[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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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