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Formic acid cu ti bantuk hydrogen caan saupi chiahnak caah a ttha bikmi pakhat a si. Hika ah hin chawlehnak ah hmuh khawhmi asiloah fawi tein sermi xanthos-type tridentate POP clamp ligands hmangin a tlangpi formula [RuHCl(POP)(PPh3)] he ruthenium clamp complex thar phunphun kan langhter. Hi complex pawl hi formic acid kha dehydrogenate tuahnak caah kan hman i CO2 le H2 chuah khawhnak ding caah a nemmi, reflux-free dirhmun tangah ionic liquid BMIM OAc (1-butyl-3-methylimidazolium acetate) kha solvent ah kan hman. A tam bik thlennak frequency zoh tikah, a ttha bikmi catalyst cu cauk chung ah theihmi [RuHCl(xantphos)(PPh3)]Ru-1 complex a si, cu nih cun 90 °C ah 10 min chung 4525 h-1 a tam bik thlennak frequency a ngei. A hnu thlennak rate cu 74% a si, cun thlennak cu suimilam 3 chungah a dih (>98%). Khatlei kam in, a ttha bikmi a dihlak in riantuannak a ngeimi catalyst, novel [RuHCl(iPr-dbfphos)(PPh3)]Ru-2 complex nih 1 h chung ah tling tein thlennak a chuahter, cu nih cun a dihlak in 1009 h-1 a chuahter. Cun, 60 °C tiang lumnak ah catalytic cawlcanghnak zong hmuh khawh a si. Gas tthen ah, CO2 le H2 lawng hmuh an si; CO cu hmuh a si lo. A ttha ngaimi mass spectrometry nih N-heterocyclic carbene complexes cu thlennak cawhmi ah a um ti a langhter.
A karh chin lengmangmi thlen khawhmi thazaang le aa thleng lengmangmi nih hin thazaang, lumnak, riantuannak le thilri phurhnak lei ah riantuannak-tluk in thazaang chiahnak thiamnak a herhter1,2. Hydrogen cu a tam bikmi thazaang phurtu pakhat ah ruah a si3, cun ti bantuk organic hydrogen phurtu (LOHCs) cu naite ah hlathlainak ah a biapi bikmi ah an cang, hydrogen kha fawi tein tuah khawhmi phun in pressurization asiloah cryogenic thiamnak he aa pehtlaimi buaibainak um loin chiah khawhnak biakamnak an pek4. ,5,6. An taksa sining ruangah, gasoline le a dang ti bantuk meihol caah a um cangmi thilri phurhnak thilri tampi cu LOHC7,8 phurhnak caah hman khawh a si. Formic acid (FA) a sining nih hydrogen ritnak 4.4%9,10 he hydrogen chiahnak caah ruahchannak a ngeimi a siter. Sihmanhsehlaw, formic acid dehydrogenation caah chuahmi catalytic system hna nih a tlangpi in a tthawngmi organic solvents, ti asiloah a thiangmi formic acid hman a herh,11,12,13,14 cu nih cun condensation tibantuk solvent vapor thleidannak thiamnak hman a herhter khawh, cu nih cun mipi hmannak ah buainak a chuahter khawh. application, a dang thilrit. Hi buainak hi ionic liquids tibantuk a tlawmte lawng a ummi thlihrannak thilri hmannak in tei khawh a si. A hlan ah, kan riantuannak phu nih ionic liquid butylmethylimidazolium acetate (BMIM OAc) cu chawlehnak ah hmuh khawhmi fixing complex Ru-PNP Ru-MACHO phun 15 hmangin hi thil cangmi ah aa tlakmi thlennak a si ti kha an rak langhter. Tahchunhnak ah, FA dehydrogenation kha pehzulh tein a luangmi system ah BMIMA hmangin kan rak langhter, TON cung ah 18,000,000 cu 95°C ah a si. System cheukhat nih a hlan ah TON sang an rak hmuh cang ko nain, tampi nih a rawk khomi organic solvents (THF asiloah DMF tibantuk) asiloah hmanmi additives (bases tibantuk) kha an i bochan. Cu he aa dang in, kan riantuannak nih a taktak ahcun a rawk kho lomi ionic ti (ILs) le chapmi thilri a hman lo.
Hazari le Bernskoetter nih dioxane le LiBF4 a um lio ah Fe-PNP catalyst hmangin 80 °C ah formic acid (FA) dehydrogenation kong an thanh, cu nih cun 1,000,00016 hrawng a ttha ngaimi thlennak nambar (TON) a hmuh. Laurenci nih Ru(II)- complex catalyst TPPPTS cu pehzulh tein FA dehydrogenation system ah a hman. Hi lam nih hin 80 °C17 ah CO tlawmte lawng hmuhmi he FA ti tlawmte lawng a chuahter. Hi riantuannak hi thanchoter chinchin awkah, Pidko nih DMF/DBU le DMF/NHex3 cawhmi ah Ru-PNP clamp catalysts hmangin FA a thlen khawhmi ti tlawmternak kha a langhter, 90 °C18 ah 310,000 in 706,500 tiang TON man a hmuh. Hull, Himeda le Fujita nih binuclear Ir complex catalyst an hlathlai i cu ah cun KHCO3 le H2SO4 an thah hna, CO2 hydrogenation le FA dehydrogenation an i thleng. An system nih 30°C ah hydrogenation, CO2/H2 (1:1), 1 bar pressure le 60 le 90°C19 karlak ah hydrogenation caah 3,500,000 le 308,000 leng TONs an hmuh. Sponholz, Junge le Beller nih 90 °C20 ah CO2 hydrogenation le FA dehydrogenation caah Mn-PNP complex an ser.
Hika ah IL lam kan hman, asinain Ru-PNPs hman loin, Ru-POP catalysts hmannak kha kan hlathlai, kan theih ning ahcun hi kong he pehtlai in a hlan ah langhter a si rih lo.
An ttha tukmi thir-ligand pehtlaihnak (MLC) ruangah, Noyori-phunkhat ruahnak cung ah hram bunhmi amino-PNP clamp complexes cu aa pehtlaimi secondary amino functional groups 21 (Ru-MACHO-BH tibantuk) he a tlangpi in molecule hmete riantuannak cheukhat ah an lar chin lengmang. A lar ngaimi tahchunhnak ah CO22, alkenes le carbonyls hydrogenation, transfer hydrogenation23 le alcohols cohlang loin ti chuahnak24 hna an i tel. PNP clamp ligands N-methylation nih catalyst cawlcanghnak kha a ngolter dih tiah report an tuah cang25, cucu amines nih proton hrampi ah rian an ttuan timi nih a fianter khawh, cucu MLC hmangin catalytic cycle chungah a biapi tukmi a herhmi a si. Sihmanhsehlaw, formic acid dehydrogenation ah aa ralchanhmi sining cu Beller nih naite ah a hmuh, cuka ahcun N-methylated Ru-PNP complexes nih an unmethylated counterparts nakin formic acid catalytic dehydrogenation a ttha deuhmi an langhter taktak26. A hlan i a ummi complex cu amino unit hmangin MLC ah aa tel kho lo caah, MLC, cucaah amino unit nih, a hlan i ruahnak nakin (de)hydrogenation thlennak cheukhat ah a biapi lo deuhmi rian a ttuan kho men ti kha fakpi in a langhter.
POP clamps he tahchunh ahcun, POP clamps i ruthenium complexes pawl cu hi hmun ah hin tling tein hlathlainak an tuah rih lo. POP ligands cu hlanlio tein hydroformylation caah hman a si tawn, cuka ahcun clamping ligands caah 120° hrawng a simi a sining bidentate bite angle si loin chelating ligands bantuk in rian an ttuan, cu hna cu linear le branched products caah thim khawhnak tthaternak caah hman an si cang27,28,29. Cu hnu cun, Ru-POP complexes cu hydrogenation catalysis ah hman a si ti lo, asinain thlennak hydrogenation ah an cawlcanghnak tahchunhnak hna cu a hlan ah an rak langhter cang30. Hika ah Ru-POP complex cu formic acid ti chuahnak caah a ttha ngaimi bawmtu a si ti kan langhter, Beller nih a hmuhmi cu Ru-PNP amine catalyst chung i amino unit cu hi thil sining ah a biapi lo deuh tiah a hmuhmi kha a fehter.
Kan hlathlainak cu a tlangpi formula [RuHCl(POP)(PPh3)] (Fig. 1a) he a tlangpi in thlennak pahnih sernak in aa thawk. Steric le electronic sining remh awkah, dibenzo[b,d]furan cu chawlehnak ah hmuh khawhmi 4,6-bis(diisopropylphosphino) chungin thim a si (Fig. 1b) 31. Hi rian ah hlathlainak tuahmi catalysts pawl cu Whittlesey32 nih a sermi a tlangpi lam hmangin an ser hna, [RuHCl(PP3]3333] aluct/32 adduct ah hman in a hlankan. Thir hramthawknak le POP clamp ligand kha THF ah ti um lo le thli um lo dirhmun ah cawh. Cu thil cangmi cu a senmi in a senmi ah a langmi rong thlennak he aa pehtlai i suimilam 4 chung thlennak asiloah 40°C ah suimilam 72 chung thlennak hnu ah a thiangmi thil a chuahter. THF cu vacuo ah chuah hnu le hexane asiloah diethyl ether in voihnih tawl hnu ah, triphenylphosphine cu chuah a si i thilri cu a senmi vun bantuk in a tammi chuah khawhnak caah a si.
Ru-1 le Ru-2 fonhmi sernak. a) Complex pawl sernak lam. b) Sermi thilri sining.
Ru-1 cu cauk chungin theih a si cang32, cun a dang sining langhternak nih Ru-2 kha a biapi ah a chiah. Ru-2 i 1H NMR spectrum nih hydride pahnih i ligand chung i phosphine atom i cis sining kha a fehter. Peak dt plot (Fig. 2a) nih 2JP-H pehtlaihnak 28.6 le 22.0 Hz a langhter, cu hna cu a hlan report hna i an i ruahchanmi chung ah an um32. Hydrogen decoupled 31P{1H} spectrum (Fig. 2b) ah, 2JP-P coupling constant 27.6 Hz hrawng hmuh a si, cu nih cun clamp ligand phosphines le PPh3 pahnih hi cis-cis an si ti a fehter. Cun, ATR-IR nih 2054 cm-1 ah a langhtermi ruthenium-hydrogen tthencheunak band a langhter. A sining fianternak caah, Ru-2 complex cu X-ray hlathlainak caah a tlingmi tthatnak he khaan lumnak ah thli thletnak in a tlongmi ah a cang (Fig. 3, Supplementary Table 1). Cell pakhat ah cocrystalline benzene unit pakhat he vancung phu P-1 i triclinic system ah a cang. A kau ngaimi P-Ru-P occlusal angle 153.94° a langhter, cucu bidentate DBFphos34 130° occlusal angle nakin a kau deuh ngaingai. 2.401 le 2.382 Å ah, Ru-PPOP pehtlaihnak sauhnak cu Ru in PPh3 pehtlaihnak sauhnak 2.232 Å nakin a sau deuh ngaingai, cucu a laifang 5-ring nih a chuahtermi DBFphos i a kau ngaimi hngawng tthennak nih a chuahpimi a si kho men. Thir laifang i a sining cu a tlangpi in octahedral a si i O-Ru-PPh3 angle 179.5° a si. H-Ru-Cl pehtlaihnak cu a tlarimi a si lo, triphenylphosphine ligand in 175° hrawng a si. Atom hlatnak le pehtlaihnak saunak cu Table 1 ah langhter a si.
Ru-2 NMR spectrum. a) Ru-H dt signal a langhtermi 1H NMR spectrum i Hydride peng. b) 31 P{ 1 H} NMR spectrum nih triphenylphosphine (sen) le POP ligand (hring) in signal a langhter.
Ru-2 dirhmun. Thermal ellipsoids cu 70% a si khomi in langhter an si. A fiang deuh nakhnga, carbon cung i cocrystalline benzene le hydrogen atom pawl cu an hlonh hna.
Formic acid ti a tlawmter khawhnak ding caah complexes hna nih an ngeihmi thilti khawhnak kha tuaktan awkah, aa pehtlaimi PNP-clamp complexes (tahchunhnak ah, Ru-MACHO-BH) hna cu an cawlcang ngaingai15. 0.5 ml (13.25 mmol) formic acid 0.1 mol% (1000 ppm, 13 μmol) ruthenium complex Ru-1 asiloah Ru-2 hmangin 1.0 ml (5.35 mmol) ionic liquid (IL) BMIM OAc (table-fire) hmangin dehydrogenation; Hmanthlak 4);
A tlarimi hmuh khawhnak ding caah, thlennak cu a hmasa bik ah precursor adduct [RuHCl(PPh3)3]·toluene hmangin tuah a si. Cu thlennak cu 60 in 90 °C tiang lumnak ah tuah a si. Hmuh khawhmi thil sawhsawh ning in, 90°C lumnak ah caan saupi cawh hmanh ah complex cu IL ah a tling tein a rawk kho lo, asinain formic acid luhter hnu ah a rawk. 90°C ah, 56% (TOF = 3424 h-1) thlennak cu a hmasa minutes 10 chungah hmuh khawh a si, cun suimilam pathum hnu ah zat thlennak (97%) tluk hmuh khawh a si (entry 1). Lungthawhnak 80 °C tiang tlawmternak nih 10 min hnu ah thlennak kha a cheu nak tam in 24% tiang a zorter (TOF = 1467 h-1, luhnak 2), 70 °C le 60 °C ah 18% le 18% tiang a zorter chin, 6% (luhnak 3 le 4). Caan vialte ah, induction caan pakhat hmanh hmuh a si lo, cu nih cun catalyst cu a tthawngmi phun a si kho men asiloah a tthawngmi phun thlennak cu hi data set hmangin hmuh khawh a si lo tiah a langhter.
A hramthawknak zohfelnak hnu ah, Ru-POP clamp complex Ru-1 le Ru-2 cu thil sining aa khatmi tangah hman an si. 90°C ah, thlennak sang cu hmuh colh a si. Ru-1 nih hneksaknak a hmasa bik minutes 10 chungah 74% thlennak a hmuh (TOFmax = 4525 h-1, luhnak 5). Ru-2 nih tlawmpal a tlawm deuh nain aa khat deuhmi cawlcanghnak a langhter, 10 min chung ah 60% thlennak (TOFmax = 3669 h-1) le 60 min chung ah tling tein thlennak (>99%) (entry 9) a thanchoter. Ru-2 cu a hlan i a rak ummi thir le Ru-1 nakin a tlingmi thlennak ah a ttha deuh ti cu hngalh awk ngai a si. Cucaah, thir hramthawknak le Ru-1 nih thlennak a dih tikah TOFoverall man aa khatmi an ngeih lio ah (330 h-1 le 333 h-1, ciocio), Ru-2 nih TOFoverall 1009 h-1 a ngei.
Ru-1 le Ru-2 cu lumnak thlennak an tuah hna i cu lumnak cu 10 °C in a tlawmbik 60 °C tiang tlawmpal in an zorter (Fig. 3). 90°C ah complex nih a rannak in cawlcanghnak a langhter ahcun, suimilam pakhat chungah a tlingmi thlennak a chuak, cun a niam deuhmi lumnak ah cawlcanghnak cu a zor ngaingai. Py-1 thlennak cu 80°C le 70°C ah 10 min hnu ah 14% le 23% a si, cun 30 min hnu ah 79% le 73% tiang a karh (entries 6 le 7). Hneksaknak pahnih nih suimilam pahnih chungah ≥90% thlennak rate an langhter. Cu bantuk ziaza cu Ru-2 (luhnak 10 le 11) caah hmuh a si. Hngalh a nuammi cu, Ru-1 cu 70 °C ah thlennak a donghnak ah tlawmpal a uk i a dihlak TOF cu 315 h-1 a si i Ru-2 caah 292 h-1 le thir hramthawknak caah 299 h-1 he tahchunh tikah.
Lungthawhnak 60 °C tiang a zor tthan tikah hneksaknak minutes 30 chung ah thlennak pakhat hmanh hmuh a si lo. Ru-1 cu hneksaknak hramthawk ah a niam bik lumnak ah a cawlcang lo ngaingai i a hnu ah a cawlcangh ning a karh, cu nih cun Ru-1 precatalyst cu catalytically a cawlcangmi phun ah aa thlengmi cawlcangh caan a herhnak a langhter. Mah cu lumnak kip ah a si kho ko nain, hneksaknak hramthawk ah minutes 10 cu lumnak sang deuh ah riantuan caan hmuh khawhnak caah a za lo. Cu bantuk ziaza cu Ru-2 caah hmuh a si. le 60 °C ah, hneksaknak a hmasa 10 min chung ah thlennak pakhat hmanh hmuh a si lo. Hlathlainak pahnih ah, carbon monoxide sernak cu kan thilri hmuh khawhnak ri (<300 ppm) chung ah hmuh a si lo ti kha hngalh a biapi, H2 le CO2 lawng hmuh khawhmi thilri an si.
Hi riantuannak phu ah a hlan ah hmuhmi formic acid dehydrogenation hmuhmi tahchunhnak, a tu lio thil sining aiawhtu le Ru-PNP clamp complexes hmannak nih, a thar in sermi Ru-POP clamp cu a PNP counterpart 15 he aa lo ngaimi cawlcanghnak a ngei ti a langhter. POP clamp nih 326 h-1 TOFovertal man aa khatmi a hmuh, cun Ru-1 le 1590 h-1 TOFmax man hmuh a si. pakhat hnu pakhat, 1988 h-1 le 1590 h-1 an si. Ru-2 cu 80 °C ah 1 a si, Ru-1 cu 4525 h-1 a si i Ru-1 cu 90 °C ah 3669 h-1 a si.
Ru-1 le Ru-2 catalysts hmangin formic acid dehydrogenation lumternak thlennak. Thil sining: 13 μmol catalyst, 0.5 ml (13.25 mmol) formic acid, 1.0 ml (5.35 mmol) BMIM OAc.
NMR cu lehrulhnak mechanism hngalhthiamnak caah hman a si. Hydride le phosphine ligands karlak ah 2JH-P ah a biapi tukmi thleidannak a um caah, hi hlathlainak nih a biapi in a chiahmi cu hydride peak kha a si. Ru-1 caah, hydrogenation unit i a tlangpi in dt pattern cu ti tlawmternak minutes 60 chung ah hmuh a si. −16.29 in −13.35 ppm tiang a tanglei lei thlennak a um ko nain, phosphine he aa pehtlaihnak aa thleng lomi cu 27.2 le 18.4 Hz an si (Figure 5, Peak A). Mah cu hydrogen ligand cu cis dirhmun ah a ummi phosphine pathum he aa tlak i ligand dirhmun cu a ttha bikmi lehrulhnak dirhmun tangah suimilam pakhat hrawng IL ah a tlawmpal a fekmi a si tiah a langhter. A tthawngmi downfield thlennak cu chlorinated ligands hlohnak le aa pehtlaimi acetyl-formic acid complexes sernak, NMR tube chung i d3-MeCN complex in situ sernak, asiloah aa pehtlaimi N-heterocycles sernak ruangah a si kho. a fianter. Carbene (NHC) complex. Dehydrogenation reaction chung ah, hi signal a tthawnnak cu a zor thluahmah, cun minutes 180 hnu ah signal cu hmuh khawh a si ti lo. Cu nakin, signal thar pahnih an hmuh. Pakhatnak nih -6.4 ppm (peak B) ah a cangmi dd pattern fiang tein a langhter. Doublet nih 130.4 Hz hrawng a nganmi pehtlaihnak a ngei, cu nih cun phosphine unit pakhat cu hydrogen he aa pehtlai in aa thlen ti a langhter. Mah nih hin POP clamp cu κ2-P,P dirhmun ah remh tthan a si tinak a si kho. Catalysis a donghnak ah hi complex a langhnak nih hin hi phun nih hin caan saupi chung riantuan lonak lam a hruai i, catalyst sink a ser ti kha a langhter men lai. Khatlei kam in, a tlawmmi chemical thlennak nih dihydrogenous phun a si kho men tiah a langhter15. A pahnihnak sang bik cu -17.5 ppm ah a um. A tthencheunak cu theih a si lo nain, 17.3 Hz a tlawmmi pehtlaihnak a ngeimi pathum a si tiah kan zumh, cucu hydrogen ligand nih POP clamp i phosphine ligand lawng a pehtlaih ti a langhter, cu nih cun triphenylphosphine (peak C) chuahnak zong a langhter. A dang ligand nih a thlen khawh, cu bantuk cu acetyl phu asiloah ionic ti chungin a hmun ah sermi NHC tibantuk a si. PPh3 i tthencheunak cu -5.9 ppm ah a fekmi singlet nih a langhter chin. Ru-1 31P{1H} spectrum ah 90 °C ah minutes 180 hnu ah (a dang theihternak zoh).
Formic acid dehydrogenation lio ah Ru-1 1H NMR spectrum i hydride pengtlang. Reaction dirhmun: 0.5 ml formic acid, 1.0 ml BMIM OAc, 13.0 μmol catalyst, 90 °C. NMR cu MeCN-d 3 in lak a si, 500 μl deuterated solvent, 10 μl hrawng a simi thlennak cawhmi.
Catalytic system ah a cawlcangmi phun a um le um lo fehternak caah, 90 °C ah 10 min chung formic acid thun hnu ah Ru-1 i a sangmi resolution mass spectrometry (HRMS) hlathlainak tuah a si. Mah nih hin thlennak cawhmi ah chlorine ligand precatalyst a ngei lomi phun an um ti a langhter. cun NHC complex pahnih, an i ruahchanmi dirhmun cu hmanthlak 6 ah hmuh khawh a si. Aa pehtlaimi HRMS spectrum cu Supplementary hmanthlak 7 ah hmuh khawh a si.
Hi data cungah hram bunh in, Beller nih a chuahpimi he aa lo mi intrasphere lehrulhnak mechanism kan chuahpi, cu ah cun N-methylated PNP clamps nih mah bantuk lehrulhnak kha a chuahter. Ionic liquids telh loin hneksaknak dang nih zeihmanh cawlcanghnak a langhter lo, cucaah a direct in i telnak cu a herhmi a lo. Ru-1 le Ru-2 riantuannak cu chloride tthennak in a chuak i cu hnu ah NHC chapnak le triphenylphosphine tthennak (Scheme 1a) nih a zulh tiah kan ruah. Hi cawlcanghnak hi saram phun vialte ah HRMS hmangin a hlan ah hmuh a si cang. IL-acetate cu formic acid nakin a tthawng deuhmi Bronsted base a si i a hnu bik kha fakpi in a deprotonate khawh35. Catalytic cycle (Scheme 1b) chungah, NHC asiloah PPh3 a ngeimi a cawlcangmi phun A cu formate hmangin phun B ser awkah an i fonh tiah kan ruah. Hi complex kha C ah remh ṭhannak nih a donghnak ah CO2 le trans-dihydrogen complex D a chuahter. dihydro complex E ser cu Beller nih N-methylated PNP clamp homologues hmangin a chuahpimi a biapi bikmi step he aa lo. Cun, EL = PPh3 aa khatmi cu a hlan ah sodium chiti he chloride chuah hnu ah Ru-1 hmangin hydrogen boruak ah stoichiometric reaction in sermi a si. Hydrogen chuahnak le formate i fonhnak nih A a pek i a dih.
Fixing complex Ru-POP Ru-1 hmangin formic acid dehydrogenation intrasphere reaction caah mechanism pakhat an chuahpi.
Complex thar [RuHCl(iPr-dbfphos)(PPh3)] cu ser a si cang. Cu complex cu NMR, ATRIR, EA le X-ray diffraction hlathlainak in single crystals in thleidan a si. Formic acid kha CO2 le H2 ah ti tlawmternak ah Ru-POP pincer complexes hman hmasa bik hlawhtlinnak zong kan thanh. Thir hramthawknak nih aa lo ngaimi cawlcanghnak (3424 h-1 tiang) a hmuh ko nain, complex nih 90 °C ah 4525 h-1 tiang a sangbik thlennak frequency a phan. Cun, 90 °C ah, complex thar [RuHCl(iPr-dbfphos)(PPh3)] nih formic acid dehydrogenation dih khawhnak ding caah a dihlak in a zuang caan (1009 h-1) a hmuh, cucu thir hlan deuh (330 h-1) nakin a sang deuh ngaingai. le a hlan ah report tuahmi complex [RuHCl(xantphos)(PPh3)] (333 h-1). Cu bantuk thil sining tangah, catalytic tthatnak cu Ru-PNP clamp complex he tahchunh khawh a si. HRMS data nih a tlawmte lawng a si ko nain, thlennak cawhmi ah carbene complex a um ti a langhter. A tu ah carbene complexes nih a chuahpimi thlennak kong kan hlathlai cuahmah lio a si.
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