[3 + 2] versus [2 + 2] addition: a density functional...

[3 + 2] Versus [2 + 2] Addition: A Density Functional Theory Study on the Mechanistic Aspects of Transition-Metal-Assisted Formation of 1,2-Dinitrosoalkanes

Ernest Opoku, Richard Tia* and Evans Adei

Theoretical and Computational Chemistry Laboratory, Department of Chemistry, Kwame Nkrumah University of Science and Technology, Kumasi, Ghanaernopoku@gmail.com, richtiagh@yahoo.com, eadei@yahoo.com

Figure S1: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpCo(NO)2

and propene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 1

Figure S2: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpRh(NO) 2

and propene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 2

Figure S3: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpIr(NO) 2

and propene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 3

Figure S4: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpCo(NO)2

and transbutene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 4

Figure S5: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpRh(NO) 2

and transbutene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 5

Figure S6: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpIr(NO) 2

and transbutene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 6

Figure S7: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpCo(NO) 2

and vinyl fluoride. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 7

Figure S8: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpRh(NO) 2

and vinyl fluoride. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 8

Figure S9: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpIr(NO) 2

and vinyl fluoride. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 9

Figure S10: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpCo(NO)2

and ethenol. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 10

Figure S11: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpRh(NO)2

and ethenol. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 11

Figure S12: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpIr(NO)2

and ethenol. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 12

Figure S13: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpCo(NO)2

and aminoethene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 13

Figure S14:1 Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpRh(NO)2 and aminoethene. Relative energies in kcalmol-1. All bond distances are measured in

Å.

Page | 14

Figure S15: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpIr(NO)2

and aminoethene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 15

Figure S16: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpCo(NO)2

and acrylonitrile. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 16

Figure S17: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpRh(NO)2

and acrylonitrile. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 17

Figure S18: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpIr(NO) 2

and acrylonitrile. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 18

Figure S19: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpCo(NO) 2

and 3,3,3-trifluoro-1-propene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 19

Figure S20: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpRh(NO)2

and 3,3,3-trifluoro-1-propene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 20

Figure S21: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpIr(NO) 2

and 3,3,3-trifluoro-1-propene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 21

Figure S22: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpCo(NO)2

and 2,3-dimethyl-2-butene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 22

Figure S23: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpRh(NO)2

and 2,3-dimethyl-2-butene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 23

Figure S24: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpIr(NO)2

and 2,3-dimethyl-2-butene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 24

Figure S25: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpCo(NO)2

and cyclobutene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 25

Figure S26: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpRh(NO) 2

and cyclobutene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 26

Figure S27: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpIr(NO) 2

and cyclobutene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 27

Figure S28: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpCo(NO)2

and cyclopentene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 28

Figure S29: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpRh(NO)2

and cyclopentene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 29

Figure S30: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpIr(NO)2

and cyclopentene. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 30

Figure S31: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpCo(NO)2

and 2-cyclohexenone. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 31

Figure S32: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpRh(NO) 2

and 2-cyclohexenone. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 32

Figure S33: Free energy profile of the [3 + 2] and [2 + 2] addition reaction between CpIr(NO) 2

and 2-cyclohexenone. Relative energies in kcalmol-1. All bond distances are measured in Å.

Page | 33