Two Spin-state Reactivity in the Activation and Cleavage of CO 2 by [ReO 2 ]

Transcription

1 Page 1 of 22 vised Version: 5 May 2016 Submitted to: J. Phys. hem. Lett. Two Spin-state activity in the Activation and leavage of 2 by [ 2 ] Valentino anale, a-c, Robert Robinson Jr., d, Athanasios Zavras, a,b George N. Khairallah, a,b Nicola d Alessandro, c Brian F. Yates,*,d and Richard A. J. Hair*,a,b a School of hemistry and Bio21 Molecular Science and Biotechnology Institute, University of Melbourne, 30 Flemington Rd, Parkville, Victoria 3010, Australia b AR entre of Excellence for Free Radical hemistry and Biotechnology, University of Melbourne, Parkville, Victoria 3010, Australia c Department of Engineering and Geology (INGE), G. d'annunzio University of hieti and Pescara, Viale Pindaro, 42, I Pescara, Italy d School of Physical Sciences hemistry, University of Tasmania, Private Bag 75, Hobart, Tasmania 7001, Australia These authors contributed equally to the work. *orrespondence should be addressed to Prof Brian F. Yates ( Brian.Yates@utas.edu.au) and Prof Richard Hair ( rohair@unimelb.edu.au; Fax: (+) ) Supporting Information Full details of ref. 29: Gaussian 09, revision D.01, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; heeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; aricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao,.; Nakai, H.; Vreven, T.; Montgomery, Jr., J. A.; Peralta, J. E.; gliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; ndell, A.; Burant, J..; Iyengar, S. S.; Tomasi, J.; ossi, M.; ga, N.; Millam, J. M.; Klene, M.; Knox, J. E.; ross, J. B.; Bakken, V.; Adamo,.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev,.; Austin, A. J.; ammi, R.; Pomelli,.; chterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; rtiz, J. V.; ioslowski, J.; Fox, D. J. Gaussian, Inc.: Wallingford, T; 2009.

2 Page 2 of 22 DFT benchmarking studies: As discussed in the computational section, the calculated Gibbs energy values throughout the article were obtained at the B3LYP/BS2//B3LYP/BS1 level of theory. The validity of this was tested with respect to the experimental electron affinities for [ 2 ] and [ 3 ] that were reported by Rademann et al. 1 As such, calculations were carried out on the corresponding stationary points (quartet- 2, triplet-[ 2 ], doublet- 3 and singlet-[ 3 ] ) at different levels of theory (Tables S1 and S2). In addition, a bond length and angle comparison study was performed among optimized structures of quartet- 2 and triplet-[ 2 ] at different levels of theory (Table S3). Table S1. Effect of DFT functional methods and basis sets on the calculated electron affinity (EA) value (in kj mol -1 ) for triplet-[ 2 ]. Level of Theory EA pt/freq Basis Set SPE Basis Set [ 2] M06 SDD/6-31G(d) M06 SDD/6-31G(d) SD(T) def2-qzvp/6-311+g(2d,p) 2.24 M06 SDD/6-31G(d) M06 def2-qzvp/6-311+g(2d,p) 2.81 M06 def2-qzvp/6-311+g(2d,p) B3LYP SDD/6-31G(d) B3LYP def2-qzvp/6-311+g(2d,p) B3LYP def2-qzvp/aug-cc-pvtz B3LYP SDD/6-31G(d) M06 def2-qzvp/6-311+g(2d,p) 2.81 B3LYP SDD/6-31G(d) B3LYP def2-qzvp/6-311+g(2d,p) 2.54 BPV86 def2-qzvp/6-311+g(2d,p) PBE1 def2-qzvp/6-311+g(2d,p) SD(T) def2-qzvp/6-311+g(2d,p) MPW1PW91 def2-qzvp/6-311+g(2d,p) Experimental 2.5±0.1 Table S2. Effect of DFT functional methods and basis sets on the calculated electron affinity (EA) value (in kj mol -1 ) for singlet-[ 3 ]. Level of Theory EA pt/freq Basis Set SPE Basis Set [ 3] B3LYP def2-qzvp/6-311+g(2d,p) B3LYP def2-qzvp/aug-cc-pvtz B3LYP SDD/6-31G(d) B3LYP def2-qzvp/6-311+g(2d,p) 3.53 Experimental 3.6±0.1 Table S3. Effect of DFT functional methods and basis sets on the calculated bond lengths (in Å) and angles (in degrees) for quartet- 2 and triplet-[ 2 ]. Level of Theory Bond Length Bond Angle pt/freq Basis Set 2 [ 2] - 2 [ 2] - M06 SDD/6-31G(d) M06 def2-qzvp/6-311+g(2d,p) B3LYP def2-qzvp/6-311+g(2d,p) B3LYP def2-qzvp/aug-cc-pvtz B3LYP SDD/6-31G(d) BPV86 def2-qzvp/6-311+g(2d,p) PBE1 def2-qzvp/6-311+g(2d,p) SD(T) def2-qzvp/aug-cc-pvtz SD(T) def2-qzvp/6-311+g(2d,p) MPW1PW91 def2-qzvp/6-311+g(2d,p) Pramann, A.; Rademann, K. hem. Phys. Lett. 2001, 343, 99.

3 Page 3 of 22 Table S4. alculated thermal-corrected Gibbs (ΔG) and enthalpy (ΔH) energy values (in kj mol -1 ) and bond lengths (in Å) for selected [ 2-2 ] geometries. a,b Triplet-state η ΔG ΔH _T _T _T, _T anti _T syn _T, _T cyclic _T Singlet-state 1_S _S , a All energies are calculated at the B3LYP/BS2//B3LYP/BS1 level of theory and are relative to [ 2 ] - (1_T) and free 2. b Both anti and syn denotes the orientation of the pendent oxygen atom as it relates towards the metal center. The cyclic indicates at an oxygen atom of 2 is bound onto the metal center and an oxygen atom of [ 2 ] fragment is simultaneously bound onto the carbon atom (see Figure S1 for more details).

4 Page 4 of 22 DG (DH) kj/mol TSB7_S (114.8) 1_S (64.8) 2-P 3-P 26.8 _1T 27.1 (-7.9) (-7.9) 1_T TS2_T (0.0) 2_T -7.6 (-44.5) 2.0 (-43.2) 3_T (-90.0) TS3_T 21.6 (-20.5) _1T 75.3 (43.1) TSB3_T (-56.3) 4-P 10.9 (-25.7) 4_T 32.0 TSB4_T 40.0 (4.9) 9_S TSB3_S (-88.7) 9_T TS4_T 25.7 (-13.8) _T 20.9 (-15.2) TSB8_T (-67.0) TS5_T 73.6 (28.2) 6_T 72.7 (29.2) 1_S 6_S (-68.5) TSB5_T 65.1 (26.8) TSB6_S 41.8 (-5.1) 1_T 7-P 67.1 (27.2) 7_T (-61.9) 7_S 54.9 (5.9) 9_T (-23.7) triplet singlet MEP 3_S (-185.4) 8_T (-167.3) B3LYP/def2-QZVP,6-311+G(2d,p)//B3LYP/SDD,6-31G(d) 9_S (-181.6) Figure S1. alculated reaction pathway for the two spin-state reactivity of [ 2 ] with 2.

5 Page 5 of 22 Figure S2. Rate of decay of [ 2 ] due to gas-phase ion-molecule reactions with 2 under pseudo-first order conditions.

6 Page 6 of 22 artesian coordinates and total energies for all calculated structures: (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (RM06)= SPE (RB3LYP)= _S (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (RM06)= SPE (UB3LYP)= _T (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies=

7 Page 7 of 22 Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)= [ 2 ] (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)= P (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)=

8 Page 8 of 22 SPE (UB3LYP)= _T (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)= TS2_T (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)=

9 Page 9 of P (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)= _S (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (RM06)= SPE (RB3LYP)=

10 Page 10 of TSB3_S (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)= _T (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)=

11 Page 11 of TS3_T (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)= TSB3_T (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)=

12 Page 12 of P (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)= _T (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)=

13 Page 13 of 22 TS4_T (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)= TSB4_T (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)=

14 Page 14 of 22 5_T (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)= TS5_T (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)=

15 Page 15 of 22 TSB5_T (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)= _S (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (RM06)= SPE (RB3LYP)= TSB6_S (Hartree/Particle)

16 Page 16 of 22 Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (RM06)= SPE (RB3LYP)= _T (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)= P (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy=

17 Page 17 of 22 Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)= _S (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (RM06)= SPE (RB3LYP)= TSB7_S (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies=

18 Page 18 of 22 Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (RM06)= SPE (RB3LYP)= _T (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)= _T (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies=

19 Page 19 of 22 Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)= TSB8_T (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)= _S (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=

20 Page 20 of 22 SPE (RM06)= SPE (RB3LYP)= _T (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (UM06)= SPE (UB3LYP)= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= SPE (RM06)= SPE (RB3LYP)=

21 Page 21 of 22 3_MEP Energy of Triplet State: Energy of Singlet State: SPE (UM06, Triplet State)= SPE (UB3LYP, Triplet State)= _MEP Energy of Singlet State: Energy of Triplet State: SPE (UM06, Triplet State)= SPE (UB3LYP, Triplet State)=

22 Page 22 of 22 7_MEP Energy of Singlet State: Energy of Triplet State: SPE (UM06, Triplet State)= SPE (RB3LYP, Triplet State)= _MEP Energy of Triplet State: Energy of Singlet State: SPE (UM06, Triplet State)= SPE (UB3LYP, Triplet State)=