona wechinhu chedu (<300 ppm), neH2 neCO2 zviri izvo chete zvigadzirwa zvakaonekwa.
Kuenzanisa mhedzisiro yeformic acid dehydrogenation yakawanikwa kare muboka iri rekushanda, rinomiririra zvemazuva ano uye richishandisa Ru-PNP clamp complexes, kwakaratidza kuti Ru-POP clamp ichangobva kugadzirwa ine basa rakafanana nePNP counterpart 15. Kunyange zvazvo clamp PNP yakawana RPMs ye500-1260 h-1 mukuyedza kwebatch, POP clamp itsva yakawana TOFovertal value yakafanana ye326 h-1, uye TOFmax values ​​​​dzeRu-1 ne1590 h-1 dzakaonekwa. zvakateerana, 1988 h-1 uye 1590 h-1. Ru-2 i1 pa80 °C, Ru-1 i4525 h-1 uye Ru-1 i3669 h-1 pa90 °C, zvichiteerana.
Kuongororwa kwekupisa kwe formic acid dehydrogenation uchishandisa Ru-1 neRu-2 catalysts. Mamiriro: 13 µmol catalyst, 0.5 ml (13.25 mmol) formic acid, 1.0 ml (5.35 mmol) BMIM OAc.
NMR inoshandiswa kunzwisisa mashandiro ekuita. Sezvo paine musiyano wakakura mu2JH-P pakati pehydride nephosphine ligands, chinangwa chechidzidzo ichi chiri pa hydride peak. Kune Ru-1, patani yakajairika yedt yehydrogenation unit yakawanikwa mukati memaminitsi makumi matanhatu ekutanga ekubviswa kwehydrogenation. Kunyangwe paine shanduko yakakosha kubva pa −16.29 kusvika −13.35 ppm, ma coupling constants ayo nephosphine ari 27.2 uye 18.4 Hz, zvichiteerana (Mufananidzo 5, Peak A). Izvi zvinoenderana nema phosphines ese matatu umo hydrogen ligand iri mu cis configuration uye zvinoratidza kuti ligand configuration yakagadzikana zvishoma mu IL kweinenge awa imwe pasi pemamiriro ekugadzirisa akagadziriswa. Kuchinja kwakasimba kwepasi kunogona kunge kuri nekuda kwekubviswa kwema chlorinated ligands uye kuumbwa kwe acetyl-formic acid complexes inoenderana, kuumbwa kwe d3-MeCN complex muNMR tube, kana kuumbwa kwe N-heterocycles inoenderana. yakatsanangurwa. Carbene (NHC) complex. Munguva ye dehydrogenation reaction, simba rechiratidzo ichi rakaramba richiderera, uye mushure memaminitsi 180 chiratidzo hachina kuzoonekwazve. Pane kudaro, zviratidzo zviviri zvitsva zvakawanikwa. Chekutanga chinoratidza dd pattern yakajeka inoitika pa -6.4 ppm (peak B). Iyo doublet ine coupling constant yakakura ye130.4 Hz, zvichiratidza kuti imwe yemayuniti ephosphine yafamba zvichienzaniswa ne hydrogen. Izvi zvinogona kureva kuti POP clamp yakarongwazve kuita κ2-P,P configuration. Kuonekwa kweiyi complex pakupera kwe catalysis kunogona kuratidza kuti rudzi urwu rwunotungamira kune nzira dzekudzima nekufamba kwenguva, zvichigadzira catalyst sink. Kune rumwe rutivi, kuchinja kwemakemikari kwakaderera kunoratidza kuti inogona kunge iri mhando yehydrogenous15. Peak yechipiri itsva iri pa -17.5 ppm. Kunyangwe kupeta kwayo kusingazivikanwe, tinotenda kuti itriplet ine coupling constant diki ye17.3 Hz, zvichiratidza kuti hydrogen ligand inosunga chete kune phosphine ligand yePOP clamp, zvichiratidzawo kuburitswa kwetriphenylphosphine (peak C). Inogona kutsiviwa neimwe ligand, senge acetyl group kana NHC yakagadzirwa in situ kubva ku ionic liquid. Kuparadzaniswa kwePPh3 kunoratidzwazve ne singlet yakasimba pa -5.9 ppm. mu 31P{1H} spectrum yeRu-1 mushure memaminitsi 180 pa 90 °C (ona rumwe ruzivo).
Nzvimbo yeHydride ye1H NMR spectrum yeRu-1 panguva yekubviswa kwehydrogen yeformic acid. Mamiriro ekuita: 0.5 ml formic acid, 1.0 ml BMIM OAc, 13.0 µmol catalyst, 90 °C. NMR yakatorwa kubva kuMeCN-d 3, 500 μl ye deuterated solvent, inenge 10 μl ye reaction mixture.
Kuti zvisimbiswe zvakare kuvapo kwemarudzi anoshanda mu catalytic system, kuongororwa kwe high resolution mass spectrometry (HRMS) kweRu-1 kwakaitwa mushure mekubayiwa formic acid kwemaminitsi gumi pa90 °C. Izvi zvinoratidza kuvapo kwemarudzi asina chlorine ligand precatalyst mumusanganiswa we reaction. pamwe chete neNHC complexes mbiri, mafomu ayo anoratidzwa muMufananidzo 6. HRMS spectrum inoenderana inogona kuonekwa muMufananiso Wekuwedzera 7.
Zvichibva padata iri, tinokurudzira nzira yekuita intrasphere reaction yakafanana neyakataurwa naBeller, umo N-methylated PNP clamps inokonzeresa reaction imwechete. Kuedza kwakawedzerwa kusina ionic liquids hakuna kuratidza chero chiitiko, saka kubatanidzwa kwayo zvakananga kunoita sekudikanwa. Tinofungidzira kuti activation yeRu-1 neRu-2 inoitika kuburikidza nekupatsanurwa kwechloride kunoteverwa nekuwedzerwa kweNHC uye triphenylphosphine dissociation (Scheme 1a). Kushanda uku mumarudzi ese kwakamboonekwa uchishandisa HRMS. IL-acetate iBronsted base yakasimba kupfuura formic acid uye inogona kubvisa protonate zvakanyanya iyo yekupedzisira35. Tinofungidzira kuti panguva ye catalytic cycle (Scheme 1b), active species A bearing NHC kana PPh3 zvinobatanidzwa kuburikidza neformate kuti zviumbe species B. Kugadziriswazve kwecomplex iyi kuC kunoguma nekuburitswa kweCO2 uye trans-dihydrogen complex D Kuburitswa kweacid kunotevera kuita dihydro complex neacetic acid yakambogadzirwa kuti iumbe dihydro complex E kwakafanana nedanho guru rakataurwa naBeller achishandisa N-methylated PNP clamp homologues. Pamusoro pezvo, analogue yecomplex EL = PPh3 yakambogadzirwa ne stoichiometric reaction ichishandisa Ru-1 mumhepo yehydrogen mushure mekubviswa kwe chloride ne sodium salt. Kubviswa kwehydrogen uye kubatana kweformate kunopa A uye kunopedzisa kutenderera.
Nzira yekushanda kwemukati mechikamu cheformic acid dehydrogenation uchishandisa fixing complex Ru-POP Ru-1 inokurudzirwa.
Imwe complex itsva [RuHCl(iPr-dbfphos)(PPh3)] yakagadzirwa. Iyi complex yakaratidzwa neNMR, ATRIR, EA uye X-ray diffraction analysis yemakristaro ega. Tinoshumawo kuti kushandiswa kwekutanga kweRu-POP pincer complexes kwakabudirira mukubviswa kwehydrogenation yeformic acid kuCO2 neH2. Kunyangwe simbi yekutanga yakawana basa rakafanana (kusvika 3424 h-1), complex iyi yakasvika pahuwandu hwekuchinja hunosvika 4525 h-1 pa90 °C. Uyezve, pa90 °C, complex itsva [RuHCl(iPr-dbfphos)(PPh3)] yakawana nguva yese yekubhururuka (1009 h-1) kuti ipedze hydrogenation yeformic acid, iyo yakakwira zvakanyanya kupfuura iyo yesimbi yekutanga (330 h-1). uye complex yakambotaurwa [RuHCl(xantphos)(PPh3)] (333 h-1). Mumamiriro ezvinhu akafanana, kushanda zvakanaka kwe catalytic kwakafanana nekwe Ru-PNP clamp complex. Data reHRMS rinoratidza kuvapo kwe carbene complex mumusanganiswa we reaction, kunyangwe muhuwandu hushoma. Pari zvino tiri kudzidza nezve catalytic effects ye carbene complexes.
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