Supporting Information for. Influence of ligands and oxidation state on the. reactivity of pentacoordinated iron carbenes

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1 Supporting Information for Influence of ligands and oxidation state on the reactivity of pentacoordinated iron carbenes with olefins: metathesis versus cyclopropanation Égil de Brito Sá, a,b Luis Rodríguez-Santiago, a Mariona Sodupe, a Xavier Solans-Monfort a, * a Departament de Química, Universitat Autònoma de Barcelona, Bellaterra, Spain b Universidade Federal do Piauí, Campus Ministro Reis Velloso, Parnaíba-Piauí, Brazil S1

2 Table of contents Table S1. Comparison between OPBE and B3LYP functionals Table S2. Carbene electronic structure analysis Table S3. Relative Gibbs (G gp + D2) energies of the bridged carbene isomers of complexes 1-5 Figures S1. Optimized geometries of carbene 1 and the derived species. Figures S2. Optimized geometries of carbene 2 and the derived species. Figures S3. Optimized geometries of carbene 3 and the derived species. Figures S4. Optimized geometries of carbene 3 H and the derived species. Figures S5. Optimized geometries of carbene 4 and the derived species. Figures S6. Optimized geometries of carbene 5 and the derived species. Figures S7. Optimized geometries of carbene 1 0 and the derived species Figures S8. Optimized geometries of carbene 2 0 and the derived species Figures S9. Optimized geometries of carbene 3 H-0 and the derived species Figures S10. Optimized geometries of carbene 5 0 and the derived species Figure S11. Molecular Orbitals diagram and Natural Orbitals of the triplet state of carbene 1. Figure S12. Optimized structures for the bridged carbene isomers of complexes 1, 2 and 3 H. Figure S13. Optimized geometries of the transition states associated with the reactivity of 5 0. Figure S14. Optimized geometries of the transition states associated with the reactivity of 5 Figure S15. Gibbs Energy profile (in kcal mol -1 ) for the reaction of 5 with ethene S3 S4 S5 S6 S7 S8 S9 S10 S11 S12 S13 S14 S15 S16 S17 S18 S19 S20 S2

3 Table S1. Relative B3LYP (OPBE) Gibbs (G gp + D2) energies of the species involved in the metathesis and cyclopropanation reactions of 1 and 3. The reported values are relative energies with respect to the carbene singlet state and ethene. All values are in kcal mol -1 Complex Carbene Metallacycle Cyclopropanation S=0 S=1 S=2 S=0 S=1 S=2 S=0 S=1 S= (0.0) -7.5 (-2.3) -2.9 (3.8) (-20.7) (-23.1) (-22.3) (-28.6) (-43.8) (0.0) -2.0 (4.4) 8.2 (23.5) 10.5 (6.8) -3.2 (4.7) (-25.1) (-30.1) S3

4 Table S2. Carbene electronic structure analysis including NPA spin densities over iron (s Fe) and the carbon atom of the carbene (s C), Wiberg bond order (WO) and Atom in molecules based delocalization index (DI). S=0 S=1 S=2 Carbene a s Fe b s C WO c DI d a s Fe b s C WO c DI d a s Fe b s C WO c DI d H a Spin density over iron atom b Spin density over the carbon of the iron-carbene fragment c Wiberg bond order for Fe=CH 2 bond d AIM based delocalization index for the Fe=CH 2 bond. S4

5 Table S3. Relative Gibbs (G gp + D2) energies of the bridged carbene isomers of complexes 1-5 with respect to the standard singlet carbene. Values in kcal mol -1 Standard carbene Bridged carbene Carbene S = 0 S = 1 S = 2 S = 0 S = 1 S = H N.A N.A S5

6 S = 0 S = 1 S = 2 a) M C b = M C b = Figure S1. Optimized geometries for a) carbene 1; the metallacyclobutane resulting from the reaction of 1 with ethene and metal fragment resulting from the cyclopropanation of the same species in the singlet (S=0), triplet (S=1) and quintet (S=2) spin states. Distances are in Å. All attempts to obtain the quintet state metallacycle structure directly evolved to cyclopropanation products. S6

7 S = 0 S = 1 S = 2 a) M C b = M C b = Figure S2. Optimized geometries for a) carbene 2; the metallacyclobutane resulting from the reaction of 2 with ethene and metal fragment resulting from the cyclopropanation of the same species in the singlet (S=0), triplet (S=1) and quintet (S=2) spin states. Distances are in Å. All attempts to obtain the quintet state metallacycle structure directly evolved to cyclopropanation products. S7

8 a) S = 0 S = 1 S = 2 Fe=C = Fe=C = Fe=C = M C b = M C b = Figure S3. Optimized geometries for a) carbene 3; the metallacyclobutane resulting from the reaction of 3 with ethene and metal fragment resulting from the cyclopropanation of the same species in the singlet (S=0), triplet (S=1) and quintet (S=2) spin states. Distances are in Å. All attempts to obtain the quintet state metallacycle structure directly evolved to cyclopropanation products. S8

9 a) S = 0 S = 1 S = M C b = M C b = Figure S4. Optimized geometries for a) carbene 3 H; the metallacyclobutane resulting from the reaction of 3 H with ethene and metal fragment resulting from the cyclopropanation of the same species in the singlet (S=0), triplet (S=1) and quintet (S=2) spin states. Distances are in Å. All attempts to obtain the quintet state metallacycle structure directly evolved to cyclopropanation products. S9

10 a) S = 0 S = 1 S = M C b = M C b = M C b = Figure S5. Optimized geometries for a) carbene 4; the metallacyclobutane resulting from the reaction of 4 with ethene and metal fragment resulting from the cyclopropanation of the same species in the singlet (S=0), triplet (S=1) and quintet (S=2) spin states. Distances are in Å. All attempts to obtain the quintet state carbene lead to an optimized structure in which the carbene is inserted in the Fe-Ph bond. S10

11 a) S = 0 S = 1 S = M C b = M C b = Figure S6. Optimized geometries for a) carbene 5; the metallacyclobutane resulting from the reaction of 5 with ethene and metal fragment resulting from the cyclopropanation of the same species in the singlet (S=0), triplet (S=1) and quintet (S=2) spin states. Distances are in Å. All attempts to obtain the quintet state carbene lead to an optimized structure in which the carbene is inserted in the Fe-NHC bond. Moreover, optimization of the quintet metallacycle structure directly evolved to cyclopropanation products. S11

12 a) S = 0 S = 1 S = M C b = M C b = M C b = Figure S7. Optimized geometries for a) carbene 1 0; the metallacyclobutane resulting from the reaction of 1 0 with ethene and metal fragment resulting from the cyclopropanation of the same species in the singlet (S=0), triplet (S=1) and quintet (S=2) spin states. Distances are in Å. S12

13 S = 0 S = 1 S = 2 a) M C b = M C b = Figure S8. Optimized geometries for a) carbene 2 0; the metallacyclobutane resulting from the reaction of 2 0 with ethene and metal fragment resulting from the cyclopropanation of the same species in the singlet (S=0), triplet (S=1) and quintet (S=2) spin states. Distances are in Å. All attempts to obtain the quintet state metallacycle structure directly evolved to cyclopropanation products. S13

14 S = 0 S = 1 S = 2 a) M C b = M C b = M C b = Figure S9. Optimized geometries for a) carbene 3 H-0; the metallacyclobutane resulting from the reaction of 3 H-0 with ethene and metal fragment resulting from the cyclopropanation of the same species in the singlet (S=0), triplet (S=1) and quintet (S=2) spin states. Distances are in Å. All attempts to obtain the quintet state carbene lead to an optimized structure in without a standard carbene fragment. S14

15 S = 0 S = 1 S = 2 a) M C b = M C b = M C b = Figure S10. Optimized geometries for a) carbene 5 0; the metallacyclobutane resulting from the reaction of 5 0 with ethene and metal fragment resulting from the cyclopropanation of the same species in the singlet (S=0), triplet (S=1) and quintet (S=2) spin states. Distances are in Å S15

16 Schematic MO diagram for double bond situation z Natural Orbitals Virtual orbitals y x Partially occupied orbitals Schematic MO diagram for single bond situation z (0.12) (1.00) y x (1.00) Doubly occupied orbitals (1.88) Figure S11. Schematic Molecular Orbitals diagram and Natural Orbitals of the triplet (S = 1) state of carbene 1. S16

17 S = 0 S = 1 S = Figure S12. Optimized structures for the bridged carbene isomers of complexes 1, 2 and 3 H. Distances are in Å. S17

18 a) S= TS-OM1 Int-OM1 TS-OM S= TS-OM3 Int-OM3 TS-OM4 S= TS-CP-SW Int-CP-SW1 S= TS-CP-SW1 Int-CP-SW1 TS-CP-SW2 S= S= TS-CP-MC TS-CP-MC Figure S13. Optimized geometries for a) ethene metathesis process catalyzed by 5 0; cyclopropanation reaction involving 5 0 and ethene through the step wise mechanism and cyclopropanation involving the same species from the metallacyclobutane intermediate. The singlet (S=0) and triplet (S=1) spin states have been considered. Distances are in Å S18

19 a) S = 0 S = Figure S14 Optimized geometries for a) ethene metathesis process catalyzed by 5; cyclopropanation reaction involving 5 and ethene through the step wise mechanism and cyclopropanation involving the same species from the metallacyclobutane intermediate. The singlet (S=0) and triplet (S=1) spin states have been considered. Distances are in Å S19

20 Fe Fe Fe TS-OM TS-CP-MC = Int-OM Figure S15. Gibbs Energy profile (in kcal mol -1 ) for the reaction of 5 with ethene: alkene metathesis (black) and alkene cyclopropanation involving the metallacyclobutane intermediate in red. Solid lines are used for the singlet (S=0) state and dashed ones for the triplet (S=1) state. S20