Table of Contents 1 Supplementary Data MCD

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1 Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2017 Supporting Information for Magnetic circular dichroism and density functional theory studies of electronic structure and bonding in cobalt(ii)-nheterocyclic carbene complexes Theresa E. Iannuzzi, a Yafei Gao, b Tessa M. Baker, a Liang Deng b and Michael L. Neidig* a a Department of Chemistry, University of Rochester, Rochester, New York 14627, USA b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, , P. R. China Table of Contents 1 Supplementary Data MCD H NMR spectrum of (ICy) 2 CoCl Crystallographic and structure refinement data for (ICy) 2 CoCl Buried volume DFT studies MO Energy Level Diagrams Experimental and calculated structural parameters of cobalt complexes Additional MBO and CDA for L 2 CoCl 2 complexes Optimized Geometry Coordinates... 11

2 1. Supplementary Data 1.1 MCD Figure S1 5 K, 7 T MCD spectra of distorted tetrahedral L 2 CoCl 2 complexes. Spectra were in either 1 : 1 THF 2-MeTHF or pure 2- MeTHF. Individual transition fits are shown with dashed lines. 2

3 1.2 1 HNMR Spectrum Figure S2 1 H NMR spectrum of (ICy) 2 CoCl 2 in d 8 -THF recorded at 23 o C 3

4 1.3 Crystallographic and structure refinement data for (ICy) 2 CoCl 2 Table S1 Crystallographic and structure refinement data for (ICy) 2 CoCl 2 (ICy) 2 CoCl 2 Compound formula C 30 H 48 Cl 2 CoN 4 crystal size (mm) 0.39 x 0.35 x 0.32 fw crystal system Trigonal space group R -3 a, Å (16) b, Å (16) c, Å (14) α, deg 90 β, deg 90 γ, deg 120 V, Å (2) Z 18 D calcd, Mg/m radiation (λ), Å Mo Kα ( ) 2θ range, deg to μ, mm F(000) 5706 no. of params reflns 8717 no. of params reflnd 370 goodness of fit R wr

5 1.4 Buried Volume Table S2 Calculated buried volume of L 2 CoCl 2 and L 2 CoCl crystallographic structures % V buried volume Co(II) Co(I) (IMes) 2 CoCl (ICy) 2 CoCl (SIMes) 2 CoCl 2 - (dppp)cocl (teeda)cocl (tmpn)cocl (IMes) 2 CoCl 68.7 (SIMes) 2 CoCl 73 5

6 2. DFT Studies 2.1 MO Energy Level Diagrams Figure S3 Calculated molecular orbital energy diagram of (ICy) 2 CoCl 2 6

7 Figure S4 Calculated molecular orbital energy diagram of (dppp)cocl 2 7

8 2.2 Experimental and structural parameters of Co(II) complexes Table S3 Comparison of experimental and calculated (gas phase) structural parameters of (IMes) 2 CoCl 2 Method Basis Set GD3BJ? Co-L 1 (Å) Co-L 2 (Å) Co-Cl 1 (Å) Co-Cl 2 (Å) L 1 -Co-L 2 ( ) Cl 1 -Co-Cl 2 ( ) crystal bond lengths and angles PBE0 TZVP no yes PBE0 Def2TZVP1 no yes PBE TZVP no yes PBE Def2TZVP no yes BP862 TZVP no yes Table S4 Comparison of experimental and calculated (THF solvent model) structural parameters of (IMes) 2 CoCl 2 Method Basis Set GD3BJ? Co-L 1 (Å) Co-L 2 (Å) Co-Cl 1 (Å) Co-Cl 2 (Å) L 1 -Co-L 2 ( ) Cl 1 -Co-Cl 2 ( ) crystal bond lengths and angles PBE0 TZVP yes PBE TZVP no yes PBE Def2TZVP no yes B3LYP TZVP no yes BP86 TZVP no yes M06 3 TZVP no yes (a) F. Weigend and R. Ahlrichs, Phys. Chem. Chem. Phys., 2005, 7, (b) F. Weigend, Phys. Chem. Chem. Phys., 2006, 8, (a) A. D. Becke, Phys. Rev. A, 1988, 38, (b) J. P. Perdew. Phys. Rev. B, 1986, 33, Y. Zhao and D. G. Truhlar, Theor. Chem. Acc., 2008, 120,

9 Table S5 Comparison of experimental and calculated structural parameters of four-coordinate L 2 CoCl 2 using PBE0/TZVP with GD3BJ dispersion corrections in gas-phase Co-L 1 (Å) Co-L 2 (Å) Co-Cl 1 (Å) Co-Cl 2 (Å) L 1 -Co-L 2 ( ) Complex Exp. Calc. Exp. Calc. Exp. Calc. Exp. Calc. Exp. Calc. (IMes) 2 CoCl (simes) 2 CoCl (ICy) 2 CoCl (dppp)cocl (tmpn)cocl (teeda)cocl Table S6 Comparison of experimental and calculated structural parameters of three-coordinate L 2 CoCl complexes using PBE0/TZVP with GD3BJ dispersion corrections in gas-phase Co-L 1 (Å) Co-L 2 (Å) Co-Cl (Å) L 1-Co-L 2 ( ) L 1-Co-Cl ( ) Complex Exp. Calc. Exp. Calc. Exp. Calc. Exp. Calc. Exp. Calc. (IMes) 2CoCl (simes) 2CoCl

10 2.3 Additional MBO and CDA for L 2 CoCl 2 complexes Table S7 Mayer bond order and charge decomposition analyses for distorted tetrahedral NHC, phosphine and diamine L 2 CoCl 2 complexes optimized using PBEPBE/TZVP Mayer bond order Charge decomposition analysis (α + β) Donation: Back donation: Net charge donation Complex Co-L Co-Cl (L 2 --> Co-Cl 2 ) (Co-Cl 2 --> L 2 ) to Co-Cl 2 (ICy) 2 CoCl e e e (IMes) 2 CoCl e e e (SIMes) 2 CoCl e e e (dppp)cocl e e e (teeda)cocl e e e (tmpn)cocl e e e

11 2.4 Optimized Geometry Coordinates Table S8 (IMes) 2 CoCl 2 optimized with upbe0/tzvp (gas-phase)

12 Energy = A.U. Table S9 (SIMes) 2 CoCl 2 optimized with upbe0/tzvp (gas-phase)

14 Energy = A.U. Table S10 (ICy) 2 CoCl 2 optimized with upbe0/tzvp (gas-phase)

16 Energy = A.U. Table S11 (dppp)cocl 2 optimized with upbe0/tzvp (gas-phase)

17 Energy = A.U. Table S12 (teeda)cocl 2 optimized with upbe0/tzvp (gas-phase)

18 Energy = A.U. Table S13 (tmpn)cocl 2 optimized with upbe0/tzvp (gas-phase) Energy = A.U. 18

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