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Formic acid yana ɗaya daga cikin mafi kyawun masu amfani don adana ruwa hydrogen na dogon lokaci. A nan mun gabatar da jerin sabbin hadaddun ruthenium clamp tare da dabarar gabaɗaya [RuHCl(POP)(PPh3)] ta amfani da ligands na xanthos-type tridentate POP clamp waɗanda ake samu a kasuwa ko waɗanda aka haɗa cikin sauƙi. Mun yi amfani da waɗannan hadaddun don cire hydrogenate formic acid don samar da CO2 da H2 a ƙarƙashin yanayi mai sauƙi, mara reflux ta amfani da ionic liquid BMIM OAc (1-butyl-3-methylimidazolium acetate) a matsayin mai narkewa. Daga mahangar matsakaicin mitar juyawa, mafi kyawun mai haɓaka shine [RuHCl(xantphos)(PPh3)]Ru-1 hadaddun da aka sani a cikin wallafe-wallafe, wanda ke da matsakaicin mitar juyawa na 4525 h-1 a 90 °C na minti 10. Yawan bayan juyawa shine 74%, kuma an kammala juyawar cikin awanni 3 (>98%). A gefe guda kuma, mai haɓaka aikin da ya fi dacewa gabaɗaya, sabon [RuHCl(iPr-dbfphos)(PPh3)]Ru-2 complex, yana haɓaka cikakken juyawa cikin awa 1, wanda ke haifar da jimlar juyi na 1009 h-1. Bugu da ƙari, an kuma lura da aikin catalytic a yanayin zafi har zuwa 60 °C. A cikin yanayin iskar gas, an lura da CO2 da H2 kawai; ba a gano CO2 ba. Babban ƙudurin mass spectrometry ya nuna kasancewar hadaddun N-heterocyclic carbene a cikin cakuda amsawar.
Kasuwar makamashi mai sabuntawa da kuma bambancinsa ya haifar da buƙatar fasahar adana makamashi a fannin masana'antu a fannin wutar lantarki, zafi, masana'antu da sufuri1,2. Ana ɗaukar hydrogen a matsayin ɗaya daga cikin masu ɗaukar makamashi mafi yawa3, kuma masu ɗaukar hydrogen na ruwa (LOHCs) kwanan nan sun zama abin da bincike ya mayar da hankali a kai, suna ba da alƙawarin adana hydrogen a cikin tsari mai sauƙin sarrafawa ba tare da matsalolin da ke tattare da matsi ko fasahar cryogenic4. ,5,6. Saboda halayensu na zahiri, yawancin kayayyakin sufuri na man fetur da sauran man fetur na ruwa ana iya amfani da su don jigilar LOHC7,8. Sifofin jiki na formic acid (FA) sun sa ya zama ɗan takara mai kyau don adana hydrogen tare da nauyin hydrogen na 4.4%9,10. Duk da haka, tsarin catalytic da aka buga don dehydrogenation na formic acid yawanci yana buƙatar amfani da sinadaran Organic masu canzawa, ruwa ko tsantsar formic acid,11,12,13,14 wanda zai iya buƙatar amfani da dabarun rabuwa da tururin mai kamar condensation, wanda zai iya haifar da matsaloli a aikace-aikacen mabukaci. aikace-aikace, ƙarin kaya. Ana iya shawo kan wannan matsala ta hanyar amfani da sinadarai masu ƙarfi waɗanda ke da matsin lamba mai yawa, kamar ruwayen ionic. A baya, ƙungiyarmu ta aiki ta nuna cewa ruwayen ionic butylmethylimidazolium acetate (BMIM OAc) mai narkewa ne mai dacewa a cikin wannan amsawar ta amfani da hadaddun Ru-PNP Ru-MACHO nau'in 15 da ake da su a kasuwa. Misali, mun nuna rage yawan sinadarin hydrogenation na FA a cikin tsarin kwarara mai ci gaba ta amfani da BMIM OAc, inda muka sami TON sama da 18,000,000 a 95°C. Kodayake wasu tsarin sun riga sun sami babban TON, da yawa sun dogara da sinadarai masu narkewa masu canzawa (kamar THF ko DMF) ko ƙari da aka yi amfani da su (kamar tushe). Akasin haka, aikinmu yana amfani da ruwayen ionic marasa canzawa (ILs) kuma babu ƙari.
Hazari da Bernskoetter sun ba da rahoton rage sinadarin formic acid (FA) a digiri 80 na Celsius ta amfani da mai kara kuzari na Fe-PNP a gaban dioxane da LiBF4, wanda ya kai adadin juyawa mai ban mamaki (TON) na kimanin 1,000,00016. Laurenci ya yi amfani da mai kara kuzari na Ru(II)- TPPPTS a cikin tsarin rage sinadarin FA mai ci gaba. Wannan hanyar ta haifar da kusan cikakkiyar rage sinadarin FA tare da ƙarancin alamun CO da aka gano a digiri 80 na Celsius. Don ci gaba da wannan fanni, Pidko ya nuna rage sinadarin FA mai juyewa ta amfani da mai kara kuzari na Ru-PNP a cikin gaurayawan DMF/DBU da DMF/NHex₃, inda ya cimma ƙimar TON na 310,000 zuwa 706,500 a digiri 90 na Celsius. Hull, Himeda da Fujita sun yi nazarin wani mai kara kuzari na Ir mai kara kuzari na binuclear wanda aka yanka KHCO3 da H2SO4, suna canza sinadarin hydrogenation na CO2 da kuma rage sinadarin FA. Tsarin su ya cimma TON sama da 3,500,000 da 308,000 bi da bi don samar da hydrogenation a 30°C, CO2/H2 (1:1), matsin lamba na mashaya 1 da kuma rage hydrogenation tsakanin 60 da 90°C19. Sponholz, Junge da Beller sun haɓaka wani hadadden Mn-PNP don sake samar da hydrogenation na CO2 da kuma rage hydrogenation na FA a 90°C20.
A nan mun yi amfani da hanyar IL, amma maimakon amfani da Ru-PNPs, mun bincika amfani da Ru-POP catalysts, wanda a saninmu ba a taɓa nuna shi a baya ba a wannan fanni.
Saboda kyakkyawan haɗin gwiwar ƙarfe-ligand (MLC), hadaddun mahaɗan amino-PNP waɗanda suka dogara da ra'ayoyin nau'in Noyori tare da ƙungiyoyin amino masu aiki na sakandare 21 (kamar Ru-MACHO-BH) gabaɗaya suna ƙara shahara a wasu ƙananan ayyukan ƙwayoyin halitta. Misalai masu shahara sun haɗa da CO22, hydrogenation na alkenes da carbonyls, transfer hydrogenation23 da dehydrogenation na alcohols24 marasa yarda. An ruwaito cewa N-methylation na ligands na PNP clamp na iya dakatar da aikin catalyst25 gaba ɗaya, wanda za a iya bayyana shi ta hanyar gaskiyar cewa amines suna aiki azaman tushen proton, wanda muhimmin buƙata ne a lokacin zagayowar catalytic ta amfani da MLC. Duk da haka, kwanan nan Beller ya lura da akasin yanayin dehydrogenation na formic acid, inda hadaddun N-methylated Ru-PNP a zahiri sun nuna mafi kyawun dehydrogenation na formic acid fiye da takwarorinsu marasa methylated26. Tunda tsohon hadadden ba zai iya shiga cikin MLC ta hanyar naúrar amino ba, wannan yana nuna cewa MLC, saboda haka naúrar amino, na iya taka muhimmiyar rawa a wasu canje-canje (de) hydrogenation kamar yadda aka zata a baya.
Idan aka kwatanta da maƙallan POP, ba a yi nazari sosai kan ruthenium complexes na POP clamps a wannan fanni ba. Ana amfani da POP ligands musamman don hydroformylation, inda suke aiki azaman chelating ligands maimakon siffar bidentate cizo na kusan 120° don maƙallan ligands, waɗanda aka yi amfani da su don inganta zaɓi don samfuran layi da rassan ligands27,28,29. Tun daga lokacin, ba kasafai ake amfani da hadaddun Ru-POP a cikin catalysis na hydrogenation ba, amma an ruwaito misalan ayyukansu a cikin transfer hydrogenation a baya30. A nan mun nuna cewa hadaddun Ru-POP ingantaccen mai kara kuzari ne don rage hydrogenation na formic acid, yana tabbatar da gano Beller cewa sashin amino a cikin classic Ru-PNP amine catalyst ba shi da mahimmanci a cikin wannan amsawar.
Bincikenmu ya fara ne da haɗakar sinadarai guda biyu na yau da kullun tare da dabarar gabaɗaya [RuHCl(POP)(PPh3)] (Hoto na 1a). Don gyara tsarin steric da na lantarki, an zaɓi dibenzo[b,d]furan daga 4,6-bis(diisopropylphosphino) da ake samu a kasuwa (Hoto na 1b) 31. An haɗa abubuwan haɓaka sinadarai da aka yi nazari a kansu a cikin wannan aikin ta amfani da hanyar gabaɗaya da Whittlesey32 ta ƙirƙira, tare da amfani da [RuHCl(PPh3)3]•toluene33 adduct a matsayin precursor. A haɗa sinadarin ƙarfe da POP clamp ligand a cikin THF a ƙarƙashin yanayi mai tsauri na anhydrous da anaerobic. An haɗa wannan amsawar tare da babban canjin launi daga shunayya mai duhu zuwa rawaya kuma an ba da samfurin tsarkakakke bayan awanni 4 na reflux ko awanni 72 na reflux a 40°C. Bayan cire THF a cikin vacuo kuma an wanke sau biyu da hexane ko diethyl ether, an cire triphenylphosphine don ba da samfurin a matsayin foda mai rawaya a cikin yawan amfanin ƙasa mai yawa.
Haɗakar Ru-1 da Ru-2. a) Hanyar haɗa hadaddun abubuwa. b) Tsarin hadaddun da aka haɗa.
An riga an san Ru-1 daga wallafe-wallafen32, kuma ƙarin bayanin ya mayar da hankali kan Ru-2. Bakan 1H NMR na Ru-2 ya tabbatar da tsarin cis na atom ɗin phosphine a cikin ligand na nau'in hydride. Tsarin dt mafi tsayi (Hoto na 2a) yana nuna daidaitattun haɗin 2JP-H na 28.6 da 22.0 Hz, waɗanda ke cikin kewayon da ake tsammani na rahotannin da suka gabata32. A cikin bakan 31P{1H} da aka cire hydrogen (Hoto na 2b), an lura da daidaitaccen haɗin 2JP-P na kimanin 27.6 Hz, yana tabbatar da cewa duka phosphines na ligand da PPh3 cis-cis ne. Bugu da ƙari, ATR-IR yana nuna madaidaicin shimfiɗa ruthenium-hydrogen a 2054 cm-1. Don ƙarin bayani game da tsarin, an yi amfani da tsarin Ru-2 ta hanyar watsa tururi a zafin ɗaki tare da ingancin da ya isa don nazarin X-ray (Hoto na 3, Tebur na Ƙarin Bayani na 1). Yana yin lu'ulu'u a cikin tsarin triclinic na rukunin sararin samaniya na P-1 tare da naúrar benzene cocrystalline ɗaya a kowace ƙwayar naúrar. Yana nuna kusurwar rufewa mai faɗi ta P-Ru-P na 153.94°, wanda ya fi faɗi sosai fiye da kusurwar rufewa ta 130° na bidentate DBFphos34. A 2.401 da 2.382 Å, tsawon haɗin Ru-PPOP ya fi tsayi fiye da tsawon haɗin Ru zuwa PPh3 na 2.232 Å, wanda zai iya zama sakamakon faɗin kusurwar abun ciye-ciye na DBFphos wanda tsakiyar zobensa na 5 ya haifar. Tsarin tsakiyar ƙarfe yana da octahedral tare da kusurwar O-Ru-PPh3 na 179.5°. Daidaito tsakanin H-Ru-Cl ba ta da layi ɗaya gaba ɗaya, tare da kusurwar kusan 175° daga ligand ɗin triphenylphosphine. Nisa tsakanin atomic da tsawon haɗin an jera su a cikin Tebur 1.
Bakan NMR na Ru-2. a) Yankin Hydride na bakan NMR na 1H wanda ke nuna siginar Ru-H dt. b) 31 P{ 1 H} Bakan NMR wanda ke nuna sigina daga triphenylphosphine (shuɗi) da POP ligand (kore).
Tsarin Ru-2. Ana nuna ellipsoids na zafi da yuwuwar kashi 70%. Domin a fayyace, an cire cocrystalline benzene da atom hydrogen akan carbon.
Domin kimanta ikon hadaddun sinadaran don cire sinadarin formic acid, an zaɓi yanayin amsawa wanda a ƙarƙashinsa aka sami hadaddun PNP-clamp masu dacewa (misali, Ru-MACHO-BH) suna da ƙarfi sosai15. Rage sinadarin formic acid na 0.5 ml (13.25 mmol) ta amfani da 0.1 mol% (1000 ppm, 13 µmol) ruthenium complex Ru-1 ko Ru-2 ta amfani da 1.0 ml (5.35 mmol) ionic liquid (IL) BMIM OAc (tebur-Figure) 2; Hoto na 4);
Domin samun mizani, an fara yin wannan aikin ta amfani da abin da aka riga aka yi amfani da shi [RuHCl(PPh3)3]·toluene]. Ana yin wannan aikin ne a zafin jiki daga 60 zuwa 90 °C. A bisa ga abubuwan da aka gani a hankali, ba za a iya narkar da hadaddun gaba ɗaya a cikin IL ba koda da an daɗe ana juyawa a zafin jiki na 90 °C, amma an narkar da shi bayan an shigar da sinadarin formic acid. A zafin jiki na 90 °C, an sami canjin kashi 56% (TOF = 3424 h-1) a cikin mintuna 10 na farko, kuma an sami kusan canjin adadi (97%) bayan awanni uku (shigar 1). Rage zafin jiki zuwa 80 °C yana rage canjin da fiye da rabi zuwa kashi 24% bayan mintuna 10 (TOF = 1467 h-1, shigarwar 2), wanda hakan ya ƙara rage shi zuwa kashi 18% da 18% a zafin jiki na 70 °C da 60 °C, bi da bi 6% (shigar 3 da 4). A dukkan lokuta, ba a gano lokacin shigar da abubuwa ba, wanda ke nuna cewa mai kara kuzari na iya zama nau'in mai amsawa ko kuma cewa juyawar nau'in mai amsawa yana da sauri sosai don a gano ta amfani da wannan saitin bayanai.
Bayan kimantawa ta farko, an yi amfani da hadaddun maƙallan Ru-POP Ru-1 da Ru-2 a ƙarƙashin yanayi iri ɗaya. A zafin jiki na 90°C, an lura da babban juyawa nan da nan. Ru-1 ya sami kashi 74% na juyawa a cikin mintuna 10 na farko na gwajin (TOFmax = 4525 h-1, shigarwar 5). Ru-2 ya nuna ɗan ƙaramin aiki amma ya fi daidaito, yana haɓaka juyawar 60% cikin mintuna 10 (TOFmax = 3669 h-1) da cikakken juyawa cikin mintuna 60 (>99%) (shigar 9). Abin lura ne cewa Ru-2 ya fi ƙarfe na farko da Ru-1 girma sosai. Saboda haka, yayin da ƙarfe na farko da Ru-1 suna da ƙimar TOFoverall iri ɗaya lokacin kammala amsawa (330 h-1 da 333 h-1, bi da bi), Ru-2 yana da TOFoverall na 1009 h-1.
Daga nan aka sami canjin zafin jiki a Ru-1 da Ru-2 wanda aka rage zafin a hankali a cikin ƙara 10 °C zuwa mafi ƙarancin 60 °C (Hoto na 3). Idan a 90 °C hadaddun ya nuna aiki nan take, kusan cikakkiyar juyawa ta faru cikin awa ɗaya, to a ƙananan zafin jiki aikin ya ragu sosai. Juyawan Py-1 shine 14% da 23% bayan mintuna 10 a 80 °C da 70 °C, bi da bi, kuma bayan mintuna 30 ya karu zuwa 79% da 73% (shigarwa 6 da 7). Duk gwaje-gwajen sun nuna ƙimar juyawa na ≥90% cikin awanni biyu. An lura da irin wannan hali ga Ru-2 (shigarwa 10 da 11). Abin sha'awa, Ru-1 ya ɗan mamaye kaɗan a ƙarshen amsawar a 70 °C tare da jimlar TOF na 315 h-1 idan aka kwatanta da 292 h-1 ga Ru-2 da 299 h-1 ga abin da ya fara aiki na ƙarfe.
Ƙarin raguwar zafin jiki zuwa 60 °C ya haifar da gaskiyar cewa ba a ga wani canji ba a cikin mintuna 30 na farko na gwajin. Ru-1 bai yi aiki sosai a mafi ƙarancin zafin jiki a farkon gwajin ba kuma daga baya ya ƙara aiki, wanda ke nuna buƙatar lokacin kunnawa wanda aka canza Ru-1 precatalyst zuwa nau'in masu aiki da catalytic. Kodayake wannan yana yiwuwa a duk yanayin zafi, mintuna 10 a farkon gwajin bai isa ya gano lokacin kunnawa a mafi girman yanayin zafi ba. An sami irin wannan hali ga Ru-2. A 70 da 60 °C, ba a lura da wani canji ba a cikin mintuna 10 na farko na gwajin. Yana da mahimmanci a lura cewa a cikin gwaje-gwajen biyu, ba a lura da samuwar carbon monoxide a cikin iyakar gano kayan aikinmu (<300 ppm), tare da H2 da CO2 su ne kawai samfuran da aka lura.
Kwatanta sakamakon dehydrogenation na formic acid da aka samu a baya a cikin wannan rukunin aiki, wanda ke wakiltar yanayin zamani da kuma amfani da hadaddun maƙallan Ru-PNP, ya nuna cewa sabon maƙallin Ru-POP da aka haɗa yana da aiki iri ɗaya da takwaransa na PNP 15. Yayin da maƙallin PNP ya sami RPMs na 500-1260 h-1 a cikin gwaje-gwajen rukuni, sabon maƙallin POP ya sami ƙimar TOFovertal iri ɗaya na 326 h-1, kuma an lura da ƙimar TOFmax na Ru-1 da 1590 h-1. bi da bi, sune 1988 h-1 da 1590 h-1. Ru-2 shine 1 a 80 °C, Ru-1 shine 4525 h-1 kuma Ru-1 shine 3669 h-1 a 90 °C, bi da bi.
Binciken zafin jiki na rashin sinadarin formic acid ta amfani da sinadaran Ru-1 da Ru-2. Yanayi: 13 µmol catalyst, 0.5 ml (13.25 mmol) formic acid, 1.0 ml (5.35 mmol) BMIM OAc.
Ana amfani da NMR don fahimtar hanyoyin amsawa. Tunda akwai babban bambanci a cikin 2JH-P tsakanin ligands na hydride da phosphine, babban abin da wannan binciken ya mayar da hankali a kai shine kan kololuwar hydride. Ga Ru-1, an sami tsarin dt na yau da kullun na sashin hydrogenation a cikin mintuna 60 na farko na dehydrogenation. Kodayake akwai babban canji a ƙasa daga −16.29 zuwa −13.35 ppm, madaidaitan haɗin gwiwa tare da phosphine sune 27.2 da 18.4 Hz, bi da bi (Hoto na 5, Kololuwar A). Wannan ya yi daidai da dukkan phosphines guda uku inda ligand na hydrogen yake cikin tsarin cis kuma yana nuna cewa tsarin ligand ɗin yana da ɗan karko a cikin IL na kimanin awa ɗaya a ƙarƙashin yanayin amsawar da aka inganta. Ƙarfin canjin ƙasa na iya faruwa ne saboda kawar da ligands masu chlorinated da kuma samuwar hadaddun acetyl-formic acid masu dacewa, samuwar hadaddun d3-MeCN a cikin bututun NMR, ko kuma samuwar N-heterocycles masu dacewa. An bayyana. Hadakar Carbene (NHC). A lokacin amsawar dehydrogenation, ƙarfin wannan siginar ya ci gaba da raguwa, kuma bayan mintuna 180 ba a sake ganin siginar ba. Madadin haka, an gano sabbin sigina guda biyu. Na farko yana nuna tsarin dd bayyananne wanda ke faruwa a -6.4 ppm (kololuwar B). Doublet ɗin yana da babban ma'aunin haɗin gwiwa na kusan 130.4 Hz, yana nuna cewa ɗayan raka'a na phosphine ya motsa dangane da hydrogen. Wannan na iya nufin cewa an sake tsara maƙallin POP zuwa tsarin κ2-P,P. Bayyanar wannan hadadden a ƙarshen catalysis na iya nuna cewa wannan nau'in yana haifar da hanyoyin kashewa akan lokaci, yana samar da nutsewar catalyst. A gefe guda kuma, ƙarancin canjin sinadarai yana nuna cewa yana iya zama nau'in dihydrogenous15. Sabon kololuwar na biyu yana nan a -17.5 ppm. Duk da cewa ba a san ninkinsa ba, mun yi imanin cewa sau uku ne tare da ƙaramin ma'aunin haɗin gwiwa na 17.3 Hz, wanda ke nuna cewa ligand ɗin hydrogen yana haɗuwa ne kawai da ligand ɗin phosphine na maƙallin POP, wanda hakan ke nuna sakin triphenylphosphine (kololuwar C). Ana iya maye gurbinsa da wani ligand, kamar ƙungiyar acetyl ko NHC da aka samar a wuri daga ruwan ionic. Rabawar PPh3 yana ƙara nuna ta hanyar singlet mai ƙarfi a -5.9 ppm. a cikin bakan 31P{1H} na Ru-1 bayan mintuna 180 a 90 °C (duba ƙarin bayani).
Yankin Hydride na 1H NMR bakan Ru-1 yayin rage sinadarin formic acid. Yanayin amsawa: 0.5 ml formic acid, 1.0 ml BMIM OAc, 13.0 µmol catalyst, 90 °C. An ɗauki NMR daga MeCN-d 3, 500 μl na deuterated solvent, kimanin 10 μl na haɗin amsawa.
Domin ƙara tabbatar da kasancewar nau'ikan halittu masu aiki a cikin tsarin catalytic, an gudanar da nazarin mass spectrometry mai ƙuduri (HRMS) na Ru-1 bayan allurar formic acid na tsawon minti 10 a zafin jiki na 90 °C. Wannan yana nuna kasancewar nau'ikan halittu marasa sinadarin chlorine ligand precatalyst a cikin cakuda amsawar. da kuma hadaddun NHC guda biyu, waɗanda aka nuna tsarinsu a Hoto na 6. Ana iya ganin bakan HRMS mai dacewa a Hoto na Ƙarin 7.
Bisa ga waɗannan bayanai, mun gabatar da tsarin amsawar intrasphere irin wanda Beller ya gabatar, inda maƙallan PNP na N-methylated ke haɓaka irin wannan amsawar. Ƙarin gwaje-gwajen da ba su haɗa da ruwayen ionic ba sun nuna wani aiki, don haka shigarsa kai tsaye ya zama dole. Mun yi hasashen cewa kunna Ru-1 da Ru-2 yana faruwa ne ta hanyar rabuwar chloride sannan kuma akwai yiwuwar ƙara NHC da rabuwar triphenylphosphine (Scheme 1a). An riga an lura da wannan kunnawa a cikin dukkan nau'ikan ta amfani da HRMS. IL-acetate tushe ne mai ƙarfi na Bronsted fiye da formic acid kuma yana iya rage proton na ƙarshe35 sosai. Mun yi hasashen cewa a lokacin zagayowar catalytic (Shirin 1b), nau'in A mai ɗauke da NHC ko PPh3 ana haɗa su ta hanyar tsari don samar da nau'in B. Sake saita wannan hadadden zuwa C a ƙarshe yana haifar da sakin CO2 da hadaddun trans-dihydrogen D. Bayan haka, proton na acid zuwa cikin hadadden dihydro tare da acetic acid da aka riga aka samar don samar da hadadden dihydro E yayi kama da babban matakin da Beller ya gabatar ta amfani da N-methylated PNP clamp homologues. Bugu da ƙari, an riga an haɗa wani analog na hadadden EL = PPh3 ta hanyar stoichiometric reaction ta amfani da Ru-1 a cikin yanayin hydrogen bayan cire chloride da gishirin sodium. Cire hydrogen da daidaitawar formate yana samar da A kuma yana kammala zagayowar.
An gabatar da wata hanyar da za a bi don amsawar intrasphere na dehydrogenation na formic acid ta amfani da hadaddun gyara Ru-POP Ru-1.
An haɗa wani sabon hadadden abu [RuHCl(iPr-dbfphos)(PPh3)]. An siffanta hadadden abu ta hanyar nazarin diffraction na NMR, ATRIR, EA da X-ray na lu'ulu'u guda ɗaya. Mun kuma bayar da rahoton nasarar farko ta amfani da hadadden abu na Ru-POP wajen rage sinadarin formic acid zuwa CO2 da H2. Duk da cewa sinadarin karfe ya sami irin wannan aiki (har zuwa 3424 h-1), hadadden abu ya kai matsakaicin mitar juyawa har zuwa 4525 h-1 a 90 °C. Bugu da ƙari, a 90 °C, sabon hadadden abu [RuHCl(iPr-dbfphos)(PPh3)] ya cimma jimillar lokacin tashi (1009 h-1) don kammala dehydrogenation na formic acid, wanda ya fi na precursor na ƙarfe (330 h-1). da kuma hadadden abu da aka ruwaito a baya [RuHCl(xantphos)(PPh3)] (333 h-1). A ƙarƙashin irin wannan yanayi, ingancin catalytic yana kama da na Ru-PNP clamp complex. Bayanan HRMS sun nuna kasancewar carbene complex a cikin cakuda reaction, kodayake a cikin ƙananan adadi. A halin yanzu muna nazarin tasirin catalytic na carbene complexes.
Duk bayanan da aka samu ko aka yi nazari a kansu a lokacin wannan binciken an haɗa su a cikin wannan labarin da aka buga [da fayilolin bayanai masu goyan baya].
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