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Ko te waikawa formic tētahi o ngā mea tino whai hua mō te rokiroki roa o te hauwai wai. Kei konei mātou e whakaatu ana i tētahi raupapa o ngā matatini rawhi ruthenium hou me te tātai whānui [RuHCl(POP)(PPh3)] mā te whakamahi i ngā ligands rawhi tridentate POP momo xanthos e wātea ana i te mākete, e ngāwari ana rānei te hanga. I whakamahia e mātou ēnei matatini hei tango i te hauwai o te waikawa formic hei whakaputa i te CO2 me te H2 i raro i ngā āhuatanga ngawari, kore-reflux mā te whakamahi i te wai ionic BMIM OAc (1-butyl-3-methylimidazolium acetate) hei whakarewa. Mai i te tirohanga o te auau hurihuri mōrahi, ko te whakakorikori tino whai hua ko te matatini [RuHCl(xantphos)(PPh3)]Ru-1 e mōhiotia ana i roto i ngā tuhinga, he 4525 h-1 te auau hurihuri mōrahi i te 90 °C mō te 10 meneti. Ko te tere i muri i te tahuritanga he 74%, ā, i oti te tahuritanga i roto i ngā haora 3 (>98%). I tētahi atu taha, ko te matū whakatere me te mahi whānui pai rawa atu, ko te matatini hou [RuHCl(iPr-dbfphos)(PPh3)]Ru-2, e whakatairanga ana i te huringa katoa i roto i te 1 hāora, ka hua ake he tere hurihanga whānui o te 1009 h-1. Hei tāpiri, i kitea anō hoki te mahi whakatere i ngā pāmahana tae atu ki te 60 °C. I roto i te wāhanga hau, ko te CO2 me te H2 anake i kitea; kāore i kitea te CO. I whakaatuhia e te ine papatipu taumira teitei te aroaro o ngā matatini N-heterocyclic carbene i roto i te ranunga tauhohenga.
Ko te tipu haere o te wāhi mākete o te pūngao whakahou me tōna rerekētanga kua arahi ki te tono mō ngā hangarau rokiroki pūngao tauine ahumahi i roto i ngā rāngai hiko, wera, ahumahi me te kawe waka1,2. E kiia ana ko te hauwai tētahi o ngā kaikawe pūngao tino nui3, ā, kua noho ko ngā kaikawe hauwai waro wai (LOHC) hei arotahi rangahau i ngā wā tata nei, e tuku ana i te oati ki te penapena hauwai i roto i te āhua ngāwari ki te tukatuka me te kore he raruraru e pā ana ki te pēhanga, ki ngā hangarau cryogenic rānei4. ,5,6. Nā ō rātou āhuatanga ā-tinana, he maha ngā hanganga kawe waka o nāianei mō te penehīni me ētahi atu wahie wai ka taea te whakamahi hei kawe i te LOHC7,8. Ko ngā āhuatanga ā-tinana o te waikawa formic (FA) e waiho ana hei kaitono whai hua mō te rokiroki hauwai me te ihirangi taumaha hauwai o te 4.4%9,10. Heoi, ko ngā pūnaha catalytic kua whakaputaina mō te tango hauwai waikawa formic e hiahia ana ki te whakamahi i ngā whakarewa waro ahua, te wai, te waikawa formic parakore rānei,11,12,13,14 e hiahia ana pea ki te whakamahi i ngā tikanga wehenga kohu whakarewa pēnei i te hauhautanga, ka arahi pea ki ngā raruraru i roto i ngā tono kaihoko. tono, kawenga tāpiri. Ka taea te whakakore i tēnei raruraru mā te whakamahi i ngā whakarewa he iti noa te pēhanga kohu, pērā i ngā wai ionic. I mua, i whakaaturia e tā mātou rōpū mahi ko te wai ionic butylmethylimidazolium acetate (BMIM OAc) he whakarewa tika i roto i tēnei tauhohenga mā te whakamahi i te matatini whakapiri Ru-PNP Ru-MACHO momo 15 e wātea ana i te hokohoko. Hei tauira, i whakaaturia e mātou te tangohanga hauwai FA i roto i tētahi pūnaha rere tonu mā te whakamahi i te BMIM OAc, ā, i tutuki ai he TON neke atu i te 18,000,000 i te 95°C. Ahakoa kua tutuki i ētahi pūnaha te TON teitei i mua, he maha kua whakawhirinaki ki ngā whakarewa waro pūngoi (pērā i te THF, i te DMF rānei) me ngā tāpiringa i whakamahia (pērā i ngā turanga). He rerekē, ko tā mātou mahi he whakamahi i ngā wai ionic kore-pūngoi (IL) me te kore tāpiringa.
I kōrero a Hazari rāua ko Bernskoetter mō te tango i te hauwai o te waikawa formic (FA) i te 80 °C mā te whakamahi i te whakakorikori Fe-PNP i te aroaro o te dioxane me te LiBF4, ā, i tutuki ai he tau hurihuri whakamiharo (TON) tata ki te 1,000,00016. I whakamahia e Laurenci he whakakorikori matatini Ru(II)-TPPPTS i roto i te pūnaha tango hauwai FA tonu. Nā tēnei tikanga i tata oti te tango hauwai FA me te iti noa o ngā tohu o te CO i kitea i te 80 °C17. Hei whakatairanga ake i tēnei mara, i whakaatu a Pidko i te tango hauwai whakahurihuri o te FA mā te whakamahi i ngā whakakorikori rawhi Ru-PNP i roto i ngā ranunga DMF/DBU me DMF/NHex₃, ā, i tutuki ai ngā uara TON o te 310,000 ki te 706,500 i te 90 °C18. I ako a Hull, Himeda rāua ko Fujita i tētahi whakakorikori matatini binuclear Ir i patua ai te KHCO3 me te H2SO4, me te whakawhiti i te hauwai CO2 me te tango hauwai FA. I tutuki i ā rātou pūnaha ngā TON neke atu i te 3,500,000 me te 308,000 mō te whakahauwai i te 30°C, te CO2/H2 (1:1), te pēhanga 1 pae me te tango i te hauwai i waenga i te 60 me te 90°C19. I whakawhanakehia e Sponholz, Junge me Beller tētahi matatini Mn-PNP mō te whakahauwai CO2 whakahurihuri me te tango i te hauwai FA i te 90 °C20.
I konei i whakamahia e mātou te huarahi IL, engari hei utu mō te whakamahi i ngā Ru-PNP, i tūhuratia e mātou te whakamahinga o ngā whakakorikori Ru-POP, kāore anō kia whakaaturia i mua mō tēnei kaupapa.
Nā te pai o te hononga whakarewa-ligand (MLC), ko ngā matatini rawhi amino-PNP e hangai ana ki ngā ariā momo-Noyori me ngā rōpū mahi amino tuarua e taunekeneke ana 21 (pērā i a Ru-MACHO-BH) kei te piki haere te rongonui i roto i ētahi mahi ngota iti. Ko ngā tauira rongonui ko te CO22, te hauwai o ngā alkenes me ngā carbonyls, te hauwai whakawhiti23 me te tango hauwai kore-whakaae o ngā waipiro24. Kua pūrongohia ka taea e te N-methylation o ngā ligands rawhi PNP te aukati katoa i te mahi whakakorikori25, ka taea te whakamārama mā te meka ko ngā amines te pūtake proton, he whakaritenga nui i te huringa whakakorikori mā te whakamahi i te MLC. Heoi, i kitea tata nei e Beller te ia rerekē i roto i te tango hauwai waikawa formic, i reira i whakaatu ai ngā matatini Ru-PNP N-methylated i te tango hauwai pai ake o te waikawa formic i ō rātou hoa kore-methylated26. I te mea kāore e taea e te matatini o mua te whai wāhi ki te MLC mā te waeine amino, e kī ana tēnei he iti ake te hiranga o te mahi a te MLC, nō reira ko te waeine amino, i roto i ētahi huringa (whakakore) hauwai i tērā i whakaarohia i mua.
Ki te whakatauritea ki ngā rawhi POP, kāore anō kia tino rangahauhia ngā matatini ruthenium o ngā rawhi POP i tēnei wāhanga. Ko ngā ligands POP i whakamahia i ngā wā o mua mō te hydroformylation, e mahi ana rātou hei ligands chelating kaua ki te koki ngau bidentate āhua o te 120° mō ngā ligands rawhi, kua whakamahia hei arotau i te whiriwhiringa mō ngā hua raina me ngā hua peka27,28,29. Mai i taua wā, kāore i te maha ngā whakamahinga o ngā matatini Ru-POP i roto i te catalysis hydrogenation, engari kua pūrongohia ngā tauira o tā rātou mahi i roto i te hydrogenation whakawhiti30. I konei ka whakaatuhia e mātou he kaiwhakaoho whai hua te matatini Ru-POP mō te tango i te hauwai o te waikawa formic, e whakaū ana i te kitenga a Beller he iti ake te hiranga o te waeine amino i roto i te kaiwhakaoho amine Ru-PNP matarohia i roto i tēnei tauhohenga.
Ka tīmata tā mātou rangahau mā te hanga i ngā whakakorikori e rua me te tauira whānui [RuHCl(POP)(PPh3)] (Pikitia 1a). Hei whakarerekē i te hanganga steric me te hanganga hiko, i tīpakohia te dibenzo[b,d]furan mai i te 4,6-bis(diisopropylphosphino) e wātea ana i te hokohoko (Pikitia 1b) 31. I hangahia ngā whakakorikori i akohia i roto i tēnei mahi mā te whakamahi i tētahi tikanga whānui i whakawhanakehia e Whittlesey32, me te whakamahi i te tāpiri [RuHCl(PPh3)3]•toluene33 hei mua. Whakaranua te mua whakarewa me te ligand clamp POP ki roto i te THF i raro i ngā āhuatanga tino kore wai me te anaerobic. I haere tahi te tauhohenga me te huringa tae nui mai i te papura pouri ki te kōwhai, ā, i puta he hua parakore i muri i te 4 hāora o te reflux, i te 72 hāora rānei o te reflux i te 40°C. I muri i te tango i te THF i roto i te vacuum me te horoinga rua ki te hexane, ki te diethyl ether rānei, i tangohia te triphenylphosphine hei hanga i te hua hei paura kōwhai me te hua nui.
Te Hanganga o ngā matatini Ru-1 me Ru-2. a) Te Tikanga Hanganga o ngā matatini. b) Te Hanganga o te matatini kua Hangaia.
Kua mōhiotia kētia a Ru-1 mai i ngā tuhinga32, ā, ko te whakaahuatanga anō e aro ana ki a Ru-2. Nā te whānuitanga 1H NMR o Ru-2 i whakaū te whirihoranga cis o te ngota phosphine i roto i te ligand o te takirua hydride. Ko te kauwhata tihi dt (Pikitia 2a) e whakaatu ana i ngā pūmau hononga 2JP-H o te 28.6 me te 22.0 Hz, kei roto i te awhe e tumanakohia ana o ngā pūrongo o mua32. I roto i te whānuitanga 31P{1H} kua wehea te hauwai (Pikitia 2b), i kitea he pūmau hononga 2JP-P o te 27.6 Hz, e whakaū ana ko ngā phosphine ligand clamp me te PPh3 he cis-cis. Hei tāpiri, e whakaatu ana a ATR-IR i tētahi roopu totoro ruthenium-hauwai āhuatanga i te 2054 cm-1. Mō ētahi atu whakamārama hanganga, i whakatiotia te matatini Ru-2 mā te horapa o te kohu i te pāmahana rūma me te kounga e ranea ana mō ngā rangahau hihi-X (Pikitia 3, Ripanga Tāpiri 1). Ka whakatio i roto i te pūnaha triclinic o te rōpū wāhi P-1 me te kotahi waeine benzene cocrystalline mō ia pūtau waeine. He whānui te koki occlusal P-Ru-P o te 153.94°, he whānui ake i te koki occlusal 130° o te bidentate DBFphos34. I te 2.401 me te 2.382 Å, he roa ake te roa o te here Ru-PPOP i te roa o te here Ru ki te PPh3 o te 2.232 Å, he hua pea tēnei o te koki whānui o te tuara kai o DBFphos i puta mai i tana mowhiti-5 pokapū. Ko te āhua o te pokapū whakarewa he octahedral te nuinga me te koki O-Ru-PPh3 o te 179.5°. Kāore te taunga H-Ru-Cl i te tino rārangi, me te koki tata ki te 175° mai i te ligand triphenylphosphine. Kua whakarārangihia ngā tawhiti ngota me ngā roa here ki te Ripanga 1.
Te whānuitanga NMR o Ru-2. a) Te rohe hydride o te whānuitanga 1H NMR e whakaatu ana i te tohu Ru-H dt. b) Te whānuitanga 31 P{ 1 H} NMR e whakaatu ana i ngā tohu mai i te triphenylphosphine (kikorangi) me te POP ligand (kakariki).
Hanganga o Ru-2. E whakaaturia ana ngā porowhita wera me te tūponotanga 70%. Hei mārama ake, kua tangohia ngā ngota benzene me te hauwai cocrystalline i runga i te waro.
Hei aromatawai i te kaha o ngā matatini ki te tango i te hauwai o te waikawa formic, i tīpakohia ngā āhuatanga tauhohenga i raro i te kaha o ngā matatini PNP-rawhi e rite ana (hei tauira, Ru-MACHO-BH)15. Te tango i te hauwai o te 0.5 ml (13.25 mmol) waikawa formic mā te whakamahi i te matatini ruthenium 0.1 mol% (1000 ppm, 13 µmol) Ru-1, Ru-2 rānei mā te whakamahi i te 1.0 ml (5.35 mmol) wai ionic (IL) BMIM OAc (tīpurangi-ahua) 2; Pikitia 4);
Hei whiwhi i te paerewa, i whakahaerea tuatahitia te tauhohenga mā te whakamahi i te tāpiringa mua [RuHCl(PPh3)3]·toluene. Ka whakahaerea te tauhohenga i te pāmahana mai i te 60 ki te 90 °C. E ai ki ngā tirohanga tirohanga māmā, kāore i taea te rewa katoa o te matatini ki roto i te IL ahakoa te whakaoho roa i te pāmahana o te 90°C, engari i puta te rewa i muri i te whakaurunga o te waikawa formic. I te 90°C, i tutuki te huringa o te 56% (TOF = 3424 h-1) i roto i ngā meneti 10 tuatahi, ā, i tutuki te huringa tata ki te rahinga (97%) i muri i ngā haora e toru (whakaurunga 1). Mā te whakaiti i te pāmahana ki te 80 °C ka whakaitihia te huringa mā te neke atu i te haurua ki te 24% i muri i te 10 meneti (TOF = 1467 h-1, whakaurunga 2), ka whakaitihia anō ki te 18% me te 18% i te 70 °C me te 60 °C, ia 6% (whakaurunga 3 me te 4). I ngā wā katoa, kāore i kitea he wā whakaoho, e tohu ana tera pea he momo tauhohe te whakakorikori, he tere rawa rānei te hurihanga o ngā momo tauhohe ki te kitea mā te whakamahi i tēnei huinga raraunga.
I muri i te aromatawai i ngā matū mua, i whakamahia ngā matatini rawhi Ru-POP, a Ru-1 me Ru-2, i raro i ngā āhuatanga ōrite. I te 90°C, i kitea tonutia te huringa teitei. I eke a Ru-1 ki te 74% te huringa i roto i ngā meneti 10 tuatahi o te whakamātautau (TOFmax = 4525 h-1, whakaurunga 5). I whakaatu a Ru-2 i te mahi iti ake engari he rite tonu, e whakatairanga ana i te huringa 60% i roto i te 10 meneti (TOFmax = 3669 h-1) me te huringa katoa i roto i te 60 meneti (>99%) (whakaurunga 9). He mea nui kia mōhiotia he pai ake a Ru-2 i te konganuku mua me Ru-1 i te huringa katoa. Nō reira, ahakoa he rite ngā uara TOFoverall o te matū mua me Ru-1 i te otinga o te tauhohenga (330 h-1 me 333 h-1, ia), ko te TOFoverall a Ru-2 he 1009 h-1.
Kātahi ka tukuna a Ru-1 me Ru-2 ki tētahi whakarerekētanga pāmahana, ā, ka whakaitihia mārire te pāmahana i roto i ngā pikinga 10 °C ki te iti rawa o te 60 °C (Pikitia 3). Mena i te 90°C i whakaatu te matatini i te mahi tonu, tata tonu te hurihanga i roto i te haora, kātahi ka heke tere te mahi i ngā pāmahana iti iho. Ko te hurihanga o Py-1 he 14% me te 23% i muri i te 10 meneti i te 80°C me te 70°C, ia, ā, i muri i te 30 meneti ka piki ki te 79% me te 73% (ngā whakaurunga 6 me te 7). I whakaatuhia e ngā whakamātautau e rua he tere hurihanga ≥90% i roto i ngā haora e rua. I kitea te whanonga ōrite mō Ru-2 (ngā whakaurunga 10 me te 11). He mea whakamīharo, he paku kaha te Ru-1 i te mutunga o te tauhohenga i te 70 °C me te TOF katoa o te 315 h-1 i whakaritea ki te 292 h-1 mō Ru-2 me te 299 h-1 mō te matū whakarewa.
Nā te hekenga anō o te pāmahana ki te 60 °C, kāore i kitea he huringa i roto i ngā meneti 30 tuatahi o te whakamātautau. Kāore i tino kaha te mahi a Ru-1 i te pāmahana iti rawa i te tīmatanga o te whakamātautau, ā, i muri mai ka piki ake te mahi, e tohu ana i te hiahia mō tētahi wā whakahohenga i roto i te wā e hurihia ai te kaiwhakaoho Ru-1 hei momo kaha whakakorikori. Ahakoa ka taea tēnei i ngā pāmahana katoa, kāore i ranea te 10 meneti i te tīmatanga o te whakamātautau ki te kite i tētahi wā whakahohenga i ngā pāmahana teitei ake. I kitea he whanonga ōrite mō Ru-2. I te 70 me te 60 °C, kāore i kitea he huringa i roto i ngā meneti 10 tuatahi o te whakamātautau. He mea nui kia mōhio i roto i ngā whakamātautau e rua, kāore i kitea te hanganga hauota waro i roto i te rohe kitenga o tā mātou taputapu (<300 ppm), ko te H2 me te CO2 anake ngā hua i kitea.
Ko te whakataurite i ngā hua o te tango waikawa formic i whiwhihia i mua i roto i tēnei rōpū mahi, e whakaatu ana i te āhua o te hangarau me te whakamahi i ngā matatini rawhi Ru-PNP, i whakaatu ko te rawhi Ru-POP hou i hangaia he rite te mahi ki tōna hoa PNP 15. I te mea i tutuki i te rawhi te RPM o te 500-1260 h-1 i roto i ngā whakamātautau puranga, i tutuki i te rawhi POP hou te uara TOFovertal rite o te 326 h-1, ā, i kitea ngā uara TOFmax o Ru-1 me te 1590 h-1. Ko te Ru-2 he 1 i te 80 °C, ko te Ru-1 he 4525 h-1, ā, ko te Ru-1 he 3669 h-1 i te 90 °C.
Te tirotiro i te pāmahana o te tangohanga waikawa formic mā te whakamahi i ngā whakakōkī Ru-1 me Ru-2. Ngā āhuatanga: whakakōkī 13 µmol, 0.5 ml (13.25 mmol) waikawa formic, 1.0 ml (5.35 mmol) BMIM OAc.
Ka whakamahia te NMR hei mārama ki ngā tikanga tauhohenga. Nā te mea he tino rerekētanga nui kei roto i te 2JH-P i waenga i ngā ligands hydride me ngā ligands phosphine, ko te arotahi o tēnei rangahau kei runga i te tihi hydride. Mō Ru-1, i kitea he tauira dt noa o te waeine hydrogenation i roto i ngā meneti 60 tuatahi o te dehydrogenation. Ahakoa he nekehanga nui ki raro mai i te −16.29 ki te −13.35 ppm, ko ōna pūmau hononga ki te phosphine he 27.2 me te 18.4 Hz, ia (Pikitia 5, Teitei A). He rite tēnei ki ngā phosphine e toru kei reira te ligand hauwai i roto i te whirihoranga cis, ā, e kī ana he pumau te whirihoranga ligand i roto i te IL mō te haora pea i raro i ngā āhuatanga tauhohenga kua arotauhia. Ko te nekehanga kaha ki raro pea nā te whakakorenga o ngā ligands chlorinated me te hanganga o ngā matatini waikawa acetyl-formic e rite ana, te hanganga in situ o te matatini d3-MeCN i roto i te ngongo NMR, te hanganga rānei o ngā N-heterocycles e rite ana. whakamārama. Te matatini o te warowaihā (NHC). I te wā o te tauhohenga tango-waihā, ka heke haere tonu te kaha o tēnei tohu, ā, i muri i te 180 meneti kāore i kitea te tohu. Engari, e rua ngā tohu hou i kitea. Ko te tuatahi e whakaatu ana i tētahi tauira dd mārama e puta ana i te -6.4 ppm (tihi B). He nui te pūmau hononga o te takirua, tata ki te 130.4 Hz, e tohu ana kua neke tētahi o ngā waeine phosphine e pā ana ki te hauwai. Ko te tikanga pea tēnei kua whakaritea anōtia te rawhi POP ki tētahi whirihoranga κ2-P,P. Ko te putanga mai o tēnei matatini i te mutunga o te whakakorikori ka tohu pea ka arahi tēnei momo ki ngā ara whakakore i roto i te wā, ka hanga he totohu whakakorikori. I tētahi atu taha, ko te nekehanga matū iti e kī ana he momo dihydrogenous pea15. Ko te tuarua o ngā tihi hou kei te -17.5 ppm. Ahakoa kāore i te mōhiotia tōna takai, e whakapono ana mātou he toru-ira me te pūmau hononga iti o te 17.3 Hz, e tohu ana ko te ligand hauwai ka herea anake ki te ligand phosphine o te rawhi POP, e tohu ana hoki i te tukunga o te triphenylphosphine (te tihi C). Ka taea te whakakapi ki tētahi atu ligand, pērā i te rōpū acetyl, i te NHC rānei i hangaia i roto i te wāhi mai i te wai ionic. Ko te wehenga o PPh3 ka tohua anō e te kotahi-ira kaha i te -5.9 ppm. i roto i te whānuitanga 31P{1H} o Ru-1 i muri i te 180 meneti i te 90 °C (tirohia ētahi atu kōrero).
Te rohe haidīri o te whānuitanga 1H NMR o Ru-1 i te wā o te tango hauwai o te waikawa formic. Ngā tikanga tauhohenga: 0.5 ml waikawa formic, 1.0 ml BMIM OAc, 13.0 µmol whakakorikori, 90 °C. I tangohia te NMR mai i te MeCN-d 3, 500 μl o te whakarewa tango-whakakorikori, tata ki te 10 μl o te ranunga tauhohenga.
Hei whakaū anō i te aroaro o ngā momo hohe i roto i te pūnaha whakaterenga, i whakahaerehia te tātaritanga ine papatipu taumira teitei (HRMS) o Ru-1 i muri i te werohanga o te waikawa formic mō te 10 meneti i te 90 °C. E whakaatu ana tēnei i te aroaro o ngā momo kāore he kaiwhakaoho ligand chlorine i roto i te ranunga tauhohenga, me ngā matatini NHC e rua, ko ngā hanganga whakapae e whakaaturia ana i te Pikitia 6. Ka kitea te ine HRMS e rite ana i te Pikitia Tāpiri 7.
I runga i ēnei raraunga, ka whakaarohia e mātou he tikanga tauhohenga ā-roto e rite ana ki tā Beller i whakatakoto ai, e whakakorikori ana ngā rawhi PNP N-methylated i te tauhohenga kotahi. Kāore i whakaatuhia he mahi i roto i ētahi atu whakamātautau kāore i whakaurua ngā wai ionic, nō reira me whai wāhi tika mai. E whakapae ana mātou ka puta te whakahohenga o Ru-1 me Ru-2 mā te wehenga o te chloride, ā, ka whai ake ko te tāpiri pea o te NHC me te wehenga o te triphenylphosphine (Kaupapa 1a). Kua kitea tēnei whakahohenga i roto i ngā momo katoa mā te whakamahi i te HRMS. He kaha ake te IL-acetate i te waikawa formic, ā, ka taea e ia te tango i te protonation o muri35. E whakapae ana mātou i te wā o te huringa whakaterenga (Kaupapa 1b), ka honoa ngā momo hohe A e mau ana i te NHC, i te PPh3 rānei mā te formate hei hanga i ngā momo B. Ko te whirihoranga anō o tēnei matatini ki te C ka hua ake te tukunga o te CO2 me te matatini trans-dihydrogen D. Ko te whakapūtātanga o te waikawa ki roto i te matatini dihydro me te waikawa acetic i hangaia i mua hei hanga i te matatini dihydro E he rite ki te taahiraa matua i whakatakotoria e Beller mā te whakamahi i ngā hononga rawhi PNP N-methylated. Hei tāpiri, i hangaia i mua he rite o te matatini EL = PPh3 mā te tauhohenga stoichiometric mā te whakamahi i te Ru-1 i roto i te hau hauwai i muri i te tangohanga o te pūhaumāota me te tote konutai. Ko te tango i te hauwai me te honotanga o te formate ka whakarato i te A, ā, ka oti te huringa.
Kua whakaarohia he tikanga mō te tauhohenga ā-roto o te tangohanga hauwai waikawa formic mā te whakamahi i te matatini whakapiri Ru-POP Ru-1.
Kua hangaia he matatini hou [RuHCl(iPr-dbfphos)(PPh3)]. I whakaahuatia te matatini mā te NMR, ATRIR, EA me te tātaritanga hihi-X o ngā tioata takitahi. Ka ripoatahia hoki e mātou te tono angitu tuatahi o ngā matatini Ru-POP pincer i roto i te tangohanga hauwai o te waikawa formic ki te CO2 me te H2. Ahakoa i tutuki i te matū whakarewa te mahi rite (tae atu ki te 3424 h-1), i eke te matatini ki te auau huringa mōrahi tae atu ki te 4525 h-1 i te 90 °C. I tua atu, i te 90 °C, i tutuki i te matatini hou [RuHCl(iPr-dbfphos)(PPh3)] te wā rere katoa (1009 h-1) hei whakaoti i te tangohanga hauwai o te waikawa formic, he nui ake i tērā o te matū whakarewa (330 h-1). me te matatini i ripoatahia i mua [RuHCl(xantphos)(PPh3)] (333 h-1). I raro i ngā āhuatanga ōrite, he rite te whai huatanga o te whakaterenga ki tērā o te matatini rawhi Ru-PNP. E whakaatu ana ngā raraunga HRMS i te aroaro o te matatini waropene i roto i te ranunga tauhohenga, ahakoa he iti noa iho. Kei te ako mātou i ngā pānga whakaterenga o ngā matatini waropene i tēnei wā.
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