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Deciphering key intermediates Collection home page

The identification of catalytic intermediates in the conversion of carbon dioxide is vital for improved catalyst design and optimization of structure–reactivity relationships, but remains elusive. Here, we report that intermolecular hydrogen bonding interactions between an epoxy alcohol, water and the catalyst structure are crucial towards the formation of a cyclic carbonate from carbon dioxide. A combination of multiple in situ and ex situ techniques including substrate labelling, kinetic studies, computational analysis, operando infrared spectroscopy and X-ray diffraction was applied to identify and support the structural connectivities of several previously unknown intermediates. An epoxy alcohol–water cluster formed by hydrogen bonding was identified as the initial intermediate able to trap CO2 and an elusive alkyl carbonate anion was also detected. The synergistic spectroscopic and computational analysis shown here offers a unique insight under operando conditions, as well as a useful analytical blueprint for key suggested intermediates in other mechanistically related CO2 conversion processes.

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Please use this identifier to cite or link to this collection: DOI: 10.19061/iochem-bd-1-58

This dataset derived results are published in:

Manuscript title: Deciphering key intermediates in the transformation of carbon dioxide into heterocyclic products

Journal: Nature Catalysis

View as
  • ROOT
    • Extra_Calculations
      • Alcohol_AcidityAnalysis
        • Catalyst
        • Ep_Alkoxide
        • Free_Alkoxide
          • FAIL
          • Frozen
        • Glycidol
        • H_Cat
        • Hydronium
        • Hydroxide
        • IC
        • Water
      • Aldehyde
        • Int
          • No_H
      • CCSD
        • IC
        • TS
      • CyclohexeneOx_Tests
        • Al_OH2
        • Before
          • Scan2
            • Frozen_OH
              • Zoom
                • Guess
                  • Frozen
                    • Opt
                  • TS
            • Zoom
              • Frozen_OH
              • Next
        • From_Back
          • Scan
            • Zoom1
            • Zoom2
            • Zoom3
        • Frozen_FromTS
      • DFTAnalysis_Concerted_TS_CC
        • B3LYP_D3
          • DZP
            • Guess
          • IC
          • Reactants
            • Al
            • CO2
            • Glycidol
            • Water
        • B3LYP_D3BJ
          • IC
          • Reactants
            • Al
            • CO2
            • Glycidol
            • Water
        • B97_EmpD3
          • IC
          • Reactants
            • Al
            • CO2
            • Glycidol
            • Water
          • TS
            • Freq
        • BP86
          • IC
          • Reactants
            • Al
            • CO2
            • Glycidol
            • Water
        • Bp86_D3
          • DZP
          • IC
          • Reactants
            • Al
            • CO2
            • Glycidol
            • Water
        • M06
          • IC
          • Reactants
            • Al
            • CO2
            • Glycidol
            • Water
        • M062X
          • IC
          • Reactants
            • Al
            • CO2
            • Glycidol
            • Water
          • TS
        • wB97xD
          • Down
            • Down_FAIL
            • Down_H2O
              • FAIL
              • Frozen2
              • Frozen3
                • Opt_FAIL
            • Scan_Down
              • B97D3
              • wB97XD_FAIL
            • Scan_Down2
              • B97d3
                • FAIL2
                • Scan2_FAIL
                • Scan3
                • Scan4_FAIL
              • FAIL
          • FAIL
          • Freq_FAIL
            • Opt
          • Frozen
            • Opt_FAIL
          • Frozen_CO2_FAIL
          • Scan_2D
            • FAIL
            • TS
              • Guess_Freq
              • TZ2P
                • Scan
                  • Zoom
      • Dimer
        • Alkoxide
        • Alkoxide_1
        • CC
        • CC_H
        • Carbonate
          • Frozen
        • Carbonate_2
        • Dimer
        • Ensemble
        • IC
      • Epoxide_Isomerization
        • Alk_Isom
          • Zoom
            • Zoom
              • Guess_TS_FAIL
              • TS_Frozen_FAIL
                • Frozen2_FAIL
        • FAIL
      • IC_Isomerization
        • Alkoxide
          • Zoom
            • Zoom_Zoom
              • Back
              • Forward
                • Guess
                  • Frozen_FAIL
                  • Opt_FAIL
        • Alkoxide2
          • Zoom
        • Zoom
          • Guess_FromScan
          • Guess_Modified
      • Ligand_BasicityAnalysis
        • Al_OH
        • Al_OH2
        • Guess_TS_H
          • Guess
        • TS_H
      • M06_2X_Tests
        • Al
        • CO2
        • Glycidol
        • IC_M062X
        • TS_M062X
        • Water
      • NBO
        • Alkoxide
        • IC
      • O_Al_BondAnalysis
        • Ep
          • Ep
        • Ox
          • Ox
        • THF
          • THF
      • Protonated_Cat
        • B97D3
        • wB97xD
      • TS_PM6
      • tBu_Ligand
        • Carbonate_tBu
          • Relaxed
        • Cat_tBu
        • Dimer_tBu
    • Mechanisms
      • Alternative_Mechanisms
        • Chelate_EpOH
          • 1Al_Oh
            • Chelate
            • Ensemble
              • Prev_Frozen
            • Post
            • Scan
              • Next
                • Reverse_FAIL
              • Relaxed
              • Zoom
                • Guess_FAIL
                • Relaxed_FAIL
            • Scan_2D
              • Freq
                • OPT2_FAIL
                • OPT_FAIL
              • Guess
                • Opt
              • Scan_1D
                • Guess
                  • Restart
              • Zoom_SmallBasis
                • Guess
                  • Opt
            • Scan_H
              • Zoom
            • Scan_Insertion
            • Scan_Isom
            • TS_2
              • Freq
                • Frozen
            • TS_Freq
              • OPT
            • TS_H
              • CC
            • TS_isom
          • 1Al_Oh_Ep
            • Alkoxide
            • Chelate
            • Ensemble
            • Hemi_Carb
              • Frozen
            • IC
            • Scan_H
              • Next
            • Scan_H2
              • Zoom
            • Scan_Insertion
        • Open_Ligand
          • Alkoxide
          • Alkoxide_OL
          • CC
          • Carbonate
            • Scan2
              • Next
            • Scan_FC_FAIL
              • Zoom
          • Carbonate2_FAIL
          • Carbonate_Oh
            • Restart
            • Scan_FAIL
              • Guess_FAIL
              • Zoom
          • Ensemble
          • Scan_CC
            • Guess_FAIL
            • Zoom
              • Guess_FAIL
              • Zoom_FAIL
          • Scan_Insertion
            • Zoom
          • TS_CC
            • Guess
              • Opt
          • TS_CC_Tests
            • TS
              • Freq
              • TZDP
                • After
                • Before
            • TS_H
              • After
              • Before
              • Freq
              • TZDP
          • TS_Insertion
            • Guess
              • Opt
      • No_Al
        • Uncatalyzed
          • Bicarb_Ep
          • COOH
          • Carb_Ep
          • Ensemble
          • Ep_Ep
          • Product
          • Scans
            • Scan_2
              • Zoom
            • Scan_2D
            • Scan_2_2
              • FAIL
            • Scan_2_5
              • Zoom
            • Scan_2_6
            • Scan_FC_Ep
              • 2Ep
          • TS
            • Scan
            • Scan2
            • Scan3
            • TS_Guess
              • Frozen
            • TS_Guess2
            • TS_Guess3
        • Water_Catalyzed
          • Ensemble_Wat
            • Scan
            • TS_Guess
              • Guess
              • Guess2
          • Product_Water
          • Scans
            • Scan_2Water_CC
              • Frozen
            • Scan_Water
            • Scan_Water_CC
            • Scan_Water_CC2
              • Zoom
            • Scan_Water_CC3
              • Ensemble
              • Guess
                • Guess
                • TZDP
                  • After
          • TS_CC_2Water
            • TZDP
              • After
          • TS_Water
            • After_COOH
            • Before
            • Freq
      • OEp_Insertion
        • Bimetallic
          • Alkoxide
          • Carbonate
          • Ensemble
          • Ensemble_CC
          • Ensemble_CO2
          • L_Carbonate
            • Alter
          • Scan_CC
          • Scan_CC2
            • Zoom
          • Scan_CC3
            • Guess
          • Scan_CC4
            • Next
          • Scan_Insertion
          • Scan_Insertion2
            • Guess
              • Freq
            • Zoom
              • Guess
          • Scan_Isom
            • Guess
              • opt
          • Scan_RO
            • Guess1_FAIL
            • Zoom
          • TS_CC
          • TS_Insertion
            • FAIL
          • TS_Isom
          • TS_RO
        • Monometallic
          • Alkoxide
          • Carbonate
          • Carbonate2
          • Ensemble
            • iFreq
          • Glycidol_Alk
          • IC
          • Methyl_Model
            • Alkoxide
            • CC
            • Carbonate
            • Carbonate2
              • i_Freq
            • Ensemble
            • IC
            • Methanol
            • Methoxide
            • Scan_CC
              • Alter
                • Next
            • Scan_Insertion
              • Guess
              • Next
            • Scan_Isom
              • Zoom
            • Scan_RO
              • Next
              • Scan_2D
            • TS_Insertion
            • TS_Isom
          • TS_Insertion
          • TS_Isom
      • OH_Insertion
        • Bimetallic
          • Carb_2Al
          • Ensemble
          • FC_2Al
            • 1_Al
          • FC_2Al_2Gly
            • Isom
              • Restart
          • FC_H_2Al
            • 1_Al
          • Lineal_Carbonate
          • Scan_Coord
            • Zoom
          • TS_FC_2Al
            • 1_Al
              • Post
            • Scan
              • Scan_Frozen
            • Scan2D
              • FAIL
          • TS_FC_H
            • 1_Al
          • TS_Insertion_2Al
        • Monometallic
          • OH_Insertion_Gly_coCat
            • CC_Ep
            • Carb_Ep
            • Carb_EpDown
            • Carbonate
              • Guess2
            • Carbonate_Isom
            • Scan
              • Frozen
              • Scan_F
            • Scan_CC2
              • Water
                • Zoom
                • Zoom2
            • Scan_CC3
              • Zoom
                • Guess1_FAIL
                • Guess2_FAIL
                  • OPT
                • Guess3
                  • TS
            • Scan_CC4
              • No_Opt
            • Scan_Insertion
            • Scans_CC
              • Guess
                • TS
              • Zoom
            • TS_CC
            • TS_Insertion
          • OH_Insertion_NoWater
            • Alkoxide
            • Carbonate
            • Carbonate_Isom
              • FAIL
              • Restart
            • Ensemble
            • FC
            • FC_H
            • HBonding
              • Freq
            • IC
            • Product
            • TS_FC
            • TS_FC_H
            • TS_H
            • TS_Insertion
          • OH_Insertion_SN1
            • Inversion
              • Aldehyde_Formation
              • CC_H2O
              • Carb_H2O
            • Retention
              • CC_H2O
              • Carb_H2O
              • TS_Isom
          • OH_Insertion_Water_SN2
            • Alkoxide
            • CC
            • Carbonate
            • Carbonate_Water
            • FC_H
            • IC
            • Product
            • TS_CC
              • No_Water
              • Water
            • TS_H
            • TS_Insertion
          • OH_Insertion__Water_Concerted
            • Alkoxide
            • CC
            • Carbonate
              • Frozen_Angle
              • Frozen_OAl
              • Frozen_OC
            • Ensemble
            • FC_H_Isom
            • IC
            • Linear_Carb
            • Linear_Carbonate_Water
            • Prod_Isom
              • Alk_FC
              • BnNH2
                • Restart
              • BnNH3
              • CC_Alk
              • EnsembleBnN_OCC
              • Ep_Alk
              • Int
              • Prod_Isom
              • TS_H
              • TS_Isom
            • Product
            • Reactants
              • Al
              • CO2
              • Glycidol
              • Water
            • TS
              • Frozen
                • FAIL
                • Opt
                  • TS_Ins_CC
            • TS_H
          • Scans
            • Scan_Ep_H
            • Scan_FC
              • Zoom
            • Scan_FC2
              • Zoom
            • Scan_FC3
              • Freq
                • Opt
              • Freq_Zoom
              • TZ2P
              • Zoom
            • Scan_FC_H_1Al
            • Scan_FC_H_2Al
            • Scan_FC_OH
            • Scan_FC_isom
              • Zoom
            • Scan_H
            • Scan_Insertion
              • Cont
              • Freq
                • Opt
              • Test
            • Scan_Insertion_O
            • Scan_Insertion_OH
            • Scan_Insertion_OH2
            • Scan_Isomerisation
              • Zoom
            • Scan_Isomerisation2
      • Reactants
        • Al
        • CO2
        • Glycidol
          • Density
        • MEK
        • Water
      • Side_Intermediates
        • Carb_Free_NoH
          • Scan_CC
        • Carb_HBond_HL_OEp
        • Carb_HBond_OC_HL
        • Carb_HBond_OEp_HL
          • Scan_CC
            • Zoom
        • Carb_HOep
        • Ens_Chelate_CO2
          • CO2_Bonded_Frozen
        • Ens_IC_Ep_CO2
        • Ens_IC_OH_CO2
        • HCarb_HBond_Ligand
          • Scan_CC
            • Zoom
              • Scan_2Coord
                • Zoom
        • HCarb_HLigand
        • OH_Insertion_2Al
          • Scan_GlyCoord
        • TS_CC_Down_OH
          • From_Frozen
          • Modified_631G
        • TS_CC_FreeAlk
          • Guess
        • TS_Isom_Alk
          • Guess
    • NMR_IR
      • IR
        • BP86
          • Acid
          • CarbH_Eq
          • Carbonate
          • Carbonate_Water
            • HCarb_Water
              • Frozen
          • Carbonate_Water_NoAl
          • HCarb
          • HCarb2
          • Linear_Carbonate_Water
          • Product
          • TBDH_HCO3
            • Freq
            • Opt_Freq
          • TBD_CO2
            • Freq
            • Opt_Freq
          • Water
        • wB97xD
          • CarbH_Ax
          • CarbH_Eq
            • Restart
          • HCarb
            • B3LYP
            • BP86
            • Cyclohexane
            • Free
            • Gas
          • HCarb2
            • H_Bond
              • Frozen
                • Opt
            • No_H
          • HCarb_Water
          • Product
            • B3LYP
            • BP86
            • Cyclohexane
            • Gas
            • wB97xD
      • NMR
        • B3LYP
          • OH
            • Glycidol
              • Glycidol_2
                • NMR
              • Glycidol_3
                • NMR
              • NMR
              • Opt
            • IC
              • IC_2
                • Opt
              • IC_3
                • Opt
              • NMR
              • Opt
              • Rot_3
                • 10
                • 11
              • Rot_4
                • 10
                • 11
          • OMe
            • Glycidol_Me
              • Glycidol_2
                • NMR
              • Glycidol_3
                • NMR
              • NMR
              • Opt
            • IC_Me
              • IC_Me_2
                • Opt
              • IC_Me_3
                • Opt
              • NMR
              • Opt
          • TMS
            • NMR
            • Opt
        • BP86
          • OH
            • Glycidol
              • Glycidol_2
                • NMR
              • Glycidol_3
                • NMR
              • NMR
              • Opt
            • IC
              • IC_2
                • Opt
              • IC_3
                • Opt
              • NMR
              • Opt
          • OMe
            • Glycidol_Me
              • Glycidol_2
                • NMR
              • Glycidol_3
                • NMR
              • NMR
              • Opt
            • IC_Me
              • IC_Me_2
                • Opt
              • IC_Me_3
                • Opt
              • NMR
              • Opt
          • TMS
            • NMR
            • Opt
        • wB97xD
          • OH
            • Glycidol
              • NMR
              • Opt
            • IC
              • Butanone
              • NMR
              • Opt
          • OMe
            • Glycidol_Me
              • NMR
              • Opt
            • IC_Me
              • NMR
              • Opt
          • TMS
            • NMR
            • Opt
    • Racemization
      • BnNH2
      • BnNH3
      • CC_Alk
      • Ensemble
      • EnsembleBn_OCC
      • Ep_Alk
      • From6RingTo5
        • Al_Cat
          • CO2_Insertion
            • TS_CC
              • Next
              • TS_Ax
              • TS_Eq
            • TS_H
              • FC
              • FC_H
              • TS_FC_H
            • TS_Insertion
              • After
              • Before
              • Scan
              • TS_Insertion
          • No_CO2
            • FC_Alter
            • FC_H
            • Scan
              • Zoom
            • Scan_Alter
        • No_Cat
          • After
          • Before
        • Product_5
        • Product_6
      • Int
      • Prod
      • Prod_H
      • Scan1
      • Scan2
        • Prod
      • Scan2_2
        • Next
        • TZDP
      • Scan_H
        • TS_FAIL
      • TS_H
        • Alk_FC
        • Scan
          • DZP
            • Zoom_TZDP
          • Killed
        • TS
      • TS_Rac
        • Freq
        • Int_Rac
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