Daalụ maka ịga leta Nature.com. Ụdị ihe nchọgharị ị na-eji nwere nkwado CSS pere mpe. Maka nsonaazụ kacha mma, anyị na-akwado ka ị jiri ụdị ihe nchọgharị gị ọhụrụ (ma ọ bụ gbanyụọ Ụdị Ndakọrịta na Internet Explorer). Ka ọ dị ugbu a, iji hụ na nkwado na-aga n'ihu, anyị na-egosi saịtị ahụ na-enweghị nhazi ma ọ bụ JavaScript.
Asịd Formic bụ otu n'ime ihe ndị kacha ekwe nkwa maka nchekwa ogologo oge nke hydrogen mmiri mmiri. N'ebe a, anyị na-egosi usoro nke mgbagwoju anya ruthenium ọhụrụ yana usoro izugbe [RuHCl(POP)(PPh3)] site na iji ligands xanthos-type tridentate POP clamp nke a na-emepụta n'ahịa ma ọ bụ nke a na-emepụta ngwa ngwa. Anyị jiri mgbagwoju ndị a wepụ formic acid iji mepụta CO2 na H2 n'okpuru ọnọdụ dị nro, nke na-enweghị reflux site na iji ionic liquid BMIM OAc (1-butyl-3-methylimidazolium acetate) dị ka ihe mgbaze. Site n'echiche nke ugboro ntụgharị kachasị, ihe na-akpali akpali kachasị dị irè bụ [RuHCl(xantphos)(PPh3)]Ru-1 complex nke a maara n'akwụkwọ, nke nwere ugboro ntụgharị kachasị nke 4525 h-1 na 90 °C maka nkeji iri. Ọnụego mgbanwe mgbe mgbanwe gasịrị bụ 74%, a rụchakwara mgbanwe ahụ n'ime awa 3 (>98%). N'aka nke ọzọ, ihe na-akpali akpali nke nwere arụmọrụ kachasị mma n'ozuzu ya, akwụkwọ akụkọ [RuHCl(iPr-dbfphos)(PPh3)]Ru-2 complex, na-akwalite mgbanwe zuru oke n'ime awa 1, na-ebute ọnụego ntụgharị zuru oke nke 1009 h-1. Na mgbakwunye, a hụkwara ọrụ catalytic na okpomọkụ ruo 60 °C. N'oge gas, naanị CO2 na H2 ka a hụrụ; achọpụtaghị CO. Spectrometry mass resolution-resolution gosiri ọnụnọ nke N-heterocyclic carbene complexes na ngwakọta mmeghachi omume.
Oke ahịa nke ike mmeghari ohuru na mgbanwe ya emeela ka a chọọ teknụzụ nchekwa ike n'ọkwa ụlọ ọrụ mmepụta ihe na ngalaba ike, okpomọkụ, ụlọ ọrụ mmepụta ihe na njem1,2. A na-ewere hydrogen dị ka otu n'ime ndị na-ebu ike kachasị ukwuu3, ndị na-ebu hydrogen organic mmiri mmiri (LOHCs) abụrụla isi ihe nyocha n'oge na-adịbeghị anya, na-enye nkwa nke ịchekwa hydrogen n'ụdị nhazi dị mfe na-enweghị nsogbu ndị metụtara nrụgide ma ọ bụ teknụzụ cryogenic4. ,5,6. N'ihi ihe onwunwe ha, enwere ike iji ọtụtụ akụrụngwa njem dị ugbu a maka mmanụ ụgbọala na mmanụ mmiri mmiri ndị ọzọ ibuga LOHC7,8. Njirimara anụ ahụ nke formic acid (FA) na-eme ka ọ bụrụ ihe na-ekwe nkwa maka nchekwa hydrogen nwere ọdịnaya dị arọ hydrogen nke 4.4%9,10. Agbanyeghị, sistemụ catalytic ebipụtara maka formic acid dehydrogenation na-achọkarị iji ihe mgbaze organic na-agbanwe agbanwe, mmiri ma ọ bụ acid formic dị ọcha,11,12,13,14 nke nwere ike ịchọ ka e jiri usoro nkewa nkewa solvent vapor dị ka condensation, nke nwere ike ibute nsogbu na ngwa ndị ahịa. ngwa, ibu ọzọ. Enwere ike imeri nsogbu a site na iji ihe mgbaze nwere nrụgide uzuoku dị ntakịrị, dị ka mmiri ionic. Na mbụ, ndị otu ọrụ anyị gosipụtara na mmiri ionic butylmethylimidazolium acetate (BMIM OAc) bụ ihe mgbaze kwesịrị ekwesị na mmeghachi omume a site na iji ụdị Ru-PNP Ru-MACHO dị n'ahịa. Dịka ọmụmaatụ, anyị gosipụtara mwepụ mmiri FA na sistemụ mmiri na-aga n'ihu site na iji BMIM OAc, na-enweta TON nke karịrị 18,000,000 na 95°C. Ọ bụ ezie na ụfọdụ sistemụ enwetala TON dị elu na mbụ, ọtụtụ adaberela na ihe mgbaze organic na-agbanwe agbanwe (dị ka THF ma ọ bụ DMF) ma ọ bụ ihe mgbakwunye ejiri (dị ka ntọala). N'ụzọ dị iche, ọrụ anyị na-eji mmiri ionic na-adịghị agbanwe agbanwe (ILs) na enweghị ihe mgbakwunye.
Hazari na Bernskoetter kọrọ na a na-ebelata mmiri ọgwụ formic acid (FA) na 80 °C site na iji ihe na-akpali Fe-PNP n'ihu dioxane na LiBF4, wee nweta ọnụọgụ ntụgharị dị egwu (TON) nke ihe dị ka 1,000,00016. Laurenci jiri ihe na-akpali Ru(II)-complex catalyst TPPPTS na sistemụ FA na-aga n'ihu. Usoro a butere ihe fọrọ nke nta ka ọ bụrụ mmebi mmiri ọgwụ FA zuru oke yana obere obere ihe CO achọpụtara na 80 °C17. Iji mee ka ubi a ka mma, Pidko gosipụtara mbelata mmiri ọgwụ FA na-agbanwe agbanwe site na iji ihe na-akpali Ru-PNP clamp catalyst na ngwakọta DMF/DBU na DMF/NHex₃, na-enweta uru TON nke 310,000 ruo 706,500 na 90 °C18. Hull, Himeda na Fujita mụrụ ihe na-akpali ọgwụ Ir binuclear nke e ji chụọ KHCO3 na H2SO4 n'àjà, na-agbanwe hydrogenation CO2 na mwepụ mmiri ọgwụ FA. Sistemụ ha nwetara TON karịrị 3,500,000 na 308,000 n'otu n'otu maka hydrogenation na 30°C, CO2/H2 (1:1), nrụgide otu bar na maka dishydrogenation n'etiti 60 na 90°C19. Sponholz, Junge na Beller mepụtara Mn-PNP complex maka reversible CO2 hydrogenation na FA dehydrogenation na 90°C20.
N'ebe a, anyị jiri ụzọ IL mee ihe, mana kama iji Ru-PNPs, anyị lere anya n'iji Ru-POP catalyst, nke anyị maara na mbụ egosighi na nke a.
N'ihi njikọ ha dị mma nke metal-ligand (MLC), mgbagwoju amino-PNP nke dabere na echiche ụdị Noyori yana otu amino ọrụ nke abụọ na-akpakọrịta 21 (dịka Ru-MACHO-BH) na-aghọwanye ewu ewu na ụfọdụ obere ọrụ molekul. Ihe atụ ndị a ma ama gụnyere CO22, hydrogenation nke alkenes na carbonyls, transfer hydrogenation23 na dehydrogenation nke alcohols24 na-anabataghị. Akọpụtala na N-methylation nke ligands clamp PNP nwere ike ịkwụsị ọrụ catalyst25 kpamkpam, nke enwere ike ịkọwa site n'eziokwu ahụ bụ na amine na-eje ozi dị ka isi iyi proton, nke bụ ihe dị mkpa n'oge usoro catalytic na-eji MLC. Agbanyeghị, Beller hụrụ usoro dị iche na formic acid dehydrogenation n'oge na-adịbeghị anya, ebe mgbagwoju N-methylated Ru-PNP gosipụtara catalytic dehydrogenation nke formic acid karịa ndị otu ha na-enweghị methylated26. Ebe ọ bụ na ihe mgbagwoju anya mbụ enweghị ike isonye na MLC site na amino unit, nke a na-egosi nke ọma na MLC, ya mere amino unit, nwere ike ịrụ ọrụ dị obere na mgbanwe ụfọdụ (de) hydrogenation karịa ka e chere na mbụ.
Ma e jiri ya tụnyere POP clamps, a kabeghị amụcha ruthenium complexes nke POP clamps nke ọma n'ebe a. A na-ejikarị POP ligands eme ihe maka hydroformylation, ebe ha na-arụ ọrụ dị ka chelating ligands kama ịbụ akụkụ bidentate nke ihe dị ka 120° maka clamping ligands, nke ejirila mee ka nhọrọ dịkwuo mma maka ngwaahịa linear na branched27,28,29. Kemgbe ahụ, a naghị eji Ru-POP complexes eme ihe na hydrogenation catalysis, mana akọọla ihe atụ nke ọrụ ha na transfer hydrogenation na mbụ30. N'ebe a, anyị na-egosi na Ru-POP complex bụ ihe na-akpali akpali nke ọma maka dehydrogenation nke formic acid, na-akwado nchọpụta Beller na amino unit dị na Ru-PNP amine catalyst klasịk adịghị mkpa na mmeghachi omume a.
Ọmụmụ ihe anyị na-amalite site na njikọta nke ihe mkpali abụọ a na-ahụkarị na usoro izugbe [RuHCl(POP)(PPh3)] (Foto 1a). Iji gbanwee nhazi steric na eletrọniki, ahọpụtara dibenzo[b,d]furan site na 4,6-bis(diisopropylphosphino) dị na azụmaahịa (Foto 1b) 31. Ejiri usoro izugbe nke Whittlesey32 mepụtara mepụta ihe mkpali ndị a mụrụ n'ọrụ a. Gwakọta ihe mgbakwunye ígwè na POP clamp ligand na THF n'okpuru ọnọdụ anhydrous na anaerobic siri ike. Mmeghachi omume ahụ sochiri mgbanwe agba dị ukwuu site na odo odo gbara ọchịchịrị gaa na odo ma nye ngwaahịa dị ọcha mgbe awa 4 nke reflux ma ọ bụ awa 72 nke reflux na 40°C. Mgbe ewepụsịrị THF na vacuo ma saa ya ugboro abụọ na hexane ma ọ bụ diethyl ether, ewepụrụ triphenylphosphine iji nye ngwaahịa ahụ dị ka ntụ ntụ odo na nnukwu mkpụrụ.
Njikọta nke mgbagwoju anya Ru-1 na Ru-2. a) Ụzọ esi emepụta mgbagwoju anya. b) Nhazi nke mgbagwoju anya emepụtara.
A maara Ru-1 site na akwụkwọ edemede32, njirimara ndị ọzọ na-elekwasịkwa anya na Ru-2. 1H NMR spectrum nke Ru-2 kwadoro nhazi cis nke atọm phosphine na ligand nke ụzọ hydride. Peak dt plot (Fig. 2a) na-egosi 2JP-H constants couple nke 28.6 na 22.0 Hz, nke dị n'ime oke a tụrụ anya ya na akụkọ gara aga32. Na hydrogen decoupled 31P{1H} spectrum (Fig. 2b), a hụrụ 2JP-P constant couple nke ihe dị ka 27.6 Hz, na-akwado na ma clamp ligand phosphines na PPh3 bụ cis-cis. Na mgbakwunye, ATR-IR na-egosi band ruthenium-hydrogen stretching a na-ahụkarị na 2054 cm-1. Maka nkọwapụta ọzọ gbasara nhazi, e jiri igwe ọkụ gbasaara ihe mejupụtara Ru-2 na okpomọkụ ụlọ nke zuru oke maka ọmụmụ ihe X-ray (Foto 3, Tebụl Mgbakwunye 1). Ọ na-agbaze na sistemụ triclinic nke otu oghere P-1 yana otu cocrystalline benzene nkeji kwa sel. Ọ na-egosipụta akụkụ mkpuchi P-Ru-P sara mbara nke 153.94°, nke sara mbara karịa akụkụ mkpuchi 130° nke bidentate DBFphos34. Na 2.401 na 2.382 Å, ogologo njikọ Ru-PPOP dị ogologo karịa ogologo njikọ Ru ruo PPh3 nke 2.232 Å, nke nwere ike ịbụ nsonaazụ nke akụkụ nri azụ sara mbara nke DBFphos nke mgbanaka 5 etiti ya kpatara. Ọdịdị nke etiti ígwè ahụ bụ octahedral nke nwere akụkụ O-Ru-PPh3 nke 179.5°. Nhazi H-Ru-Cl abụghị nke kwụ ọtọ kpamkpam, yana akụkụ nke ihe dị ka 175° site na ligand triphenylphosphine. E depụtara anya atọm na ogologo njikọ na Tebụl 1.
NMR spectrum nke Ru-2. a) Mpaghara Hydride nke spectrum NMR 1H na-egosi akara Ru-H dt. b) 31 P{ 1 H} NMR spectrum na-egosi akara sitere na triphenylphosphine (acha anụnụ anụnụ) na POP ligand (akwụkwọ ndụ akwụkwọ ndụ).
Nhazi nke Ru-2. A na-egosi ellipsoids okpomọkụ na ohere nke 70%. Iji mee ka o doo anya, ewepụla cocrystalline benzene na atọm hydrogen dị na carbon ahụ.
Iji nyochaa ikike nke mgbagwoju anya iji wepụ mmiri formic acid, a họọrọ ọnọdụ mmeghachi omume nke ngwakọta PNP-clamp kwekọrọ (dịka ọmụmaatụ, Ru-MACHO-BH) dị oke arụ ọrụ15. Dehydrogenation nke 0.5 ml (13.25 mmol) formic acid site na iji 0.1 mol% (1000 ppm, 13 µmol) ruthenium complex Ru-1 ma ọ bụ Ru-2 site na iji 1.0 ml (5.35 mmol) ionic liquid (IL) BMIM OAc (tebụl-figure) 2; Foto 4);
Iji nweta ọkọlọtọ ahụ, e buru ụzọ mee mmeghachi omume ahụ site na iji mgbakwunye precursor [RuHCl(PPh3)3]·toluene. A na-eme mmeghachi omume ahụ na okpomọkụ site na 60 ruo 90 °C. Dịka ihe a hụrụ anya dị mfe si kwuo, enweghị ike ịgbaze mgbagwoju ahụ kpamkpam na IL ọbụlagodi na a na-akpali ya ogologo oge na okpomọkụ nke 90 °C, mana ịgbaze mere mgbe ewebatara formic acid. Na 90 °C, a gbanwere 56% (TOF = 3424 h-1) n'ime nkeji iri mbụ, a rụkwara mgbanwe fọrọ nke nta ka ọ bụrụ ọnụọgụ (97%) mgbe awa atọ gasịrị (ntinye 1). Ibelata okpomọkụ ruo 80 °C na-ebelata mgbanwe ahụ site na ihe karịrị ọkara ruo 24% mgbe nkeji iri gasịrị (TOF = 1467 h-1, ntinye 2), na-ebelata ya ruo 18% na 18% na 70 °C na 60 °C, n'otu n'otu 6% (ntinye 3 na 4). N'ọnọdụ niile, achọpụtaghị oge mkpali ọ bụla, nke na-egosi na ihe na-akpali akpali nwere ike ịbụ ụdị mmeghachi omume ma ọ bụ na mgbanwe nke ụdị mmeghachi omume dị oke ngwa ngwa iji chọpụta site na iji data a.
Mgbe enyochachara ihe mbụ, e jiri Ru-POP clamp complexes Ru-POP Ru-1 na Ru-2 mee ihe n'otu ọnọdụ ahụ. Na 90°C, a hụrụ mgbanwe dị elu ozugbo. Ru-1 nwetara mgbanwe 74% n'ime nkeji iri mbụ nke nnwale ahụ (TOFmax = 4525 h-1, ntinye 5). Ru-2 gosipụtara obere ọrụ mana ọ na-agbanwe agbanwe, na-akwalite mgbanwe 60% n'ime nkeji 10 (TOFmax = 3669 h-1) na mgbanwe zuru oke n'ime nkeji 60 (>99%) (ntinye 9). Ọ dị mkpa ịmara na Ru-2 dị elu karịa metal precursor na Ru-1 na mgbanwe zuru oke. Ya mere, ebe precursor metal na Ru-1 nwere ụkpụrụ TOFoverall yiri ya mgbe mmecha mmeghachi omume gasịrị (330 h-1 na 333 h-1, n'otu n'otu), Ru-2 nwere TOFoverall nke 1009 h-1.
E mechara gbanwee okpomọkụ Ru-1 na Ru-2 nke mere ka okpomọkụ ahụ belata nwayọ nwayọ na mmụba 10 °C ruo opekata mpe 60 °C (Foto 3). Ọ bụrụ na na 90 °C, ihe mgbagwoju anya ahụ gosipụtara ọrụ ozugbo, ihe fọrọ nke nta ka ọ bụrụ mgbanwe zuru oke mere n'ime otu awa, mgbe ahụ na obere okpomọkụ ọrụ ahụ belatara nke ukwuu. Mgbanwe nke Py-1 bụ 14% na 23% mgbe nkeji 10 gasịrị na 80 °C na 70 °C, n'otu n'otu, mgbe nkeji 30 gachara, ọ mụbara ruo 79% na 73% (ntinye 6 na 7). Nnwale abụọ ahụ gosiri ọnụego mgbanwe nke ≥90% n'ime awa abụọ. A hụrụ omume yiri nke ahụ maka Ru-2 (ntinye 10 na 11). N'ụzọ na-adọrọ mmasị, Ru-1 dị ntakịrị ike na njedebe nke mmeghachi omume na 70 °C yana mkpokọta TOF nke 315 h-1 ma e jiri ya tụnyere 292 h-1 maka Ru-2 na 299 h-1 maka ihe mmalite ígwè.
Mbelata ọzọ na okpomọkụ ruo 60 °C dugara n'eziokwu na ahụghị mgbanwe ọ bụla n'ime nkeji iri atọ mbụ nke nnwale ahụ. Ru-1 anaghị arụ ọrụ nke ọma na okpomọkụ kachasị ala na mmalite nnwale ahụ ma mechaa mụbaa ọrụ, na-egosi mkpa nke oge mkpali n'oge a na-agbanwe Ru-1 precatalyst ka ọ bụrụ ụdị ihe na-arụsi ọrụ ike. Ọ bụ ezie na nke a ga-ekwe omume na okpomọkụ niile, nkeji iri na mmalite nnwale ahụ ezughị iji chọpụta oge mkpali na okpomọkụ dị elu. A hụrụ omume yiri nke ahụ maka Ru-2. Na 70 na 60 °C, a hụghị mgbanwe ọ bụla n'ime nkeji iri mbụ nke nnwale ahụ. Ọ dị mkpa ịmara na na nnwale abụọ ahụ, ahụghị mmepụta carbon monoxide n'ime oke nchọpụta nke ngwa anyị (<300 ppm), ebe H2 na CO2 bụ naanị ngwaahịa a hụrụ.
Ntụnyere nsonaazụ mwepu mmiri ọgwụ formic acid nke e nwetara na mbụ n'ime otu ọrụ a, nke na-anọchite anya ọnọdụ kachasị elu na iji mgbagwoju anya Ru-PNP, gosiri na mwepu Ru-POP ọhụrụ a rụpụtara nwere ọrụ yiri nke PNP ya 15. Ọ bụ ezie na mwepu PNP nwetara RPM nke 500-1260 h-1 na nnwale ogbe, mwepu POP ọhụrụ nwetara uru TOFovertal yiri nke 326 h-1, a hụkwara ụkpụrụ TOFmax nke Ru-1 na 1590 h-1. n'otu n'otu, bụ 1988 h-1 na 1590 h-1. Ru-2 bụ 1 na 80 °C, Ru-1 bụ 4525 h-1 na Ru-1 bụ 3669 h-1 na 90 °C, n'otu n'otu.
Nnyocha okpomọkụ nke formic acid dehydrogenation site na iji ihe mkpali Ru-1 na Ru-2. Ọnọdụ: 13 µmol catalyst, 0.5 ml (13.25 mmol) formic acid, 1.0 ml (5.35 mmol) BMIM OAc.
A na-eji NMR aghọta usoro mmeghachi omume. Ebe ọ bụ na enwere nnukwu ọdịiche dị na 2JH-P n'etiti hydride na phosphine ligands, isi ihe ọmụmụ a bụ na elu hydride. Maka Ru-1, a hụrụ ụdị dt nkịtị nke unit hydrogenation n'ime nkeji 60 mbụ nke dehydrogenation. Ọ bụ ezie na enwere nnukwu mgbanwe ala site na −16.29 ruo −13.35 ppm, njikọ ya na phosphine bụ 27.2 na 18.4 Hz, n'otu n'otu (Foto 5, Oke A). Nke a kwekọrọ na phosphines atọ niile ebe ligand hydrogen dị na nhazi cis ma na-atụ aro na nhazi ligand ahụ kwụsiri ike na IL maka ihe dị ka otu awa n'okpuru ọnọdụ mmeghachi omume kachasị mma. Mgbanwe siri ike nke ala ala nwere ike ịbụ n'ihi mwepụ nke ligands chlorinated na nhazi nke acetyl-formic acid complexes kwekọrọ, nhazi in situ nke d3-MeCN complex na tube NMR, ma ọ bụ nhazi nke N-heterocycles kwekọrọ. kọwara. Carbene (NHC) complex. N'oge mmeghachi omume dehydrogenation, ike nke mgbaàmà a nọgidere na-ebelata, na mgbe nkeji 180 gachara ahụghị mgbaàmà ahụ. Kama, achọpụtara akara ọhụrụ abụọ. Nke mbụ na-egosi ụkpụrụ dd doro anya na-eme na -6.4 ppm (elu B). Doublet ahụ nwere nnukwu njikọ nke ihe dị ka 130.4 Hz, na-egosi na otu n'ime nkeji phosphine agagharịla ma e jiri ya tụnyere hydrogen. Nke a nwere ike ịpụta na a na-ahazi POP clamp ka ọ bụrụ nhazi κ2-P,P. Ọdịdị nke mgbagwoju a n'oge catalysis nwere ike igosi na ụdị a na-eduga na ụzọ nkwụsị ka oge na-aga, na-emepụta sink catalyst. N'aka nke ọzọ, obere mgbanwe kemịkalụ na-egosi na ọ nwere ike ịbụ ụdị dihydrogenous15. Oke ọhụrụ nke abụọ dị na -17.5 ppm. Ọ bụ ezie na amaghị mpịachi ya, anyị kwenyere na ọ bụ triplet nwere obere njikọ nke 17.3 Hz, nke na-egosi na hydrogen ligand na-ejikọ naanị na phosphine ligand nke POP clamp, na-egosikwa mwepụta nke triphenylphosphine (elu C). Enwere ike iji ligand ọzọ dochie ya, dị ka otu acetyl ma ọ bụ NHC nke e guzobere na situ site na mmiri ionic. Nkewa nke PPh3 na-egosikwa site na singlet siri ike na -5.9 ppm. na 31P{1H} spectrum nke Ru-1 mgbe nkeji 180 gachara na 90 °C (lee ozi ndị ọzọ).
Mpaghara Hydride nke 1H NMR spectrum nke Ru-1 n'oge mwepụ nke formic acid. Ọnọdụ mmeghachi omume: 0.5 ml formic acid, 1.0 ml BMIM OAc, 13.0 µmol catalyst, 90 °C. E si na MeCN-d 3, 500 μl nke deuterated solvent were NMR, ihe dị ka 10 μl nke ngwakọta mmeghachi omume.
Iji gosikwa na ụdị ihe ndị na-arụ ọrụ n'ime sistemụ catalytic ahụ dị elu, e mere nyocha nke Ru-1 nke nwere mkpebi dị elu (HRMS) mgbe a gbanyere formic acid ruo nkeji iri na okpomọkụ 90 °C. Nke a na-egosi ọnụnọ nke ụdị ndị na-enweghị chlorine ligand precatalyst na ngwakọta mmeghachi omume. yana mgbagwoju anya NHC abụọ, nke egosiri na eserese nke 6. Enwere ike ịhụ ụdị HRMS kwekọrọ na eserese mgbakwunye 7.
Dabere na data ndị a, anyị na-atụ aro usoro mmeghachi omume intrasphere yiri nke Beller tụrụ aro, ebe N-methylated PNP clamps na-akwalite otu mmeghachi omume ahụ. Nnwale ndị ọzọ ewezuga mmiri ionic egosighi ihe ọ bụla, yabụ itinye aka kpọmkwem ya yiri ka ọ dị mkpa. Anyị na-eche na ịgbalite Ru-1 na Ru-2 na-eme site na dissociation chloride nke nwere ike isochi mgbakwunye NHC na dissociation triphenylphosphine (Scheme 1a). A hụla mmalite a na ụdị niile site na iji HRMS. IL-acetate bụ ntọala Bronsted siri ike karịa formic acid ma nwee ike iwepụ proton nke ikpeazụ35 nke ukwuu. Anyị na-eche na n'oge usoro ihe na-eme ka ihe dị ndụ pụta ìhè (Usoro 1b), a na-ahazi ụdị A na-ebu NHC ma ọ bụ PPh3 site na nhazi iji mepụta ụdị B. Nhazigharị nke mgbagwoju anya a na C na-eme ka mwepụta nke CO2 na mgbagwoju anya trans-dihydrogen D. Protonation nke acid ahụ na-esote n'ime mgbagwoju anya dihydro yana acetic acid e guzobere na mbụ iji mepụta mgbagwoju anya dihydro E yiri nzọụkwụ dị mkpa nke Beller tụrụ aro site na iji N-methylated PNP clamp homologues. Na mgbakwunye, e mepụtara analogue nke mgbagwoju anya EL = PPh3 na mbụ site na mmeghachi omume stoichiometric site na iji Ru-1 na ikuku hydrogen mgbe ewepụtara chloride na nnu sodium. Mwepụ nke hydrogen na nhazi nke formate na-enye A ma mezue okirikiri ahụ.
A na-atụ aro usoro maka mmeghachi omume intrasphere nke formic acid dehydrogenation site na iji usoro nhazi Ru-POP Ru-1.
A chịkọtala mgbagwoju anya ọhụrụ [RuHCl(iPr-dbfphos)(PPh3)]. E ji nyocha NMR, ATRIR, EA na X-ray nke kristal otu mee ihe mara mgbagwoju anya ahụ. Anyị na-akọkwa ngwa mbụ gara nke ọma nke mgbagwoju anya Ru-POP na mwepụ nke formic acid na CO2 na H2. Ọ bụ ezie na ihe mmalite ígwè ahụ nwetara ọrụ yiri nke ahụ (ruo 3424 h-1), mgbagwoju anya ahụ ruru ugboro ntụgharị kachasị elu nke ruru 4525 h-1 na 90 °C. Ọzọkwa, na 90 °C, mgbagwoju anya ọhụrụ [RuHCl(iPr-dbfphos)(PPh3)] nwetara oge zuru oke nke ịgba ọsọ (1009 h-1) iji mezue mwepụ nke formic acid, nke dị elu karịa nke ihe mmalite ígwè (330 h-1). na mgbagwoju anya akọpụtara na mbụ [RuHCl(xantphos)(PPh3)] (333 h-1). N'ọnọdụ ndị yiri ya, arụmọrụ nke catalytic yiri nke Ru-PNP clamp complex. Data HRMS na-egosi ọnụnọ nke carbene complex na ngwakọta mmeghachi omume, ọ bụ ezie na ọ dị obere. Ugbu a, anyị na-amụ banyere mmetụta catalytic nke carbene complexes.
A na-etinye data niile e nwetara ma ọ bụ nyochaa n'oge ọmụmụ ihe a n'isiokwu a ebipụtara [na faịlụ ozi ndị na-akwado ya].
Azarpour A., ​​​​Suhaimi S., Zahedi G. na Bahadori A. Nyocha nke adịghị ike nke isi mmalite ike mmeghari ohuru dị ka isi iyi na-ekwe nkwa nke ike n'ọdịnihu. Arab. J. Sayensị. injinia. 38, 317–328 (2013).
Moriarty P. na Honery D. Kedu ihe nwere ike ime ka ike mmeghari ohuru dị n'ụwa niile? mmelite. nkwado. Energy Rev 16, 244–252 (2012).
Rao, PC na Yoon, M. Sistemụ nwere ike ibufe hydrogen organic (Lohc): nyocha nke ọganihu ndị na-adịbeghị anya. Energy 13, 6040 (2020).
Niermann, M., Beckendorf, A., Kaltschmitt, M. na Bohnhoff, K. Ndị na-ebu hydrogen organic mmiri mmiri (LOHC) – nyocha dabere na ihe onwunwe kemịkalụ na akụ na ụba. mba ụwa. J. Ike hydrogen. 44, 6631–6654 (2019).
Teichmann, D., Arlt, W., Wasserscheid, P. na Freimann, R. Isi mmalite ike n'ọdịnihu dabere na mmiri mmiri hydrogen organic carriers (LOHC). Gburugburu ike. sayensị. 4, 2767–2773 (2011).
Niermann, M., Timmerberg, S., Drunert, S. na Kaltschmitt, M. Ndị na-ebu hydrogen organic mmiri mmiri na ihe ndị ọzọ maka mbupu mba ụwa nke hydrogen mmeghari ohuru. mmelite. nkwado. Energy Ed. 135, 110171 (2021).
Rong Y. na ndị otu ya. Nyocha teknụzụ na akụ na ụba mba ụwa nke nchekwa na mbufe hydrogen site na ụlọ ọrụ mmepụta hydrogen gaa na ọdụ ọdụ hydrogenation. J. Ike hydrogen. 1–12 https://doi.org/10.1016/j.ijhydene.2023.01.187 (2023).
Guo, J. et al. Formic acid dị ka ụzọ nchekwa hydrogen nwere ike isi dị n'ime ụgbọ mmiri: mmepe nke ihe na-eme ka ihe na-akpali akpali metal dị mma maka mmeghachi omume dehydrogenation. Seuss Chemistry Chemistry. 14, 2655–2681 (2021).
Muller, K., Brooks, K., na Autry, T. Nchekwa hydrogen na formic acid: ntụnyere nke nhọrọ usoro. Mmanụ ike. 31, 12603–12611 (2017).
Wang, Z., Lu, SM, Li, J., Wang, J. na Li, Q. Iridium complex nwere N,N'-diimine ligand nwere ọrụ dehydrogenation nke formic acid dị elu na mmiri. Kemịkal. – EURO. J. 21, 12592–12595 (2015).
Hong D. na ndị ọzọ. Mmetụta mmekorita nke heterobinuclear IrIII-MII complexes na mwepụta catalytic nke H2 n'oge dehydrogenation nke formic acid n'ime mmiri. Ihe na-adịghị n'ime mmiri. Chemical. 59, 11976–11985 (2020).
Fink K., Laurenci GA na ihe na-akpali akpali dị oke ọnụ ahịa maka mwepu mmiri nke formic acid nke rhodium na-eme ka ọ dị ọcha n'ime mmiri. EURO. J.Inorg. Chemical. 2381–2387 (2019).
Seraj, JJA, na ndị ọzọ. Ihe na-akpali akpali dị irè maka iwepụ mmiri mmiri nke aki oyibo ọcha. Nat. na-ekwurịta okwu. 7, 11308 (2016).
Piccirelli L. na ndị ọzọ. Ngụkọta ọrụ nke hydrogenation-dehydrogenation CO2 site na iji sistemụ mmiri mmiri Ru-PNP/ionic. J. Am. Bitch. 145, 5655–5663 (2023).
Belinsky EA na ndị ọzọ. Mwepụ mmiri nke formic acid site na iji Lewis acid site na iji ihe na-akpalite iron na nkwado Pinzer. J. Am. Bitch. 136, 10234–10237 (2014).
Henriks V., Juranov I., Autissier N. na Laurenci G. Mwepụ mmiri nke formic acid na ihe ndị na-akpali Ru-TPPTS: mmepụta CO na-achọghị na mwepụ ya nke ọma site na iji ihe na-akpali PROX. 7, 348 (2017).
Filonenko GA wdg. Nha hydrogen nke carbon dioxide dị irè ma dị mfe ịgbanwe agbanwe na-eme ka ọ bụrụ ihe a na-agbanwe agbanwe site na iji ruthenium catalyst PNP-Pinzer. Chemistry Cat. 6, 1526–1530 (2014).
Hull, J. et al. Nchekwa hydrogen a na-agbanwe agbanwe site na iji carbon dioxide na proton-switched iridium catalysts na mmiri mmiri na okpomọkụ na nrụgide dị ala. Nat. Chemical. 4, 383–388 (2012).
Wei, D. et al. A na-eji Mn-Pincer complex eme ihe maka mgbanwe hydrogenation nke carbon dioxide gaa na formic acid n'ihu lysine. Nat. vitality. 7, 438–447 (2022).
Piccirilli L., Pinheiro DL na Nielsen M. Pincer Ọganihu ndị a na-eme n'oge na-adịbeghị anya na ihe na-akpali mgbanwe ígwè maka mmepe na-adigide. ihe na-akpali akpali. 10, 773 (2020).
Wei, D., Junge, H. na Beller, M. Sistemụ amino acid maka ijide carbon dioxide na ojiji catalytic maka mmepụta formate. Kemịkalụ. sayensị. 12, 6020–6024 (2021).
Subramanian M. et al. Ruthenium na-agbanwe hydrogenation, deuteration na methylation nke ihe ndị na-arụ ọrụ na methanol n'ozuzu na nke nhọrọ. J. Cutler. 425, 386–405 (2023).
Ni Z., Padilla R., Pramanik R., Jorgensen MSB na Nielsen M. Njikọ ethanol na-enweghị isi na nke na-anaghị anabata site na iji PNP complexes. Ogologo Dalton. 52, 8193–8197 (2023).
Fu, S., Shao, Z., Wang, Y., na Liu, Q. Mmelite ethanol nke Manganese mere ka ọ bụrụ 1-butanol. J. Am. Bitch. 139, 11941–11948 (2017).