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ʻO ka waikawa Formic kekahi o nā moho hoʻohiki nui loa no ka mālama lōʻihi o ka hydrogen wai. Maanei mākou e hōʻike nei i kahi moʻo o nā hui clamp ruthenium hou me ke ʻano maʻamau [RuHCl(POP)(PPh3)] me ka hoʻohana ʻana i nā ligands clamp xanthos-type tridentate POP i loaʻa a maʻalahi hoʻi i synthesized. Ua hoʻohana mākou i kēia mau hui e dehydrogenate formic acid e hana i ka CO2 a me H2 ma lalo o nā kūlana akahai, reflux-free me ka hoʻohana ʻana i ka wai ionic BMIM OAc (1-butyl-3-methylimidazolium acetate) ma ke ʻano he solvent. Mai ka manaʻo o ka pinepine huli nui loa, ʻo ka mea hoʻouluulu maikaʻi loa ʻo ia ka hui [RuHCl(xantphos)(PPh3)]Ru-1 i ʻike ʻia ma ka palapala, nona ka pinepine huli nui loa o 4525 h-1 ma 90 °C no 10 min. ʻO ka helu ma hope o ka hoʻololi ʻana he 74%, a ua hoʻopau ʻia ka hoʻololi ʻana i loko o 3 mau hola (>98%). Ma ka ʻaoʻao ʻē aʻe, ʻo ka mea hoʻoulu me ka hana holoʻokoʻa maikaʻi loa, ʻo ka hui hou [RuHCl(iPr-dbfphos)(PPh3)]Ru-2, e paipai i ka hoʻololi piha ʻana i loko o 1 h, e hopena ana i ka helu huli holoʻokoʻa o 1009 h-1. Eia kekahi, ua ʻike ʻia ka hana catalytic ma nā mahana a hiki i ka 60 °C. I loko o ke kahua kinoea, ʻo CO2 a me H2 wale nō i ʻike ʻia; ʻAʻole i ʻike ʻia ʻo CO. Ua hōʻike ka spectrometry mass high-resolution i ke alo o nā hui N-heterocyclic carbene i loko o ka hui hopena.
ʻO ka ulu ʻana o ka mākeke o ka ikehu hou a me kona ʻano like ʻole ua alakaʻi i ka noi no nā ʻenehana mālama ikehu ʻoihana ma nā ʻāpana mana, thermal, ʻoihana a me ka halihali1,2. Ua manaʻo ʻia ʻo Hydrogen kekahi o nā mea lawe ikehu nui loa3, a ua lilo nā mea lawe hydrogen organik wai (LOHCs) i mea nui o ka noiʻi, e hāʻawi ana i ka ʻōlelo hoʻohiki o ka mālama ʻana i ka hydrogen ma ke ʻano hana maʻalahi me ka ʻole o nā pilikia e pili ana i ka pressurization a i ʻole nā ​​​​ʻenehana cryogenic4. ,5,6. Ma muli o ko lākou mau waiwai kino, hiki ke hoʻohana ʻia ka hapa nui o nā ʻōnaehana halihali e kū nei no ka gasoline a me nā wahie wai ʻē aʻe e lawe iā LOHC7,8. ʻO nā waiwai kino o ka waikawa formic (FA) e lilo ia i moho hoʻohiki no ka mālama ʻana i ka hydrogen me ka nui o ke kaumaha hydrogen o 4.4%9,10. Eia nō naʻe, ʻo nā ʻōnaehana catalytic i paʻi ʻia no ka dehydrogenation waikawa formic e koi pinepine i ka hoʻohana ʻana i nā solvents organik volatile, ka wai a i ʻole ka waikawa formic maʻemaʻe,11,12,13,14 e pono ai ka hoʻohana ʻana i nā ʻenehana hoʻokaʻawale mahu solvent e like me ka condensation, hiki ke alakaʻi i nā pilikia i nā noi mea kūʻai aku. nā noi, ukana hou. Hiki ke lanakila ʻia kēia pilikia ma ka hoʻohana ʻana i nā mea hoʻoheheʻe me ke kaomi mahu liʻiliʻi, e like me nā wai ionic. Ma mua, ua hōʻike kā mākou hui hana he mea hoʻoheheʻe kūpono ka wai ionic butylmethylimidazolium acetate (BMIM OAc) i kēia hopena me ka hoʻohana ʻana i ka paʻakikī hoʻopaʻa Ru-PNP Ru-MACHO ʻano 15. No ka laʻana, ua hōʻike mākou i ka dehydrogenation FA i loko o kahi ʻōnaehana kahe mau me ka hoʻohana ʻana i ka BMIM OAc, e hoʻokō ana i kahi TON ma mua o 18,000,000 ma 95°C. ʻOiai ua hoʻokō mua kekahi mau ʻōnaehana i ka TON kiʻekiʻe, ua hilinaʻi ka nui i nā mea hoʻoheheʻe organik volatile (e like me THF a i ʻole DMF) a i ʻole nā ​​​​mea hoʻohui i hoʻohana ʻia (e like me nā kumu). I ka hoʻohālikelike ʻana, hoʻohana maoli kā mākou hana i nā wai ionic non-volatile (ILs) a ʻaʻohe mea hoʻohui.
Ua hōʻike ʻo Hazari lāua ʻo Bernskoetter i ka dehydrogenation o ka formic acid (FA) ma 80 °C me ka hoʻohana ʻana i kahi mea hoʻouluulu Fe-PNP i ke alo o dioxane a me LiBF4, e hoʻokō ana i kahi helu huli kupaianaha (TON) ma kahi o 1,000,00016. Ua hoʻohana ʻo Laurenci i kahi mea hoʻouluulu Ru(II)- complex TPPPTS i loko o kahi ʻōnaehana dehydrogenation FA hoʻomau. Ua hopena kēia ʻano hana i ka dehydrogenation FA kokoke loa me nā koena liʻiliʻi o CO i ʻike ʻia ma 80 °C17. No ka hoʻolaha hou ʻana i kēia kahua, ua hōʻike ʻo Pidko i ka dehydrogenation hiki ke hoʻohuli ʻia o FA me ka hoʻohana ʻana i nā mea hoʻouluulu clamp Ru-PNP i nā hui DMF/DBU a me DMF/NHex₃, e hoʻokō ana i nā waiwai TON o 310,000 a 706,500 ma 90 °C18. Ua aʻo ʻo Hull, Himeda lāua ʻo Fujita i kahi mea hoʻouluulu binuclear Ir complex kahi i mōhai ʻia ai ʻo KHCO3 a me H2SO4, e hoʻololi ana i ka hydrogenation CO2 a me ka dehydrogenation FA. Ua hoʻokō kā lākou mau ʻōnaehana i nā TON ma luna o 3,500,000 a me 308,000 no ka hydrogenation ma 30°C, CO2/H2 (1:1), kaomi 1 bar a no ka dehydrogenation ma waena o 60 a me 90°C19. Ua hoʻomohala ʻo Sponholz, Junge lāua ʻo Beller i kahi paʻakikī Mn-PNP no ka hydrogenation CO2 hiki ke hoʻohuli ʻia a me ka dehydrogenation FA ma 90°C20.
Maanei ua hoʻohana mākou i kahi ala IL, akā ma kahi o ka hoʻohana ʻana i nā Ru-PNP, ua ʻimi mākou i ka hoʻohana ʻana i nā mea hoʻouluulu Ru-POP, kahi i hōʻike ʻole ʻia ma mua i kēia ʻano i ko mākou ʻike.
Ma muli o kā lākou hoʻopili metal-ligand maikaʻi loa (MLC), ʻo nā hui amino-PNP clamp e pili ana i nā manaʻo ʻano Noyori me nā hui hana amino lua 21 (e like me Ru-MACHO-BH) e lilo nei i mea kaulana i kekahi mau hana mole liʻiliʻi. ʻO nā hiʻohiʻona kaulana e pili ana iā CO22, hydrogenation o alkenes a me carbonyls, transfer hydrogenation23 a me ka dehydrogenation acceptorless o nā alcohols24. Ua hōʻike ʻia e hiki i ka N-methylation o nā ligands clamp PNP ke hoʻōki loa i ka hana catalyst25, hiki ke wehewehe ʻia e ka ʻoiaʻiʻo e lawelawe nā amines ma ke ʻano he kumu proton, he koi koʻikoʻi ia i ka wā o ke kaʻina catalytic me ka hoʻohana ʻana iā MLC. Eia nō naʻe, ua ʻike koke ʻia ke ʻano ʻē aʻe i ka dehydrogenation acid formic e Beller, kahi i hōʻike maoli ai nā hui N-methylated Ru-PNP i ka dehydrogenation catalytic maikaʻi o ka acid formic ma mua o ko lākou mau hoa unmethylated26. ʻOiai ʻaʻole hiki i ka hui mua ke komo i ka MLC ma o ka ʻāpana amino, hōʻike ikaika kēia e hiki i ka MLC, a no laila ke ʻāpana amino, ke pāʻani i kahi kuleana koʻikoʻi ʻole i kekahi mau hoʻololi (de)hydrogenation ma mua o ka mea i manaʻo ʻia ma mua.
Ke hoʻohālikelike ʻia me nā ʻūpā POP, ʻaʻole i lawa ka aʻo ʻia ʻana o nā hui ruthenium o nā ʻūpā POP ma kēia wahi. Ua hoʻohana mua ʻia nā ligands POP no ka hydroformylation, kahi e hana ai lākou ma ke ʻano he ligands chelating ma mua o ke kihi nahu bidentate hiʻohiʻona o kahi 120° no nā ligands clamping, i hoʻohana ʻia e hoʻonui i ke koho ʻana no nā huahana linear a me nā lālā27,28,29. Mai ia manawa, ʻaʻole i hoʻohana pinepine ʻia nā hui Ru-POP i ka catalysis hydrogenation, akā ua hōʻike mua ʻia nā hiʻohiʻona o kā lākou hana ma ka hydrogenation hoʻoili30. Maanei mākou e hōʻike nei he mea hoʻoulu maikaʻi ka hui Ru-POP no ka dehydrogenation o ka waikawa formic, e hōʻoia ana i ka ʻike ʻana o Beller ʻaʻole nui ka ʻāpana amino i loko o ka mea hoʻoulu amine Ru-PNP maʻamau i kēia hopena.
Hoʻomaka kā mākou haʻawina me ka synthesis o ʻelua mau catalysts maʻamau me ke ʻano laulā [RuHCl(POP)(PPh3)] (Kiʻi 1a). No ka hoʻololi ʻana i ke ʻano steric a me ka uila, ua koho ʻia ʻo dibenzo[b,d]furan mai ka 4,6-bis(diisopropylphosphino) i loaʻa ma ke kālepa (Kiʻi 1b) 31. Ua synthesized ʻia nā catalysts i aʻo ʻia ma kēia hana me ka hoʻohana ʻana i kahi ʻano laulā i hoʻomohala ʻia e Whittlesey32, me ka hoʻohana ʻana i ka [RuHCl(PPh3)3]•toluene33 adduct ma ke ʻano he precursor. E hoʻohui i ka metal precursor a me ka POP clamp ligand ma THF ma lalo o nā kūlana anhydrous a me anaerobic. Ua hele pū ʻia ka hopena me kahi loli kala koʻikoʻi mai ka poni ʻeleʻele a i ka melemele a hāʻawi i kahi huahana maʻemaʻe ma hope o 4 mau hola o ka reflux a i ʻole 72 mau hola o ka reflux ma 40°C. Ma hope o ka wehe ʻana i ka THF i loko o ka vacuo a me ka holoi ʻana i ʻelua manawa me ka hexane a i ʻole diethyl ether, ua wehe ʻia ka triphenylphosphine e hāʻawi i ka huahana ma ke ʻano he pauka melemele i ka nui o ka hua.
Ka hana ʻana o nā hui Ru-1 a me Ru-2. a) Ke ʻano o ka hana ʻana o nā hui. b) Ke ʻano o ka hui i hana ʻia.
Ua ʻike mua ʻia ʻo Ru-1 mai nā palapala32, a ke kālele nei ka wehewehe hou aku iā Ru-2. Ua hōʻoia ka spectrum 1H NMR o Ru-2 i ka hoʻonohonoho cis o ka ʻātoma phosphine i loko o ka ligand o ka hui hydride. Hōʻike ka peak dt plot (Fig. 2a) i nā constants coupling 2JP-H o 28.6 a me 22.0 Hz, aia i loko o ka laulā i manaʻo ʻia o nā hōʻike mua32. I loko o ka hydrogen decoupled 31P{1H} spectrum (Fig. 2b), ua ʻike ʻia kahi constant coupling 2JP-P o kahi o 27.6 Hz, e hōʻoia ana he cis-cis nā clamp ligand phosphine a me PPh3. Eia kekahi, hōʻike ʻo ATR-IR i kahi ʻano ruthenium-hydrogen stretching band ma 2054 cm-1. No ka wehewehe hou ʻana i ke ʻano, ua hoʻomālamalama ʻia ka paʻakikī Ru-2 e ka vapor diffusion ma ka mahana o ka lumi me ka maikaʻi kūpono no nā haʻawina X-ray (Fig. 3, Supplementary Table 1). Hoʻopili ia i loko o ka ʻōnaehana triclinic o ka hui ākea P-1 me hoʻokahi ʻāpana benzene cocrystalline no kēlā me kēia cell. Hōʻike ia i kahi kihi occlusal P-Ru-P ākea o 153.94°, ʻoi aku ka laulā ma mua o ka kihi occlusal 130° o ka bidentate DBFphos34. Ma 2.401 a me 2.382 Å, ʻoi aku ka lōʻihi o ka lōʻihi o ka pilina Ru-PPOP ma mua o ka lōʻihi o ka pilina Ru a PPh3 o 2.232 Å, ʻo ia paha ka hopena o ka kihi snack iwi kuamoʻo ākea o DBFphos i hoʻokumu ʻia e kona apo waena 5. ʻO ke ʻano o ke kikowaena metala he octahedral me kahi kihi O-Ru-PPh3 o 179.5°. ʻAʻole linear loa ka hoʻohui ʻana o H-Ru-Cl, me kahi kihi ma kahi o 175° mai ka ligand triphenylphosphine. Ua helu ʻia nā mamao atomika a me nā lōʻihi o ka pilina ma ka Papa 1.
ʻO ka spectrum NMR o Ru-2. a) ʻĀpana Hydride o ka spectrum 1H NMR e hōʻike ana i ka hōʻailona Ru-H dt. b) 31 P{ 1 H} NMR spectrum e hōʻike ana i nā hōʻailona mai ka triphenylphosphine (uliuli) a me ka ligand POP (ʻōmaʻomaʻo).
ʻAno o Ru-2. Hōʻike ʻia nā ellipsoid thermal me kahi hiki ke 70%. No ka maopopo, ua kāpae ʻia nā ʻātoma benzene cocrystalline a me nā hydrogen ma ke kalapona.
No ka loiloi ʻana i ka hiki o nā complexes ke dehydrogenate i ka formic acid, ua koho ʻia nā kūlana hopena ma lalo o ka hana nui ʻana o nā complexes PNP-clamp e pili ana (e laʻa, Ru-MACHO-BH)15. Dehydrogenation o 0.5 ml (13.25 mmol) formic acid me ka hoʻohana ʻana i ka 0.1 mol% (1000 ppm, 13 µmol) ruthenium complex Ru-1 a i ʻole Ru-2 me ka hoʻohana ʻana i ka 1.0 ml (5.35 mmol) ionic liquid (IL) BMIM OAc (papa-kiʻi) 2; Kiʻi 4);
No ka loaʻa ʻana o ke kūlana maʻamau, ua hoʻokō mua ʻia ka hopena me ka hoʻohana ʻana i ka precursor adduct [RuHCl(PPh3)3]·toluene. Hoʻokō ʻia ka hopena ma kahi mahana mai 60 a 90 °C. Wahi a nā nānā ʻike maʻalahi, ʻaʻole hiki ke hoʻoheheʻe loa ʻia ka paʻakikī i loko o IL me ka hoʻoulu lōʻihi ʻana ma kahi mahana o 90 °C, akā ua hoʻoheheʻe ʻia ma hope o ka hoʻokomo ʻana o ka waikawa formic. Ma 90 °C, ua hoʻokō ʻia kahi hoʻololi o 56% (TOF = 3424 h-1) i loko o nā minuke 10 mua, a ua hoʻokō ʻia ka hoʻololi kokoke i ka quantitative (97%) ma hope o ʻekolu hola (komo 1). ʻO ka hoʻemi ʻana i ka mahana i 80 °C e hōʻemi ana i ka hoʻololi ʻana ma mua o ka hapalua a i 24% ma hope o 10 min (TOF = 1467 h-1, komo 2), e hoʻemi hou ana iā ia i 18% a me 18% ma 70 °C a me 60 °C, kēlā me kēia 6% (nā komo 3 a me 4). I nā hihia a pau, ʻaʻohe wā hoʻokomo i ʻike ʻia, e hōʻike ana he ʻano reactive paha ka mea hoʻoulu a i ʻole he wikiwiki loa ka hoʻololi ʻana o nā ʻano reactive e ʻike ʻia me ka hoʻohana ʻana i kēia ʻikepili.
Ma hope o ka loiloi mua, ua hoʻohana ʻia nā hui Ru-POP clamp ʻo Ru-1 a me Ru-2 ma lalo o nā kūlana like. Ma 90°C, ua ʻike koke ʻia ka hoʻololi kiʻekiʻe. Ua hoʻokō ʻo Ru-1 i ka hoʻololi ʻana he 74% i loko o nā minuke 10 mua o ka hoʻokolohua (TOFmax = 4525 h-1, komo 5). Ua hōʻike iki ʻo Ru-2 i ka hana emi iki akā ʻoi aku ka paʻa, e hoʻolaha ana i ka hoʻololi ʻana he 60% i loko o 10 min (TOFmax = 3669 h-1) a me ka hoʻololi piha i loko o 60 min (>99%) (komo 9). He mea kūpono ke hoʻomaopopo ʻia he ʻoi aku ka maikaʻi o Ru-2 ma mua o ka metala mua a me Ru-1 i ka hoʻololi piha. No laila, ʻoiai he like nā waiwai TOFoverall o ka metala mua a me Ru-1 i ka pau ʻana o ka hopena (330 h-1 a me 333 h-1, kēlā me kēia), loaʻa iā Ru-2 kahi TOFoverall o 1009 h-1.
A laila ua hoʻololi ʻia ʻo Ru-1 a me Ru-2 i kahi loli mahana kahi i hoʻemi mālie ʻia ai ka mahana i nā piʻi 10 °C a hiki i ka liʻiliʻi o 60 °C (Kiʻi 3). Inā ma 90 °C ua hōʻike koke ka paʻakikī i ka hana, ua kokoke ka hoʻololi piha ʻana i loko o hoʻokahi hola, a laila ma nā mahana haʻahaʻa ua hāʻule koke ka hana. ʻO ka hoʻololi ʻana o Py-1 he 14% a me 23% ma hope o 10 min ma 80 °C a me 70 °C, kēlā me kēia, a ma hope o 30 min ua piʻi aʻe i 79% a me 73% (nā komo 6 a me 7). Ua hōʻike nā hoʻokolohua ʻelua i ka helu hoʻololi o ≥90% i loko o ʻelua hola. Ua ʻike ʻia ke ʻano like no Ru-2 (nā komo 10 a me 11). ʻO ka mea hoihoi, ua mana iki ʻo Ru-1 i ka hopena o ka hopena ma 70 °C me ka huina TOF o 315 h-1 i hoʻohālikelike ʻia me 292 h-1 no Ru-2 a me 299 h-1 no ka mea mua o ka metala.
ʻO ka emi hou ʻana o ka mahana i 60 °C i alakaʻi i ka ʻoiaʻiʻo ʻaʻohe hoʻololi i ʻike ʻia i loko o nā minuke 30 mua o ka hoʻokolohua. ʻAʻole hana nui ʻo Ru-1 ma ka mahana haʻahaʻa loa i ka hoʻomaka ʻana o ka hoʻokolohua a ma hope iho ua hoʻonui ʻia ka hana, e hōʻike ana i ke koi o kahi manawa hoʻāla i ka wā e hoʻololi ʻia ai ka precatalyst Ru-1 i mau ʻano hana catalytically. ʻOiai hiki kēia ma nā mahana āpau, ʻaʻole lawa ka 10 mau minuke i ka hoʻomaka ʻana o ka hoʻokolohua e ʻike i kahi manawa hoʻāla ma nā mahana kiʻekiʻe. Ua loaʻa ke ʻano like no Ru-2. Ma 70 a me 60 °C, ʻaʻohe hoʻololi i ʻike ʻia i loko o nā minuke 10 mua o ka hoʻokolohua. He mea nui e hoʻomaopopo i loko o nā hoʻokolohua ʻelua, ʻaʻole i ʻike ʻia ka hoʻokumu ʻia ʻana o ke kalapona monoxide i loko o ka palena ʻike o kā mākou mea hana (<300 ppm), me H2 a me CO2 wale nō nā huahana i ʻike ʻia.
ʻO ka hoʻohālikelike ʻana o nā hopena dehydrogenation formic acid i loaʻa ma mua ma kēia hui hana, e hōʻike ana i ke kūlana o ke akamai a me ka hoʻohana ʻana i nā complexes clamp Ru-PNP, ua hōʻike ʻia he like ka hana o ka clamp Ru-POP i hoʻohui hou ʻia me kāna hoa PNP 15. ʻOiai ua hoʻokō ka PNP i nā RPM o 500-1260 h-1 i nā hoʻokolohua batch, ua hoʻokō ka clamp POP hou i kahi waiwai TOFovertal like o 326 h-1, a ua ʻike ʻia nā waiwai TOFmax o Ru-1 a me 1590 h-1. ʻO Ru-2 he 1 ma 80 °C, ʻo Ru-1 he 4525 h-1 a ʻo Ru-1 he 3669 h-1 ma 90 °C, kēlā me kēia.
Ka nānā ʻana i ka mahana o ka dehydrogenation waikawa formic me ka hoʻohana ʻana i nā mea hoʻoulu Ru-1 a me Ru-2. Nā kūlana: mea hoʻoulu 13 µmol, 0.5 ml (13.25 mmol) waikawa formic, 1.0 ml (5.35 mmol) BMIM OAc.
Hoʻohana ʻia ʻo NMR e hoʻomaopopo i nā ʻano hana. ʻOiai he ʻokoʻa koʻikoʻi loa ma 2JH-P ma waena o nā ligands hydride a me phosphine, ʻo ke kiko o kēia haʻawina ma ka piko hydride. No Ru-1, ua loaʻa kahi ʻano dt maʻamau o ka ʻāpana hydrogenation i nā minuke 60 mua o ka dehydrogenation. ʻOiai aia kahi neʻe ʻana o ka downfield koʻikoʻi mai −16.29 a i −13.35 ppm, ʻo kona mau kūpaʻa hoʻopili me ka phosphine he 27.2 a me 18.4 Hz, kēlā me kēia (Kiʻi 5, Peak A). He kūlike kēia me nā phosphine ʻekolu a pau kahi i noho ai ka ligand hydrogen i loko o ka hoʻonohonoho cis a hōʻike i ka paʻa iki o ka hoʻonohonoho ligand ma ka IL no hoʻokahi hola ma lalo o nā kūlana hana i hoʻonui ʻia. ʻO ka neʻe ʻana o ka downfield ikaika ma muli paha o ka hoʻopau ʻana o nā ligands chlorinated a me ka hoʻokumu ʻia ʻana o nā complexes acetyl-formic acid like, ka hoʻokumu ʻana o ka complex d3-MeCN i loko o ka paipu NMR, a i ʻole ka hoʻokumu ʻana o nā N-heterocycles like. ua wehewehe ʻia. ʻO ka paʻakikī Carbene (NHC). I ka wā o ka hopena dehydrogenation, ua hoʻomau ka emi ʻana o ka ikaika o kēia hōʻailona, ​​a ma hope o 180 mau minuke ʻaʻole i ʻike hou ʻia ka hōʻailona. Akā, ua ʻike ʻia ʻelua mau hōʻailona hou. Hōʻike ka mea mua i kahi ʻano dd maopopo e hana ana ma -6.4 ppm (peak B). Loaʻa i ka doublet kahi mau hoʻopili nui ma kahi o 130.4 Hz, e hōʻike ana ua neʻe kekahi o nā ʻāpana phosphine e pili ana i ka hydrogen. ʻO ke ʻano paha kēia ua hoʻonohonoho hou ʻia ka clamp POP i loko o kahi hoʻonohonoho κ2-P,P. ʻO ke ʻano o kēia paʻakikī i ka hopena o ka catalysis e hōʻike paha e alakaʻi kēia ʻano i nā ala deactivation i ka hala ʻana o ka manawa, e hana ana i kahi poho catalyst. Ma ka ʻaoʻao ʻē aʻe, hōʻike ka neʻe kemika haʻahaʻa he ʻano dihydrogenous paha ia15. Aia ka lua o ka piko hou ma -17.5 ppm. ʻOiai ʻaʻole ʻike ʻia kona pelu, ke manaʻoʻiʻo nei mākou he triplet ia me kahi kūpaʻa liʻiliʻi o 17.3 Hz, e hōʻike ana ua hoʻopaʻa wale ka ligand hydrogen i ka ligand phosphine o ka POP clamp, e hōʻike ana hoʻi i ka hoʻokuʻu ʻia ʻana o ka triphenylphosphine (peak C). Hiki ke pani ʻia e kahi ligand ʻē aʻe, e like me kahi hui acetyl a i ʻole kahi NHC i hoʻokumu ʻia ma kahi mai ka wai ionic. Hōʻike hou ʻia ka dissociation o PPh3 e kahi singlet ikaika ma -5.9 ppm. ma ka spectrum 31P{1H} o Ru-1 ma hope o 180 mau minuke ma 90 °C (e ʻike i ka ʻike hou aku).
ʻO ka ʻāpana Hydride o ka spectrum 1H NMR o Ru-1 i ka wā o ka dehydrogenation o ka waikawa formic. Nā kūlana hopena: 0.5 ml waikawa formic, 1.0 ml BMIM OAc, 13.0 µmol catalyst, 90 °C. Ua lawe ʻia ʻo NMR mai MeCN-d 3, 500 μl o ka deuterated solvent, ma kahi o 10 μl o ka hui hopena.
No ka hōʻoia hou ʻana i ke alo o nā ʻano hana i loko o ka ʻōnaehana catalytic, ua hana ʻia ka loiloi spectrometry mass resolution kiʻekiʻe (HRMS) o Ru-1 ma hope o ka hoʻokomo ʻana o ka waikawa formic no 10 min ma 90 °C. Hōʻike kēia i ke alo o nā ʻano i nele i ka chlorine ligand precatalyst i loko o ka hui hopena. a me ʻelua mau complexes NHC, nā ʻano putative i hōʻike ʻia ma ke Kiʻi 6. Hiki ke ʻike ʻia ka spectrum HRMS pili ma ke Kiʻi Hoʻohui 7.
Ma muli o kēia ʻikepili, ke hāpai nei mākou i kahi ʻano hana intrasphere e like me ka mea i hāpai ʻia e Beller, kahi e hoʻoulu ai nā clamps PNP N-methylated i ka hopena like. ʻAʻole i hōʻike ʻia kekahi hana i nā hoʻokolohua hou e kāpae ana i nā wai ionic, no laila me he mea lā pono kona komo pololei ʻana. Ke kuhi nei mākou e hana ʻia ka hoʻoulu ʻana o Ru-1 a me Ru-2 ma o ka dissociation chloride a ukali ʻia e ka hoʻohui NHC hiki a me ka dissociation triphenylphosphine (Scheme 1a). Ua ʻike mua ʻia kēia hoʻoulu ʻana i nā ʻano āpau me ka hoʻohana ʻana iā HRMS. ʻO IL-acetate kahi kumu Bronsted ikaika ma mua o ka waikawa formic a hiki ke hoʻopau ikaika i ka mea hope35. Ke kuhi nei mākou i ka wā o ke kaʻina hana catalytic (Scheme 1b), ua hoʻonohonoho ʻia nā ʻano hana A e lawe ana iā NHC a i ʻole PPh3 ma o formate e hana i nā ʻano B. ʻO ka hoʻonohonoho hou ʻana o kēia paʻakikī i C ka hopena i ka hoʻokuʻu ʻia ʻana o CO2 a me ka trans-dihydrogen complex D ʻO ka protonation ma hope o ka waikawa i loko o kahi dihydro complex me ka acetic acid i hana mua ʻia e hana i ka dihydro complex E ua like ia me ke kaʻina hana nui i hāpai ʻia e Beller me ka hoʻohana ʻana i nā homologues clamp N-methylated PNP. Eia kekahi, ua synthesized mua ʻia kahi analog o ka complex EL = PPh3 e kahi hopena stoichiometric e hoʻohana ana iā Ru-1 i loko o kahi lewa hydrogen ma hope o ka unuhi ʻana o ka chloride me ka paʻakai sodium. ʻO ka wehe ʻana o ka hydrogen a me ka hoʻonohonoho ʻana o ka formate e hāʻawi iā A a hoʻopau i ke kaʻina hana.
Ua hāpai ʻia kahi ʻano hana no ka hopena intrasphere o ka dehydrogenation waikawa formic me ka hoʻohana ʻana i ka paʻakikī hoʻopaʻa ʻo Ru-POP Ru-1.
Ua hoʻohui ʻia kahi hui hou [RuHCl(iPr-dbfphos)(PPh3)]. Ua hōʻike ʻia ka hui e ka NMR, ATRIR, EA a me ka loiloi diffraction X-ray o nā kristal hoʻokahi. Hōʻike pū mākou i ka hoʻopili mua ʻana o nā hui Ru-POP pincer i ka dehydrogenation o ka waikawa formic i CO2 a me H2. ʻOiai ua hoʻokō ka mea mua o ka metala i ka hana like (a hiki i 3424 h-1), ua hōʻea ka hui i kahi alapine huli kiʻekiʻe loa a hiki i 4525 h-1 ma 90 °C. Eia kekahi, ma 90 °C, ua hoʻokō ka hui hou [RuHCl(iPr-dbfphos)(PPh3)] i ka manawa holo holoʻokoʻa (1009 h-1) e hoʻopau i ka dehydrogenation waikawa formic, ʻoi aku ka kiʻekiʻe ma mua o ka mea mua o ka metala (330 h-1). a me ka hui i hōʻike mua ʻia [RuHCl(xantphos)(PPh3)] (333 h-1). Ma lalo o nā kūlana like, ua like ka pono catalytic me ko ka Ru-PNP clamp complex. Hōʻike ka ʻikepili HRMS i ke alo o kahi carbene complex i loko o ka hui hopena, ʻoiai he liʻiliʻi nā nui. Ke aʻo nei mākou i nā hopena catalytic o nā carbene complexes.
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