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Asidi foromiki ye layidu talenba dɔ ye min bɛ se ka kɛ sababu ye ka idɔrɔzi jilama mara waati jan kɔnɔ. Yan, an bɛ rutɛniyɔmu sirilan kura dɔw jira ni formula caman ye [RuHCl(POP)(PPh3)] ka baara kɛ ni xanthos suguya tridentate POP klamp ligandiw ye minnu bɛ sɔrɔ jagokɛyɔrɔw la walima minnu bɛ se ka dilan nɔgɔya la. An ye o fɛnɲɛnɛmaw kɛ ka asidi foromiki dehidrozɛni bɔ walasa ka CO2 ni H2 dilan cogoya nɔgɔmanw na, minnu tɛ kɔsegin kɛ ni ji ionique BMIM OAc (1-butyl-3-methylimidazolium acetate) ye i n’a fɔ furaji. Ni an y’a lajɛ ni fɛnw jiginni hakɛ cayalenba ye, fɛn min bɛ se ka kɛ kosɛbɛ, o ye [RuHCl(xantphos)(PPh3)]Ru-1 complexe ye min dɔnna sɛbɛnw kɔnɔ, min jiginni hakɛ cayalenba ye 4525 h-1 ye 90 °C la miniti 10 kɔnɔ. Yɛlɛma kɔfɛ hakɛ kɛra 74% ye, wa jiginni dafara sanga 3 kɔnɔ (>98%). Faan wɛrɛ fɛ, katalisita min ka baara bɛɛ lajɛlen ka fisa, n’o ye [RuHCl(iPr-dbfphos)(PPh3)]Ru-2 complexe kura ye, o bɛ fɛn caman tigɛli dafalen sabati lɛrɛ 1 kɔnɔ, o bɛ na ni fɛn bɛɛ lajɛlen jiginni hakɛ ye 1009 h-1 kɔnɔ. Ka fara o kan, katalizi baara fana Kɔlɔsira funteni na fo ka Se 60 °C ma. Gazi fasa kɔnɔ, CO2 ni H2 dɔrɔn de kɔlɔsira; CO ma sɔrɔ ka sɔrɔ. Massa spectrométrie haute résolution y’a jira ko N-hétérocyclique carbene complexes bɛ sɔrɔ reaction mixture kɔnɔ.
Kuran kura sɔrɔcogo suguya bonya n’a caman ɲɔgɔnnabɔli kɛra sababu ye ka fanga maracogo fɛɛrɛw ɲini iziniw kɔnɔ fanga, funteni, izini ani mɔbiliko siratigɛ la1,2. Idɔrɔzi jatera fanga tabaga caman dɔ ye3, wa idɔrɔzi jilama fɛnɲɛnamafagalanw (LOHC) kɛra ɲininiw ɲɛsinnen ye kɔsa in na, u bɛ layidu di ka idɔrɔzi mara cogo la min bɛ baara kɛ nɔgɔya la, k’a sɔrɔ gɛlɛyaw ma sɔrɔ minnu bɛ tali kɛ degun walima kiriyɔzɛni fɛɛrɛw la ,5,6 ye. K’a sababu kɛ u farikolo ta ye, gazi ni fɛnɲɛnamafagalan jilama wɛrɛw tacogo minnu bɛ yen, olu fanba bɛ se ka kɛ ka LOHC7,8 ta. Asidi foromiki (FA) farikolo cogoya b’a kɛ layidu talen ye hidrɔzɛni marali la ni idɔrɔzi girinya hakɛ ye 4,4%9,10 ye. Nka, asidi formiki dehidrozɛni bɔli katalitiki sira minnu bɔra kɛnɛ kan, a ka c’a la, olu bɛ tali kɛ fɛnɲɛnamafagalanw na minnu bɛ wuli, ji walima asidi foromiki saniyalen,11,12,13,14 o bɛ se ka kɛ sababu ye ka fɛnɲɛnamafagalanw lafiɲɛbɔ fɛɛrɛw kɛ i n’a fɔ kondenasiyɔn, o bɛ se ka kɛ sababu ye ka gɛlɛyaw lase mɔgɔw ma. applications, doni wɛrɛw. O gɛlɛya bɛ se ka kunbɛn ni furajiw ye minnu ka lafiɲɛbɔ tansiyɔn tɛ jate, i n’a fɔ jilama ioniquew. Ka kɔn o ɲɛ, an ka baarakɛjɛkulu y’a jira ko butilimɛtilimidazɔliyɔmu jilama ionique (BMIM OAc) ye fɛnɲɛnamafagalan bɛnnen ye nin wale in na ni fixing complex Ru-PNP Ru-MACHO suguya 15 ye min bɛ sɔrɔ jagokɛyɔrɔw la 95°C ye. Hali ni sigida dɔw ye TON caman sɔrɔ ka tɛmɛ, u caman y’u jigi da fɛnɲɛnamafagalanw kan minnu bɛ wuli (i n’a fɔ THF walima DMF) walima faralifɛnw kan minnu bɛ kɛ (i n’a fɔ basiw). O ni ɲɔgɔn cɛ, an ka baara bɛ baara kɛ tiɲɛ na ni ji ionique non volatile (ILs) ye ani faralifɛn si tɛ kɛ.
Hazari ni Bernskoetter ye asidi foromiki (FA) jibɔcogo fɔ 80 °C la ni Fe-PNP katalisita ye dioxane ni LiBF4 sɔrɔli la, o kɛra sababu ye ka jatebɔ hakɛ kabakoma (TON) sɔrɔ min bɛ se 1.000.00016 ma. Laurenci ye Ru(II)- complex catalyst TPPPTS kɛ FA dehydrogenation system kɔnɔ min bɛ taa ɲɛ. O fɛɛrɛ in kɛra sababu ye ka FA dehydrogenation (ji bɔli dafalen) kɛ ni CO taamasiɲɛ dɔɔnin dɔrɔn de sɔrɔla 80 °C17 la. Walasa ka nin baara in taa ɲɛ ka taa a fɛ, Pidko ye FA ka jibɔcogo kɔsegincogo jira ni Ru-PNP sirilanw ye DMF/DBU ni DMF/NHex3 ɲagaminenw na, ka TON hakɛ sɔrɔ 310.000 fo 706.500 na 90 °C Hull, Himeda ani Fujita ye Ir complexe katalisita binuklɛri dɔ sɛgɛsɛgɛ min kɔnɔ KHCO3 ni H2SO4 sarakara, ka CO2 hidrɔzɛni ni FA dehydrogenation ɲɔgɔn falen-falen. U ka sigidaw ye TONw sɔrɔ minnu ka ca ni 3.500.000 ni 308.000 ye hidrɔzɛni sɔrɔli la 30°C la, CO2/H2 (1:1), 1 bar tansiyɔn na ani dehidrɔzɛni sɔrɔli la 60 ni 90°C19 cɛ. Sponholz, Junge ani Beller ye Mn-PNP complexe dɔ labɛn walasa ka CO2 hydrogenation reversible ani FA dehydrogenation kɛ 90 °C20 la.
Yan, an ye IL fɛɛrɛ dɔ kɛ, nka sanni an ka baara kɛ ni Ru-PNPw ye, an ye Ru-POP katalisitaw baaracogo sɛgɛsɛgɛ, an ka dɔnniya la, minnu ma jira fɔlɔ o siratigɛ la.
K’a sababu kɛ u ka nɛgɛ ni ligandi jɛɲɔgɔnya ɲuman ye (MLC), amino-PNP sirili jɛkulu minnu sinsinnen bɛ Noyori suguya hakilinaw kan ni amino baarakɛjɛkulu filananw ye minnu bɛ ɲɔgɔn sɔrɔ 21 (i n’a fɔ Ru-MACHO-BH), a ka c’a la, olu bɛ ka caya ka taa a fɛ mɔlikulu misɛnnin dɔw ka baara la. Misali minnu bɛ fɔ kosɛbɛ, olu ye CO22 ye, alkɛniw ni karɔbɔniliw ka hidrɔzɛni, transfert hidrɔzɛni23 ani alikɔliw ka hidrɔzɛni tali min tɛ sɔn ka kɛ24 ye. A fɔra ko PNP klamp ligandiw ka N-metilasi bɛ se ka katalisita baara jɔ pewu25, o bɛ se ka ɲɛfɔ ni a ye ko aminɛw bɛ kɛ porotɔni sɔrɔyɔrɔw ye, o ye wajibi nafama ye katalisita sɛgɛsɛgɛli waati la ni MLC ye. Nka, asidi foromiki dehidrozɛni bɔli cogoya kɔfɛ, o kɔlɔsira Beller fɛ, yɔrɔ min na Ru-PNP complexes N-methylated ye asidi formiki dehydrogenation katalitiki ɲuman jira tiɲɛ na ka tɛmɛ u ɲɔgɔnnaw kan minnu ma metilasi Ikomi kɔrɔlen complexe tɛ se ka sen don MLC la amino unit fɛ, o b’a jira kosɛbɛ ko MLC, o la amino unit, bɛ se ka jɔyɔrɔba ta (de)hydrogenation jiginni dɔw la ka tɛmɛ a tun bɛ miiri min na fɔlɔ.
Ni an y’a suma ni POP sirilanw ye, POP sirilanw ka rutɛniyɔmu kɔmplɛsiw ma sɛgɛsɛgɛ ka ɲɛ o yɔrɔ la. POP ligandiw tun bɛ kɛ laada la fɔlɔ hidroformylation kama, yɔrɔ min na u bɛ kɛ i n’a fɔ ligandi chelating sanni ka kɛ bidentate bite angle characteristic 120° ɲɔgɔn ye clamping ligands kama, minnu kɛra ka sugandili kɛcogo ɲuman kɛ linear ni branched products27,28, Kabini o waati, Ru-POP complexes (Ru-POP complexes) man teli ka kɛ hidrɔzɛni katalizi la, nka u ka baara kɛcogo misaliw fɔra ka tɛmɛ hidrɔzɛni jiginni na30. Nin yɔrɔ in na, an b’a jira ko Ru-POP kɔmplɛsi ye fɛn ye min bɛ se ka asidi foromiki ka ji bɔli kɛ, o bɛ Beller ka sɔrɔli sinsin ko amino yɔrɔ min bɛ Ru-PNP amine katalisita klasiki kɔnɔ, o nafa ka dɔgɔ o wale in na.
An ka kalan bɛ daminɛ ni katalisita suguya fila labɛnni ye ni formula caman ye [RuHCl(POP)(PPh3)] (Ja 1a). Walasa ka stɛriki ni ɛlektroniki sigicogo sɛmɛntiya, dibɛnzo[b,d]furan sugandira ka bɔ 4,6-bis(diisopropylphosphino) la min bɛ sɔrɔ jagokɛyɔrɔw la (Ja 1b) 31. Katalisita minnu kalanna nin baara in na, olu kɛra ni fɛɛrɛ caman ye min labɛnna Whittlesey32 fɛ, ni [RuHCl(PPh3)3]•toluyɛni33 farankan kɛra a ɲɛbila ye. Aw bɛ nɛgɛ ɲɛfɛla ni POP sirilan ligandi ɲagami THF kɔnɔ ji tɛ min na kosɛbɛ ani ni fiɲɛ tɛ a la. O wale in kɛra ni kulɛri caman yeli ye ka bɔ bulama dibiman na ka taa jɛman na ani ka fura saniyalen di lɛri 4 kɔsegin kɔfɛ walima sanga 72 kɔsegin kɔfɛ 40°C la. THF bɔlen kɔfɛ fɛnɲɛnamafagalan na ani ka a ko siɲɛ fila ni hɛkɛsi walima diɛtili ɛtiri ye, tripɛnɛlifosifini bɔra walasa ka fura in di i n’a fɔ mugu jɛman min bɛ sɔrɔ hakɛ caman na.
Ru-1 ni Ru-2 ɲɔgɔndanw dilanni. a) Fɛnɲɛnɛmaw labɛncogo. b) Komplekisi min dilannen don, o jɔcogo.
Ru-1 dɔnna kaban sɛbɛnw kɔnɔ32, wa jogo wɛrɛw bɛ sinsin Ru-2 kan. Ru-2 ka 1H NMR spektrum ye fosifini atomu cis cogoya Sɛmɛntiya hidridi fila ligandi la. Peak dt plot (Ja 2a) b 2JP-H coupling constants jira min ye 28,6 ani 22,0 Hz ye, minnu b b nkan makɔnɔn kɔnɔ Hidrɔzɛni decouplé 31P{1H} spectrum kɔnɔ (Ja 2b), 2JP-P coupling constant min bɛ 27,6 Hz ɲɔgɔn na, o kɔlɔsira, o b’a jira ko clamp ligand phosphines ni PPh3 fila bɛɛ ye cis-cis ye. Ka fara o kan, ATR-IR bɛ rutɛni-hidrɔzɛni sɔgɔlilan taamasiyɛn jira santimɛtɛrɛ 2054-1 na. Walasa ka jɔcogo ɲɛfɔ ka taa a fɛ, Ru-2 complexe kɛra kristali ye ni lafiɲɛbɔ ye so funteni na ni jogo ye min bɛ se ka kɛ X-ray kalanw kama (Ja 3, Tablo 1 faralen). A bɛ kristali kɛ yɔrɔ kulu P-1 ka triclinique systeme kɔnɔ ni cocrystalline benzene unit kelen ye unité cellule kelen na. A bɛ P-Ru-P dakun janya jira min ye 153,94° ye, o min ka bon kosɛbɛ ka tɛmɛ DBFphos34 ɲin fila dawolo 130° kan. Ni 2,401 ani 2,382 Å ye, Ru-PPOP jɛɲɔgɔnya janya ka jan kosɛbɛ ka tɛmɛ Ru ni PPh3 jɛɲɔgɔnya janya kan min ye 2,232 Å ye, o bɛ se ka kɛ DBFphos kɔkolo misɛnninw janya bonya sababu ye min bɛ sɔrɔ a cɛmancɛ 5-bololan fɛ. Nɛgɛ cɛmancɛ jateminɛcogo ye octahedral ye a jɔyɔrɔba la ni O-Ru-PPh3 kɛrɛ ye 179,5°. H-Ru-Cl jɛɲɔgɔnya tɛ tilennen ye pewu, a kɛrɛ bɛ 175° ɲɔgɔn bɔ ka bɔ triphenylphosphine ligandi la. Atomiki yɔrɔjanw ni jɛɲɔgɔnya janya bɛ sɔrɔ jatebɔsen 1 na.
Ru-2 ka NMR spektrum. a) Hidridi yɔrɔ min bɛ 1H NMR spectre la min bɛ Ru-H dt taamasiɲɛ jira. b) 31 P{ 1 H} NMR spectre min bɛ taamasiɲɛw jira ka bɔ triphenylphosphine (bulu) ani POP ligand (green) la.
Ru-2 ka sigicogo. Elipsoïdes funtenimaw bɛ jira ni 70% ye. Walasa ka jɛya, bɛnzɛni ni idɔrɔzi atomu kokirisitali minnu bɛ karɔbɔli kan, olu bɔra yen.
Walasa ka kɔmplɛsiw seko jateminɛ ka asidi foromiki dehidrozɛni bɔ, farikoloɲɛnajɛ cogoyaw sugandira minnu kɔnɔ, PNP-klamp kɔmplɛsi bɛnninw (misali la, Ru-MACHO-BH) tun bɛ baara kɛ kosɛbɛ Asidi formiki mililitiri 0,5 (13,25 mmol) ji bɔli ni 0,1 mol% (1000 ppm, 13 μmol) ruthenium complex Ru-1 walima Ru-2 ye ni mililitiri 1,0 (5,35 mmol) ion jilama (IL) BMIM OAc ye (tabali ja) 2 Jaa 4nan na);
Walasa ka sariya sɔrɔ, o wale in kɛra fɔlɔ ni precursor adduct [RuHCl(PPh3)3]·toluene ye. O wale in bɛ Kɛ ni funteni ye min bɛ Bɔ 60 na ka Se 90 ma. Ka kɛɲɛ ni kɔlɔsili nɔgɔmanw ye minnu kɛra ɲɛ na, o fɛnɲɛnamafagalan tun tɛ se ka wuli pewu IL la hali ni a wulila ka mɛn ni a funteni ye 90°C ye, nka a wulilen kɛra asidi foromiki donna kɔfɛ. Ni 90°C ye, fɛn caman tigɛli kɛra 56% (TOF = 3424 h-1) ye miniti 10 fɔlɔ kɔnɔ, wa fɛn caman tigɛli bɛ se ka kɛ hakɛ la (97%) sanga saba kɔfɛ (don 1). Ni funteni dɔgɔyara ka se 80 °C ma, o bɛ dɔ bɔ fɛn caman tigɛli la ka tɛmɛ tila kan ka se 24% ma miniti 10 kɔfɛ (TOF = 1467 h-1, donsen 2), o bɛ dɔ bɔ ka taa a fɛ ka se 18% ni 18% ma 70 °C ni 60 °C la, o bɛ kɛ 6% ye (donna 3 ani 4). O bɛɛ la, induction (daminɛ) waati si ma Sɔrɔ, o b’a Jira ko katalisita bɛ Se ka Kɛ suguya ye min bɛ Se ka Kɛ fɛn ye min bɛ Se ka Kɛ walima ko suguya minnu bɛ Se ka Kɛ fɛn ye, olu jiginni teliya kojugu fo a tɛ Se ka Kɔlɔsi ni nin kunnafonidilan in ye.
Precurseurs jateminɛ kɔfɛ, Ru-POP clamp complexes Ru-1 ni Ru-2 kɛra cogo kelen na. Ni 90°C ye, fɛn caman tigɛli bɛ ye o yɔrɔnin bɛɛ. Ru-1 ye 74% jiginni sɔrɔ k’a lajɛ miniti 10 fɔlɔ kɔnɔ (TOFmax = 4525 h-1, donsen 5nan). Ru-2 ye baara dɔgɔya dɔɔni nka a bɛ kɛ cogo basigilen na, a ye 60% jiginni sabati miniti 10 kɔnɔ (TOFmax = 3669 h-1) ani fɛn caman tigɛli dafalen miniti 60 kɔnɔ (>99%) (don 9). A kɔlɔsira ko Ru-2 ka fisa kosɛbɛ ni nɛgɛ ɲɛfɛla ye ani Ru-1 jiginni dafalen na. O la, hali ni nɛgɛ ɲɛfɛla ni Ru-1 ka TOFoverall hakɛw bɛ ɲɔgɔn ta farikoloɲɛnajɛ dafalen na (330 h-1 ani 333 h-1, o cogo kelen na), Ru-2 ka TOFoverall ye 1009 h-1 ye.
O kɔfɛ, Ru-1 ni Ru-2 kɛra funteni caman yeli ye min kɔnɔ funteni bɛ dɔgɔya dɔɔnin dɔɔnin ni 10 °C ye ka se 60 °C ma a dɔgɔyalenba la (Ja 3). Ni 90°C la, complexe ye baara jira teliya la, a bɛ se ka fɔ ko fɛn caman tigɛli bɛ kɛ lɛrɛ kelen kɔnɔ, o tuma na ni funteni dɔgɔyara, baara bɛ jigin kosɛbɛ. Py-1 jiginni kɛra 14% ni 23% ye miniti 10 kɔfɛ 80°C ni 70°C la, miniti 30 kɔfɛ a cayara ka se 79% ni 73% ma (don 6 ani 7). Kɔrɔbɔli fila bɛɛ y’a jira ko mɔgɔw jiginni hakɛ ye ≥90% ye sanga fila kɔnɔ. O kɛcogo kelen de kɔlɔsira Ru-2 fana na (donna 10 ani 11). A nafa ka bon kosɛbɛ, Ru-1 tun bɛ fanga sɔrɔ dɔɔnin farikoloɲɛnajɛ laban na 70 °C la ni TOF bɛɛ lajɛlen ye 315 h-1 ye ni i y’a suma ni 292 h-1 ye Ru-2 ta la ani 299 h-1 ye nɛgɛ ɲɛfɛla la.
Funteni dɔgɔyali wɛrɛ fo ka se 60 °C ma, o kɛra sababu ye ka fɛn caman tigɛli ma ye k’a lajɛ miniti 30 fɔlɔw kɔnɔ. Ru-1 tun tɛ baara kɛ kosɛbɛ funteni dɔgɔyalenba la k’a daminɛ na k’a daminɛ na, o kɔfɛ, a ye baara caya, o b’a jira ko baarakɛwaati dɔ wajibiyalen don, min kɔnɔ Ru-1 precatalyst bɛ wuli ka kɛ suguya ye min bɛ baara kɛ ni katalizi ye. Hali n’o bɛ se ka kɛ funteni bɛɛ la, miniti 10 min kɛra k’a daminɛ na, o ma se ka kɛ sababu ye ka baarakɛwaati dɔ dɔn funteni caman na. O kɛcogo kelen de sɔrɔla Ru-2 fana na. Ni 70 ni 60 °C ye, fɛn caman tigɛli ma ye k’a lajɛ miniti 10 fɔlɔw kɔnɔ. A nafa ka bon k’a dɔn ko nin kɔrɔbɔli fila bɛɛ la, gazi monokisidi sɔrɔli ma kɔlɔsi an ka minɛn ka dɔnni dan kɔnɔ (<300 ppm), ni H2 ni CO2 dɔrɔn de ye fɛnw ye minnu kɔlɔsira.
Asidi foromiki dehidrozɛni jaabiw sumalen minnu sɔrɔla ka tɛmɛ nin baarakɛjɛkulu in kɔnɔ, n’o ye seko ni dɔnko cogoya jirabaga ye ani ka baara kɛ ni Ru-PNP sirilan complexes ye, o y’a jira ko Ru-POP sirilan kura min dilannen don, o baara bɛ tali kɛ a PNP ɲɔgɔnna 15. K’a sɔrɔ klamp PNP ye RPM sɔrɔ 500-1260 h-1 na batch experiments kɔnɔ, POP clamp kura ye o ɲɔgɔnna TOFovertal value sɔrɔ 326 h-1, ani Ru-1 ni 1590 h-1 ka TOFmax hakɛw kɔlɔsira. o cogo kelen na, olu ye 1988 h-1 ani 1590 h-1 ye. Ru-2 ye 1 ye 80 °C la, Ru-1 ye 4525 h-1 ye ani Ru-1 ye 3669 h-1 ye 90 °C la.
Asidi formiki dehidrozɛni bɔli funteni sɛgɛsɛgɛli ni Ru-1 ni Ru-2 katalisita ye. A kɛcogo : 13 μmol katalisita, mililitiri 0,5 (13,25 mmol) asidi formiki, mililitiri 1,0 (5,35 mmol) BMIM OAc.
NMR bɛ kɛ ka farikoloɲɛnajɛ kɛcogo faamuya. Ikomi danfaraba bɛ 2JH-P la hidridi ni fosifini ligandiw cɛ, nin kalan in sinsinnen bɛ hidridi kuncɛyɔrɔ kan. Ru-1 ta la, dt cogoya danma dɔ sɔrɔla hidrɔzɛni bɔli yɔrɔ la miniti 60 fɔlɔw la. Hali ni jiginɛba jiginniba bɛ kɛ ka bɔ −16,29 na ka se −13,35 ppm ma, a ni fosifini ka jɛɲɔgɔnya sabatilenw ye 27,2 ani 18,4 Hz ye (Jaa 5, A kuncɛ). O bɛ bɛn fosifini saba bɛɛ ma, hidrɔzɛni ligandi bɛ minnu na cis cogoya la, wa o b’a jira ko ligandi cogoya bɛ sabati dɔɔnin IL kɔnɔ sanga kelen ɲɔgɔn kɔnɔ, farikoloɲɛnajɛ kɛcogo ɲumanw na. Jiginni barikama bɛ se ka kɛ sababu ye ka bɔ ligandi kulorilenw bɔli la ani asidi asetili-fɔrimuki ɲɔgɔndanw sɔrɔli la, d3-MeCN ɲɔgɔndan sɔrɔli yɔrɔ la NMR tubabukan na, walima N-hɛtɛrosiklɛtiw sɔrɔli fɛ minnu bɛ bɛn o ma. o ɲɛfɔra. Karbɛni (NHC) complexe. Dehydrogenation reaction (ji bɔli) kɛtuma na, o taamasiɲɛ in fanga tora ka dɔgɔya, wa miniti 180 tɛmɛnen kɔfɛ, taamasiyɛn ma kɔlɔsi tugun. O nɔ na, ​​taamasiyɛn kura fila sɔrɔla. Fɔlɔ bɛ dd cogoya jɛlen jira min bɛ kɛ -6,4 ppm (B kuncɛyɔrɔ). Doublet in ka coupling constant belebele bɛ 130,4 Hz ɲɔgɔn na, o b’a jira ko fosifini unit dɔ wulila ka kɛɲɛ ni hydrogène ye. O bɛ se ka kɛ ko POP sirilan bɛ labɛn kokura ka kɛ κ2-P,P cogoya ye. Nin fɛnɲɛnɛma in bɔli katalizi kɔfɛ, o bɛ se k’a jira ko nin sugu in bɛ na ni baarakɛbaliya siraw ye waati kɔnɔ, ka katalizi sinsinni kɛ. Faan wɛrɛ fɛ, kemikoro jiginni dɔgɔyali b’a jira ko a bɛ se ka kɛ suguya fila ye15. O kulu kura filanan bɛ sɔrɔ -17,5 ppm la. Hali n’a foli ma dɔn, an dalen b’a la ko a ye saba ye min ka ɲɔgɔndan hakɛ fitinin ye 17,3 Hz ye, o b’a jira ko hidrɔzɛni ligandi bɛ siri POP sirilan fosifini ligandi dɔrɔn de la, o fana b’a jira ko triphenylphosphine bɔli (C kuncɛ). A bɛ se ka bila ligandi wɛrɛ nɔ na, ​​i n’a fɔ asetili kulu walima NHC min dilannen don a yɔrɔ la ka bɔ ion ji la. PPh3 farali bɛ jira ka taa a fɛ ni kelen barikama ye -5,9 ppm. ka Ru-1 31P{1H} spectrum kɔnɔ miniti 180 kɔfɛ 90 °C la (aw ye kunnafoni wɛrɛw lajɛ).
Ru-1 ka 1H NMR spektrum hidridi yɔrɔ la asidi foromiki ka jibɔ waati. A kɛcogo : asidi formiki mililitiri 0,5, BMIM OAc mililitiri 1,0, katalisita 13,0 μmol, 90 °C. NMR bɔra MeCN-d 3 la, 500 μl deuterated solvent, 10 μl ɲɔgɔn ye reaction mixte ye.
Walasa ka fɛnɲɛnɛma suguya baarakɛtaw sɔrɔli dafa ka taa a fɛ katalitiki siratigɛ la, Ru-1 sɛgɛsɛgɛli kɛra asidi foromiki pikiri kɛlen kɔfɛ miniti 10 kɔnɔ 90 °C la. O b’a jira ko suguya minnu tɛ ni kulori ligandi precatalyst ye, olu bɛ sɔrɔ farikoloɲɛnajɛ ɲagaminen na. ka fara NHC complexe fila kan, minnu ka sigicogo miirilenw jiralen don ja 6. HRMS spectre correspondant bɛ se ka ye ja 7 kɔnɔ.
Ka da nin kunnafoniw kan, an bɛ intrasphere reaction mechanism dɔ labɛn min ni Beller ye min fɔ, o bɛ tali kɛ ɲɔgɔn na, N-methylated PNP clamps bɛ o reaction kelen in kɛ min kɔnɔ. Kɔrɔbɔli wɛrɛw minnu Kɛra ni ion jilamaw ma Kɛ, olu ma baara si Jira, o la a bɛ iko a sendonli tilennen ka kan. An bɛ hakilina ta ko Ru-1 ni Ru-2 baarakɛli bɛ kɛ ni kuloridi farali ye o kɔfɛ NHC farali bɛ se ka kɛ ani trifenilifosifini farali (Scheme 1a). O waleyali in suguya bɛɛ la, o Kɔlɔsira ka Tɛmɛ ni HRMS ye. IL-acetate ye Bronsted basi barikama ye ka tɛmɛ asidi foromiki kan, wa a bɛ se ka kɔfɛta in bɔ ni poroton ye kosɛbɛ35. An bɛ hakilina ta ko katalitiki sɛrɛkili kɔnɔ (Scheme 1b), suguya A baarakɛtaw minnu bɛ NHC walima PPh3 ta, olu bɛ ɲɔgɔn sɔrɔ foromati fɛ walasa ka suguya B dilan o ni Beller ye fɛɛrɛ jɔnjɔn min sugandi ni N-methylated PNP clamp homologues ye, o bɛ tali kɛ ɲɔgɔn na. Ka fara o kan, EL = PPh3 complexe analogue dɔ tun bɛ labɛn ka tɛmɛn ni stoikiometriki ye ni Ru-1 ye hidrɔzɛni fiɲɛ kɔnɔ, kulori bɔlen kɔfɛ ni sodiyɔmu kɔgɔ ye. Hidrɔzɛni bɔli ni fɔmati ka ɲɔgɔndɛmɛ bɛ A di ani ka sɛrɛkili dafa.
Fɛɛrɛ dɔ jirala min bɛ kɛ ka asidi foromiki dehidrozɛni kɛcogo intrasphère kɔnɔ ni fixing complex Ru-POP Ru-1 ye.
Komplekisi kura [RuHCl(iPr-dbfphos)(PPh3)] dɔ labɛnna. O complexe in kɛra ni NMR, ATRIR, EA ani X-ray diffraction analysis ye kristalɛ kelenw na. An bɛ Ru-POP pincer complexes (pinɛtiri complexes) kɛcogo fɔlɔ min ɲɛnabɔra kosɛbɛ, o fana fɔ asidi formiki dehydrogenation (jibɔli) la ka kɛ CO2 ni H2 ye. Hali ni nɛgɛ ɲɛfɛla ye o baara kelen sɔrɔ (fo ka se 3424 h-1 ma), o complexe sera a jiginni hakɛ maksimali ma fo ka se 4525 h-1 ma 90 °C la. Ka fara o kan, 90 °C la, kɔmplɛsi kura [RuHCl(iPr-dbfphos)(PPh3)] ye wuluwulu waati bɛɛ lajɛlen sɔrɔ (1009 h-1) walasa ka asidi foromiki dehydrogenation dafa, o min ka bon kosɛbɛ ka tɛmɛ nɛgɛ ɲɛfɛla ta kan (330 h-1). ani complexe [RuHCl(xantphos)(PPh3)] (333 h-1) min kofɔra ka tɛmɛ. O cogo kelen na, katalizi baarakɛcogo bɛ se ka suma ni Ru-PNP klamp complexe ta ye. HRMS kunnafoniw b’a jira ko karɔbɔni kɔmplɛsi bɛ farikoloɲɛnajɛ ɲagaminen na, hali ni a hakɛ ka dɔgɔn. An bɛ ka karɔbɔni kɔmplɛsiw ka katalizi nɔw sɛgɛsɛgɛ sisan.
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