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Formic acid ji nibii ni hi jogbaŋŋ ni akɛtoɔ nu ni ji hydrogen lɛ he be kakadaŋŋ lɛ ateŋ ekome. Yɛ biɛ lɛ, wɔkɛ ruthenium klamp he nibii heei ni yɔɔ srɔtoi ni yɔɔ fɔmla [RuHCl(POP)(PPh3)] ni akɛ xanthos-type tridentate POP klamp ligands ni yɔɔ jarayelihe loo ni afee lɛ mlɛo lɛ tsuɔ nii lɛ haa. Wɔkɛ nɛkɛ nibii nɛɛ tsu nii ni wɔkɛjie formic acid lɛ mli nu lɛ koni wɔkɛfee CO2 kɛ H2 yɛ shihilɛi ni mli ejɔ ni sɛɛkuu bɛ mli lɛ amli kɛtsɔ ionic nu ni ji BMIM OAc (1-butyl-3-methylimidazolium acetate) lɛ nɔ akɛ nɔ ni haa nu lɛ mli tseɔ. Kɛjɛ sɛɛkuu ni fe fɛɛ lɛ he susumɔ mli lɛ, nɔ ni tsuɔ nii jogbaŋŋ fe fɛɛ ji [RuHCl(xantphos)(PPh3)]Ru-1 complex ni ale yɛ woji amli lɛ, ni yɔɔ sɛɛkuu ni fe fɛɛ ni ji 4525 h-1 yɛ 90 °C kɛha minitii 10. Nibii ni tee nɔ yɛ sɛɛ mli lɛ ayibɔ ji 74%, ni agbe tsakemɔ lɛ naa yɛ ŋmɛlɛtswai 3 mli (>98%). Yɛ gbɛ kroko nɔ lɛ, nɔ ni haa mɔ tsui nyɔɔ emli ni hi fe fɛɛ lɛ, wolo [RuHCl(iPr-dbfphos)(PPh3)]Ru-2 complex lɛ, woɔ tsakemɔ ni yeɔ emuu lɛ he hewalɛ yɛ ŋmɛlɛtswaa kome mli, ni nɔ ni jɛɔ mli baa ji 1009 h-1. Kɛfata he lɛ, ana nibii ni haa mɔ tsui nyɔɔ emli lɛ hu yɛ hulutsoo be ni shɛɔ 60 °C mli. Yɛ gas fã lɛ mli lɛ, CO2 kɛ H2 pɛ ji nɔ ni ana; Anaaa CO. Nibii ni akwɛɔ mli jogbaŋŋ lɛ tsɔɔ akɛ N-heterocyclic carbene complexes lɛ yɛ nɔ ni akɛfutuɔ nii lɛ mli.
Hewalɛ ni anyɛɔ atsakeɔ lɛ jarayeli mli gbɛfaŋnɔ ni yaa hiɛ kɛ etsakemɔ lɛ eha nibii ni ataoɔ yɛ nitsumɔhei ni akɛtoɔ hewalɛ he ŋaalee yɛ hewalɛ, la, nitsumɔhei kɛ gbɛfaa mli lɛ eba1,2. Abuɔ hydrogen akɛ eji hewalɛ ni fa babaoo fe fɛɛ lɛ ateŋ ekome3, ni nu mli nibii ni hiɛɔ hydrogen (LOHCs) ebatsɔ niiamlitaomɔ he nɔ nyɛsɛɛ nɛɛ, ni ekɛ shiwoo haa akɛ akɛ hydrogen baato yɛ gbɛ ni yɔɔ mlɛo nɔ ni naagbai ni kɛ pressurization loo cryogenic tɛknɔlɔji baa lɛ bɛ mli4. ,5,6. Yɛ amɛ gbɔmɔtsoŋ nibii ahewɔ lɛ, abaanyɛ akɛ gbɛfaa he nibii ni yɔɔ momo kɛha pɛtrol kɛ nu mli tsofai krokomɛi lɛ babaoo atsu nii kɛya LOHC7,8. Formic acid (FA) lɛ mli nibii lɛ haa efeɔ nɔ ni hi jogbaŋŋ kɛha hydrogen ni akɛtoɔ ni hydrogen tsiimɔ ni yɔɔ mli lɛ ji 4.4%9,10. Shi kɛlɛ, gbɛjianɔtoo ni akala kɛha formic acid dehydrogenation lɛ biɔ ni akɛ nibii ni wala yɔɔ mli ni sɛɛ tsɛɔ, nu loo formic acid krɔŋŋ atsu nii, 11,12,13,14 ni baanyɛ aha ehe ahia ni akɛ nibii ni haa hulu tsoɔ mligbalamɔ gbɛi tamɔ la ni hoɔ, ni baanyɛ ekɛ naagbai aba mɛi ni yeɔ nii lɛ anɔ. nitsumɔi, jatsu kroko ni fata he. Abaanyɛ aye naagba nɛɛ nɔ kɛtsɔ nibii ni haa nu mli la ni mli edɔ waaa, tamɔ ionic nu ni akɛtsuɔ nii lɛ nɔ. Be ko ni eho lɛ, wɔ nitsumɔ kuu lɛ tsɔɔ akɛ ionic nu ni ji butylmethylimidazolium acetate (BMIM OAc) lɛ ji nɔ ni sa jogbaŋŋ yɛ nɛkɛ nifeemɔ nɛɛ mli kɛtsɔ jarayeli nibii ni akɛsaa nibii ni yɔɔ mlɛo ni ji Ru-PNP Ru-MACHO type 15 lɛ nɔ. TON ni fe 18,000,000 yɛ 95°C mli. Eyɛ mli akɛ gbɛjianɔtoi komɛi ená TON ni nɔ kwɔ tsutsu moŋ, shi mɛi babaoo kɛ amɛhe efɔ nibii ni wala yɔɔ mli ni sɛɛ tsɛɔ (tamɔ THF loo DMF) loo nibii ni akɛfataa he ni akɛtsuɔ nii (tamɔ bases) lɛ anɔ. Nɔ ni tamɔɔɔ enɛ lɛ, wɔ nitsumɔ lɛ kɛ ionic nu ni sɛɛ efooo (ILs) tsuɔ nii diɛŋtsɛ ni akɛ nɔ ko fataaa he.
Hazari kɛ Bernskoetter bɔ amaniɛ akɛ formic acid (FA) lɛ mli nu ni ajieɔ kɛjɛɔ mli lɛ mli yɛ 80 °C kɛtsɔ Fe-PNP ni haa nu lɛ mli tseɔ lɛ nɔ yɛ dioxane kɛ LiBF4 hiɛ, ni enine shɛ yibɔ ni yɔɔ naakpɛɛ (TON) ni miihe ashɛ 1,000,00016 nɔ. Laurenci kɛ Ru(II)- ni ji nɔ ko ni haa mɔ tsui nyɔɔ emli ni ji TPPPTS tsu nii yɛ FA ni yaa nɔ ejieɔ nu kɛjɛɔ mli lɛ mli. Gbɛ nɛɛ ha FA dehydrogenation ni miihe ashɛ naagbee kɛ CO fioo ko pɛ ni ana yɛ 80 °C17. Kɛha nɛkɛ nitsumɔ nɛɛ hiɛyaa lɛ, Pidko tsɔɔ bɔ ni FA lɛ mli nu ni ajieɔ kɛjɛɔ mli lɛ baanyɛ aku sɛɛ aba kɛtsɔ Ru-PNP klamp ni haa mɔ tsui nyɔɔ emli lɛ nɔ yɛ DMF/DBU kɛ DMF/NHex3 futumɔi amli, ni enine shɛ TON jara ni ji 310,000 kɛyashi 706,500 nɔ yɛ 90 °C18. Hull, Himeda kɛ Fujita kase nuklea Ir nibii ni haa mɔ tsui nyɔɔ emli ni akɛ KHCO3 kɛ H2SO4 shaa afɔle yɛ mli lɛ he nii, ni amɛtsakeɔ CO2 ni akɛwoɔ nu mli kɛ FA ni akɛwoɔ nu mli lɛ. Amɛ gbɛjianɔtoo lɛ nine shɛ TONs ni fe 3,500,000 kɛ 308,000 nɔ kɛha nu ni ajieɔ kɛjɛɔ mli yɛ 30°C, CO2/H2 (1:1), 1 bar nɔnyɛɛ kɛ kɛha nu ni ajieɔ kɛjɛɔ mli yɛ 60 kɛ 90°C19 teŋ. Sponholz, Junge kɛ Beller fee Mn-PNP ni yɔɔ srɔtoi kɛha CO2 ni anyɛɔ atsakeɔ kɛ FA ni ajieɔ kɛjɛɔ mli yɛ 90 °C20.
Yɛ biɛ lɛ, wɔkɛ IL gbɛ ko tsu nii, shi yɛ Ru-PNPs ni wɔkɛbaatsu nii lɛ najiaŋ lɛ, wɔtao Ru-POP nibii ni haa mɔ tsui nyɔɔ emli lɛ ni akɛtsuɔ nii lɛ mli, ni yɛ wɔ nilee naa lɛ, ajieee lɛ kpo yɛ enɛ he dã.
Yɛ amɛ dade-ligand coupling (MLC) ni hi jogbaŋŋ lɛ hewɔ lɛ, amino-PNP klamp ni damɔ Noyori-henɔ susumɔi anɔ kɛ amino nitsumɔ kui ni ji enyɔ 21 (tamɔ Ru-MACHO-BH) lɛ miihe gbɛi waa yɛ molecule bibii komɛi anitsumɔi amli. Nɔkwɛmɔnii ni ale waa ji CO22, alkenes kɛ carbonyls mli nu ni akɛwoɔ mli, nu ni akɛwoɔ mli ni akɛyaa he kroko23 kɛ dãa mli nu ni mli tseee24. Abɔ amaniɛ akɛ N-methylation ni ji PNP clamp ligands lɛ baanyɛ akpa tsɔne ni haa mɔ tsui nyɔɔ emli lɛ nitsumɔ lɛ kwraa25, ni abaanyɛ atsɔɔ mli kɛtsɔ anɔkwale ni eji akɛ amines tsuɔ nii akɛ proton jɛɛhei, ni ji taomɔ nii ni he hiaa waa yɛ tsɔne ni haa mɔ tsui nyɔɔ emli lɛ sɛɛkuu lɛ mli kɛtsɔ MLC nɔ lɛ nɔ. Shi kɛlɛ, nɔ ni tamɔɔɔ nakai yɛ formic acid mli nu ni ajieɔ kɛjɛɔ mli lɛ mli lɛ ji nɔ ni Beller na nyɛsɛɛ nɛɛ, he ni N-methylated Ru-PNP complexes lɛ jie formic acid mli nu ni ajieɔ kɛjɛɔ mli lɛ ni hi jogbaŋŋ fe amɛhefatalɔi ni bɛ methylated lɛ26. Akɛni tsutsu nɔ ni yɔɔ srɔto lɛ nyɛɛɛ ekɛ ehe awo MLC mli kɛtsɔ amino kuu lɛ nɔ hewɔ lɛ, enɛ tsɔɔ akɛ MLC, kɛ no hewɔ lɛ amino kuu lɛ, baanyɛ atsu gbɛfaŋnɔ ko ni he ehiaaa tsɔ yɛ (de)hydrogenation tsakemɔi komɛi amli fe bɔ ni asusuɔ tsutsu lɛ.
Kɛ akɛto POP klampii ahe lɛ, akaseko ruthenium ni yɔɔ POP klampii amli lɛ he nii jogbaŋŋ yɛ nɛkɛ he nɛɛ. Akɛ POP ligands tsuɔ nii titri kɛha hydroformylation, he ni amɛtsuɔ nii akɛ chelating ligands moŋ fe su ni ji bidentate bite angle ni miihe ashɛ 120° kɛha ligands ni akɛfiɔ he, ni akɛtsu nii koni akɛhala nibii ni yɔɔ linear kɛ nibii ni yɔɔ niji amli lɛ jogbaŋŋ27,28,29. Kɛjɛ nakai beaŋ kɛbaa nɛɛ, akɛ Ru-POP nibii ni yɔɔ srɔtoi lɛ tsuuu nii yɛ hydrogenation catalysis mli, shi abɔ amɛ nitsumɔ he nɔkwɛmɔnii yɛ hydrogenation ni akɛyaa he kroko lɛ he amaniɛ momo30. Yɛ biɛ lɛ, wɔtsɔɔ akɛ Ru-POP complex lɛ ji nɔ ko ni tsuɔ nii jogbaŋŋ ni haa formic acid lɛ mli nu lɛ shwieɔ shi, ni emaa Beller nibii ni ena akɛ amino unit ni yɔɔ klassik Ru-PNP amine catalyst lɛ mli lɛ he ehiaaa tsɔ yɛ nɛkɛ nifeemɔ nɛɛ mli lɛ nɔ mi.
Wɔ nikasemɔ lɛ jeɔ shishi kɛ tsɔnei enyɔ ni haa mɔ tsui nyɔɔ emli ni akɛ tsɔne ni ji [RuHCl(POP)(PPh3)] (Fig. 1a) lɛ feɔ ekome. Akɛ nibii ni haa mɔ tsui nyɔɔ emli ni akaseɔ yɛ nitsumɔ nɛɛ mli lɛ tsu nii kɛfee nibii ni haa mɔ tsui nyɔɔ emli ni Whittlesey32 fee lɛ, ni akɛ [a•Rene3uct3uh) lɛ tsu nii. nɔ ko ni tsɔɔ hiɛ. Futumɔ dade ni tsɔɔ hiɛ kɛ POP klamp ligand yɛ THF mli yɛ shihilɛi ni nu bɛ mli kɛ anaerobic shihilɛi amli. Nɔ ni fata he ji su tsakemɔ ko ni sa kadimɔ waa kɛjɛ purple ni mli edɔ kɛtee yellow mli ni ekɛ nɔ ko ni he tse ha yɛ ŋmɛlɛtswai 4 ni akɛwoɔ mli loo ŋmɛlɛtswai 72 ni akɛwoɔ mli yɛ 40°C sɛɛ. Beni ajie THF lɛ yɛ he ko ni nɔ ko bɛ mli ni akɛ hexane loo diethyl ether tsu he shii enyɔ sɛɛ lɛ, ajie triphenylphosphine lɛ koni eha nɔ ni anáa lɛ afee powda ni yɔɔ ŋmɔlɔŋmɔlɔ ni yibiiwoo babaoo yɔɔ mli.
Ru-1 kɛ Ru-2 nibii ni yɔɔ srɔtoi lɛ ahe nitsumɔ. a) Gbɛ ni atsɔɔ nɔ afeɔ nibii ni yɔɔ hwanyaŋŋ lɛ ekome. b) Gbɛjianɔtoo ni yɔɔ tsɔne ni afee lɛ ekome lɛ mli.
Ale Ru-1 momo kɛjɛ woji amli32, ni sui krokomɛi ni atsɔɔ mli lɛ kɔɔ Ru-2 he. 1H NMR spectrum ni ji Ru-2 lɛ ma cis gbɛjianɔtoo ni yɔɔ phosphine atom lɛ mli lɛ nɔ mi yɛ ligand ni yɔɔ hydride enyɔ lɛ mli lɛ mli. 2a) tsɔɔ 2JP-H coupling constants ni ji 28.6 kɛ 22.0 Hz, ni yɔɔ amaniɛbɔi ni eho lɛ amli32. Yɛ hydrogen ni ajie kɛjɛ mli lɛ mli lɛ, ana 2JP-P ni akɛfee ekome ni miihe ashɛ 27.6 Hz, ni maa nɔ mi akɛ klamp ligand phosphines kɛ PPh3 fɛɛ ji cis-cis. Kɛfata he lɛ, ATR-IR tsɔɔ ruthenium-haidrojin ni mli wa yɛ 2054 cm-1. Kɛha shishitoo mla mlitsɔɔmɔ kroko lɛ, Ru-2 tsɔne lɛ fee kristalo kɛtsɔ lasu ni gbɛɔ eshwaa yɛ tsu mli latsaa mli lɛ nɔ kɛ su ni sa kɛha X-ray nikasemɔi (Mfoniri 3, Supplementary Table 1). Efeɔ kristalo yɛ triclinic gbɛjianɔtoo ni ji ŋwɛi kuu P-1 lɛ mli kɛ cocrystalline benzene unit kome yɛ unit cell kome mli. Etsɔɔ P-Ru-P ŋwɛi ŋta ni da ni ji 153.94°, ni da fe 130° ŋwɛi ŋta ni ji bidentate DBFphos34 lɛ. Yɛ 2.401 kɛ 2.382 Å lɛ, Ru-PPOP tsakpaa lɛ sɛɛ tsɛɔ kwraa fe Ru kɛ PPh3 tsakpaa lɛ sɛɛ tsɛɔ ni ji 2.232 Å, ni baanyɛ afee nɔ ni jɛ DBFphos sɛɛgbɛ snack angle ni da ni e-central 5-ring lɛ kɛbaa lɛ mli ba. Dade teŋgbɛ jiomɛtri lɛ ji oktahedral ni O-Ru-PPh3 koŋ ji 179.5°. H-Ru-Cl tsakpaa lɛ jeee nɔ ni yɔɔ ŋwɛigbɛ kwraa, ni eyɛ ŋwɛigbɛ ni miihe ashɛ 175° kɛjɛ triphenylphosphine ligand lɛ he. Atomik sɛɛjɛkɛmɔ kɛ tsakpaa lɛ kɛlɛ yɛ Okadi 1 mli.
NMR henɔ ni ji Ru-2. a) Hydride kpokpaa ni yɔɔ 1H NMR ŋwɛi ŋta ni tsɔɔ Ru-H dt okadi lɛ. b) 31 P{ 1 H} NMR ŋwɛi ŋta ni tsɔɔ okadii ni jɛ trifenilfosfin (bluu) kɛ POP ligand (eŋɔli) mli.
Ru-2 he gbɛjianɔtoo. Ajieɔ hulutsoo ellipsoids kpo kɛ 70% ni baanyɛ aba. Kɛha mlitsɔɔmɔ lɛ, ajie benzene kɛ hydrogen atom ni yɔɔ carbon lɛ nɔ lɛ kɛjɛ mli.
Kɛha nyɛmɔ ni nibii ni yɔɔ srɔtoi lɛ yɔɔ ni amɛkɛjieɔ formic acid lɛ mli nu lɛ he susumɔ lɛ, ahala shihilɛi ni haa mɔ tsui nyɔɔ emli ni PNP-clamp nibii ni yɔɔ srɔtoi lɛ (tamɔ, Ru-MACHO-BH) lɛ tsuɔ nii waa yɛ shishi. 1000 ppm, 13 μmol) ruthenium complex Ru-1 loo Ru-2 kɛ 1.0 ml (5.35 mmol) ionic nu (IL) BMIM OAc (okpɔlɔ-2) Mfoniri 4 lɛ);
Bɔni afee ni anyɛ ana shishitoo mla lɛ, akɛ nɔ ni tsɔɔ hiɛ ni akɛwoɔ mli lɛ [RuHCl(PPh3)·toluene tsu nii klɛŋklɛŋ. Afeɔ nɔ ni afeɔ lɛ yɛ hulutsoo be ni jeɔ shishi kɛjɛɔ 60 kɛyashi 90 °C mli. Taakɛ nibii ni anaa yɛ hiŋmɛii amli ni yɔɔ mlɛo lɛ tsɔɔ lɛ, anyɛɛɛ ajie nɔ ni mli wa lɛ kwraa yɛ IL mli kɛji akɛ atswa lɛ be kakadaŋŋ yɛ hulutsoo be ni ji 90°C mli po, shi sɛɛkuu lɛ ba yɛ be mli ni akɛ formic acid lɛ wo mli lɛ sɛɛ. Yɛ 90°C lɛ, aná tsakemɔ ni ji 56% (TOF = 3424 h-1) yɛ klɛŋklɛŋ minitii 10 lɛ mli, ni aná tsakemɔ ni miihe ashɛ yibɔ (97%) yɛ ŋmɛlɛtswai etɛ sɛɛ (botemɔ 1). Kɛji akɛ ajie hulutsoo lɛ shi kɛyashɛ 80 °C lɛ, ehaa tsakemɔ lɛ baa shi fe fã kɛyaa 24% yɛ minitii 10 sɛɛ (TOF = 1467 h-1, shishijee 2), ni ebaa shi ekoŋŋ kɛyashɛɔ 18% kɛ 18% yɛ 70 °C kɛ 60 °C, yɛ 6% (botemɔ 3 kɛ 4 mli). Yɛ shihilɛi fɛɛ amli lɛ, anaaa be ko ni akɛwoɔ mli, ni tsɔɔ akɛ nɔ ni haa nɔ ko yaa hiɛ lɛ baanyɛ afee nɔ ko ni tsuɔ nii loo akɛ nɔ ko ni tsuɔ nii lɛ tsakemɔ lɛ yaa oya tsɔ ni anyɛɛɛ ana kɛtsɔ saji nɛɛ anɔ.
Yɛ sɛɛ mli lɛ, akɛ Ru-POP klamp complexes Ru-1 kɛ Ru-2 tsu nii yɛ shihilɛ kome too lɛ nɔŋŋ mli. Yɛ 90°C lɛ, ana tsakemɔ ni nɔ kwɔ amrɔ nɔŋŋ. Ru-1 nine shɛ 74% tsakemɔ nɔ yɛ klɛŋklɛŋ minitii 10 ni akɛka lɛ mli (TOFmax = 4525 h-1, shishijee 5). Ru-2 tsɔɔ nitsumɔ ni baa shi fioo shi eyaa nɔ daa, ni ewoɔ 60% tsakemɔ he hewalɛ yɛ minitii 10 mli (TOFmax = 3669 h-1) kɛ tsakemɔ ni yeɔ emuu yɛ minitii 60 mli (>99%) (botemɔ 9). Ehe miihia ni akadi akɛ Ru-2 lɛ nɔ kwɔ kwraa fe dade ni tsɔ hiɛ lɛ kɛ Ru-1 yɛ tsakemɔ ni yeɔ emuu mli. No hewɔ lɛ, yɛ be mli ni dade ni tsɔɔ hiɛ lɛ kɛ Ru-1 yɛ TOFoverall sɛɛnamɔi ni tamɔ amɛhe yɛ nifeemɔ naagbee (330 h-1 kɛ 333 h-1, yɛ gbɛ kome nɔ lɛ), Ru-2 yɛ TOFoverall ni ji 1009 h-1.
No sɛɛ lɛ, akɛ Ru-1 kɛ Ru-2 wo hulutsoo tsakemɔ ko mli ni hulutsoo lɛ ba shi fiofio yɛ 10 °C mli kɛyashɛ 60 °C (Mfoniri 3). Kɛji akɛ yɛ 90°C lɛ, nɔ ni yɔɔ srɔtoi lɛ jie nitsumɔ kpo amrɔ nɔŋŋ lɛ, nɔ ni miihe ashɛ tsakemɔ ni yeɔ emuu lɛ ba yɛ ŋmɛlɛtswaa kome mli, no lɛ yɛ hulutsoo be ni baa shi lɛ mli lɛ, nitsumɔ lɛ baa shi kwraa. Py-1 tsakemɔ lɛ ji 14% kɛ 23% yɛ minitii 10 sɛɛ yɛ 80°C kɛ 70°C, yɛ minitii 30 sɛɛ lɛ, etee hiɛ kɛyashɛ 79% kɛ 73% (botemɔ 6 kɛ 7). Shikpamɔi enyɔ lɛ fɛɛ tsɔɔ tsakemɔ ni ji ≥90% yɛ ŋmɛlɛtswai enyɔ mli. Ana subaŋ ni tamɔ nakai nɔŋŋ yɛ Ru-2 (niŋmaai 10 kɛ 11) lɛ hu he. Nɔ ni yɔɔ miishɛɛ ji akɛ, Ru-1 ye nɔ fioo yɛ nifeemɔ lɛ naagbee yɛ 70 °C kɛ TOF fɛɛ ni ji 315 h-1 kɛ akɛto 292 h-1 kɛha Ru-2 kɛ 299 h-1 kɛha dade ni tsɔɔ hiɛ lɛ he.
Nɔ ni tee nɔ yɛ hulutsoo be lɛ mli ekoŋŋ kɛyashɛ 60 °C lɛ ha anaaa tsakemɔ ko yɛ klɛŋklɛŋ minitii 30 ni akɛka nii lɛ mli. Ru-1 lɛ tsuuu nii kwraa yɛ hulutsoo be ni baa shi fe fɛɛ lɛ mli yɛ kaa lɛ shishijee mli ni no sɛɛ lɛ, nitsumɔ lɛ tee hiɛ, ni tsɔɔ akɛ ehe miihia ni atsu nii yɛ be mli ni Ru-1 precatalyst lɛ tsakeɔ efeɔ catalytically active species lɛ. Eyɛ mli akɛ enɛ baanyɛ aba mli yɛ hulutsoo be fɛɛ mli moŋ, shi minitii 10 ni akɛje kaa lɛ shishi lɛ faaa bɔ ni sa ni akɛyooɔ be ko ni akɛtsuɔ nii yɛ hulutsoo be ni nɔ kwɔ mli. Ana subaŋ ni tamɔ nakai nɔŋŋ yɛ Ru-2 he. Yɛ 70 kɛ 60 °C lɛ, anaaa tsakemɔ ko yɛ klɛŋklɛŋ minitii 10 ni akɛkaa lɛ mli. Ehe miihia ni wɔkadi akɛ yɛ kaai enyɔ lɛ fɛɛ mli lɛ, anaaa carbon monoxide feemɔ yɛ wɔ dɛŋdade lɛ mli nibii ni ana lɛ mli (<300 ppm), ni H2 kɛ CO2 pɛ ji nibii ni ana.
Nibii ni jɛ mli ba ni akɛtoɔ formic acid dehydrogenation ni ana tsutsu yɛ nitsumɔ kuu nɛɛ mli lɛ he, ni damɔ shi kɛha shihilɛ ni yɔɔ ŋmɛnɛ lɛ kɛ Ru-PNP klamp complexes ni akɛtsuɔ nii lɛ, tsɔɔ akɛ Ru-POP klamp ni afee ehee lɛ yɛ nitsumɔ ni tamɔ e-PNP counterpart 15. POP klamp hee lɛ ná TOFovertal sɛɛnamɔ ni tamɔ nakai nɔŋŋ ni ji 326 h-1, ni ana TOFmax sɛɛnamɔi ni ji Ru-1 kɛ 1590 h-1. yɛ gbɛ kome nɔ lɛ, ji 1988 h-1 kɛ 1590 h-1. Ru-2 ji 1 yɛ 80 °C mli, Ru-1 ji 4525 h-1 kɛ Ru-1 ji 3669 h-1 yɛ 90 °C mli, yɛ gbɛ kome nɔ.
Akɛ Ru-1 kɛ Ru-2 nibii ni haa nu mli tseɔ lɛ tsuɔ nii kɛkwɛɔ bɔ ni formic acid lɛ mli dɔlɛ yɔɔ ha lɛ mli. Shihilɛi: 13 μmol ni haa mɔ tsui nyɔɔ emli, 0.5 ml (13.25 mmol) ni ji fɔmik asid, 1.0 ml (5.35 mmol) ni ji BMIM OAc.
Akɛ NMR tsuɔ nii koni anu bɔ ni nibii tsuɔ nii amɛhaa lɛ shishi. Akɛni srɔtofeemɔ ko ni sa kadimɔ waa yɛ 2JH-P mli yɛ hydride kɛ phosphine ligands lɛ ateŋ hewɔ lɛ, nɔ ni nikasemɔ nɛɛ tsɔɔ ji hydride yitso lɛ nɔ. Kɛha Ru-1 lɛ, ana dt nɔkwɛmɔnɔ ko ni kɔɔ hydrogenation unit lɛ he yɛ klɛŋklɛŋ minitii 60 ni akɛjieɔ hydrogenation lɛ mli. Eyɛ mli akɛ shikpɔŋ lɛ nɔ tsakemɔ ko ni he hiaa waa yɛ kɛjɛ −16.29 kɛyashi −13.35 ppm moŋ, shi ekɛ phosphine ni kɛ amɛhe kpaa gbee lɛ ji 27.2 kɛ 18.4 Hz, yɛ gbɛ kome nɔ (Mfoniri 5, Peak A). Enɛ kɛ phosphines etɛ fɛɛ ni hydrogen ligand lɛ yɔɔ cis gbɛjianɔtoo lɛ mli lɛ kpãa gbee ni etsɔɔ akɛ ligand gbɛjianɔtoo lɛ damɔ shi shiŋŋ yɛ IL lɛ mli aaafee ŋmɛlɛtswaa kome yɛ shihilɛ ni hi jogbaŋŋ shishi. Shishijee ni mli wa lɛ baanyɛ ajɛ chlorinated ligands ni ajieɔ kɛjɛɔ mli kɛ acetyl-formic acid ni kɛ lɛ kpãa gbee lɛ feemɔ, d3-MeCN ni yɔɔ NMR tsɔne lɛ mli lɛ feemɔ yɛ he ni eyɔɔ lɛ, loo N-heterocycles ni kɛ lɛ kpãa gbee lɛ feemɔ. tsɔɔ mli. Kaben (NHC) nibii ni yɔɔ srɔtoi. Yɛ dehydrogenation reaction lɛ mli lɛ, nɛkɛ okadi nɛɛ mli hewalɛ tee nɔ eba shi, ni yɛ minitii 180 sɛɛ lɛ, anaaa okadi lɛ dɔŋŋ. Mohu ɔ, a na okadi ehehi enyɔ. Klɛŋklɛŋ nɔ lɛ tsɔɔ dd he mfoniri ni yɔɔ faŋŋ ni baa yɛ -6.4 ppm (peak B). Doublet lɛ yɛ coupling constant agbo ko ni ji aaafee 130.4 Hz, ni tsɔɔ akɛ phosphine kui lɛ ateŋ ekome eshi kɛjɛ hydrogen lɛ he. Enɛ baanyɛ atsɔɔ akɛ ato POP klamp lɛ he gbɛjianɔ ekoŋŋ koni efee κ2-P,P gbɛjianɔtoo. Nɛkɛ nɔ ni yɔɔ hwanyaŋŋ nɛɛ kpojiemɔ yɛ sɛɛ mli yɛ sɛɛ mli lɛ baanyɛ atsɔɔ akɛ nɛkɛ nɔ̃ nɛɛ kɛ gbɛi ni haa mɔ tsui nyɔɔ emli baa yɛ be mli ni be hoɔ lɛ, ni ehaa nɔ ni haa mɔ tsui nyɔɔ emli lɛ feɔ sinki. Yɛ gbɛ kroko nɔ lɛ, tsofa tsakemɔ ni baa shi lɛ tsɔɔ akɛ ebaanyɛ efee dihydrogenous henɔ15. Yitso hee ni ji enyɔ lɛ yɛ -17.5 ppm. Eyɛ mli akɛ aleee bɔ ni ebɔleɔ ehe ehaa lɛ moŋ, shi wɔheɔ wɔyeɔ akɛ eji triplet ni yɔɔ 17.3 Hz ni kɛ ehe kpaa gbee bibioo, ni tsɔɔ akɛ hydrogen ligand lɛ kɛ phosphine ligand ni yɔɔ POP klamp lɛ mli lɛ pɛ kpaa gbee, ni etsɔɔ hu akɛ triphenylphosphine (peak C) lɛ jeɔ kpo. Abaanyɛ akɛ ligand kroko, tamɔ acetyl kuu loo NHC ni afee yɛ he ni eyɔɔ lɛ kɛjɛ ionic nu lɛ mli lɛ ato najiaŋ. PPh3 lɛ mligbalamɔ lɛ tsɔɔ singlet ni mli wa ni yɔɔ -5.9 ppm lɛ mli ekoŋŋ. yɛ 31P{1H} spectrum ni ji Ru-1 lɛ mli yɛ minitii 180 sɛɛ yɛ 90 °C (kwɛmɔ saji krokomɛi ni fata he).
Hydride kpokpaa ni ji 1H NMR spectrum ni ji Ru-1 lɛ yɛ be mli ni formic acid lɛ mli nu lɛ jeɔ kpo lɛ. Shihilɛi ni haa mɔ tsui nyɔɔ emli: 0.5 ml fɔmik asid, 1.0 ml BMIM OAc, 13.0 μmol ni haa mɔ tsui nyɔɔ emli, 90 °C. NMR lɛ ji nɔ ni ajie kɛjɛ MeCN-d 3 , 500 μl ni ji deuterated tsɔne lɛ mli, aaafee 10 μl ni ji tsɔne ni akɛfutuɔ nii lɛ mli.
Kɛha nɔmimaa ni yaa hiɛ akɛ bɔɔ nii ni tsuɔ nii yɛ tsɔne ni haa mɔ tsui nyɔɔ emli lɛ mli lɛ, afee Ru-1 lɛ mlipɛimɔ ni ji ŋwɛi ŋtayaa ni nɔ kwɔ (HRMS) lɛ mlipɛimɔ yɛ be mli ni akɛ formic acid wo mli minitii 10 yɛ 90 °C lɛ sɛɛ. Enɛ tsɔɔ akɛ nibii ni bɛ chlorine ligand precatalyst lɛ yɛ nɔ ni akɛfutuɔ nii lɛ mli. kɛ agbɛnɛ hu NHC srɔtoi enyɔ, ni atsɔɔ bɔ ni ato amɛhe gbɛjianɔ aha yɛ mfoniri 6 lɛ mli. Abaanyɛ ana HRMS spectrum ni kɛ lɛ kpãa gbee lɛ yɛ mfoniri 7 ni fata he lɛ mli.
Kɛtsɔ saji nɛɛ anɔ lɛ, wɔkɛ gbɛjianɔtoo ko ni tamɔ nɔ ni Beller tsɔɔ lɛ haa, ni N-methylated PNP clamps lɛ haa nɔ kome too lɛ nɔŋŋ baa. Kaai krokomɛi ni ionic nu fataaa he lɛ etsɔɔɔ nitsumɔ ko, no hewɔ lɛ etamɔ nɔ ni ehe miihia ni ekɛ ehe awo mli tɛ̃ɛ. Wɔsusuɔ akɛ Ru-1 kɛ Ru-2 nitsumɔ baa kɛtsɔ chloride mligbalamɔ ni NHC ni akɛfataa he kɛ triphenylphosphine mligbalamɔ ni baanyɛ aba lɛ nyiɛɔ sɛɛ (Scheme 1a). Akwɛ nɛkɛ nitsumɔ nɛɛ yɛ kooloi srɔtoi fɛɛ amli kɛtsɔ HRMS nɔ tsutsu. IL-acetate ji Bronsted shishitoo ni mli wa fe formic acid ni ebaanyɛ ejie sɛɛ mli nɔ lɛ waa35. Wɔsusuɔ akɛ yɛ be mli ni tsɔne lɛ mli nibii ni haa mɔ tsui nyɔɔ emli lɛ (Scheme 1b) lɛ, tsɔnei ni tsuɔ nii A ni hiɛ NHC loo PPh3 lɛ feɔ ekome kɛtsɔɔ formate nɔ koni amɛfee tsɔnei ni ji B. acid ni akɛfeɔ dihydro complex E lɛ tamɔ gbɛ titri ni Beller kɛ N-methylated PNP klamp homologues tsu nii lɛ. Kɛfata he lɛ, tsutsu ko lɛ, afee EL = PPh3 ni mli wa lɛ he nɔkwɛmɔnɔ ko kɛtsɔ stoichiometric nifeemɔ ko ni akɛ Ru-1 tsuɔ nii yɛ hydrogen kɔɔyɔɔ mli lɛ nɔ yɛ be mli ni ajie chloride kɛ sodium ŋmei lɛ sɛɛ. Hydrogen ni ajieɔ kɛ formate ni akɛtsuɔ nii lɛ haa A ni egbeɔ sɛɛkuu lɛ naa.
Akɛ gbɛ ko ni atsɔɔ nɔ atsuɔ formic acid dehydrogenation ni akɛ Ru-POP Ru-1 ni haa mɔ tsui nyɔɔ emli lɛ tsuɔ nii lɛ he nii lɛ etsɔɔ.
Afee nɔ ko hee ko ni yɔɔ srɔto [RuHCl (iPr-dbffos) (PPh3)]. NMR, ATRIR, EA kɛ X-ray diffraction mlipɛimɔ ni kɔɔ kristalo komekomei ahe lɛ ji nɔ ni kadiɔ nɔ ni yɔɔ srɔtoi lɛ. Wɔbɔ Ru-POP pincer nitsumɔ klɛŋklɛŋ ni ye omanye yɛ formic acid ni ajieɔ kɛjɛɔ CO2 kɛ H2 mli lɛ he amaniɛ hu. Eyɛ mli akɛ dade ni tsɔɔ hiɛ lɛ ná nitsumɔ ni tamɔ nakai nɔŋŋ moŋ (kɛyashi 3424 h-1), shi tsɔne ni yɔɔ srɔtoi lɛ shɛɔ sɛɛkuu ni fe fɛɛ ni shɛɔ 4525 h-1 he yɛ 90 °C. Agbɛnɛ hu, yɛ 90 °C mli lɛ, tsɔne hee ni ji [RuHCl(iPr-dbfphos)(PPh3)] lɛ nine shɛ be fɛɛ ni ekɛtsuɔ nii (1009 h-1) nɔ koni ekɛgbe formic acid ni ajieɔ nu kɛjɛɔ mli lɛ naa, ni no ji nɔ ni nɔ kwɔ kwraa fe dade ni tsɔɔ hiɛ lɛ (330 h-1). kɛ nɔ ni yɔɔ mlɛo ni abɔ he amaniɛ tsutsu lɛ [RuHCl (xantphos) (PPh3)] (333 h-1). Yɛ shihilɛi ni tamɔ nakai nɔŋŋ mli lɛ, nɔ ni haa tsɔne lɛ tsuɔ nii jogbaŋŋ lɛ ji nɔ ni akɛtoɔ Ru-PNP klamp complex lɛ he. HRMS adafitswaa tsɔɔ akɛ carbene complex ko yɛ nɔ ni akɛfutuɔ nii lɛ mli, eyɛ mli akɛ eyɛ fioo moŋ. Amrɔ nɛɛ wɔmiikase bɔ ni carbene complexes lɛ tsuɔ nii ehaa lɛ he nii.
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