SUPPORTING INFORMATION

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1 Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2018 SUPPORTING INFORMATION Bulky cationic ß-diketiminate magnesium complexes Alexander Friedrich, Jürgen Pahl, Holger Elsen and Sjoerd Harder* Inorganic and Organometallic Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 1, Erlangen, Germany. Contents 1. Supporting Experimental data S2 1.1 NMR spectra of synthesized compounds S2 1.2 Single crystal X-ray diffraction S12 2. DFT calculations S16 3. References S24

2 1. Supporting Experimental data 1.1. NMR spectra of synthesized compounds Spectra of [( tbu BDI)Mg benzene+ + [B(C 6 F 5 ) 4 ] Figure S1: 1 H NMR spectrum of [( tbu BDI)Mg benzene] + [B(C 6 F 5 ) 4 ] in C 6 D 5 Br. S2

3 Figure S2: 13 C{ 1 H} NMR spectrum of [( tbu BDI)Mg benzene] + [B(C 6 F 5 ) 4 ] in C 6 D 5 Br Figure S3: 19 F NMR spectrum of [( tbu BDI)Mg benzene] + [B(C 6 F 5 ) 4 ] in C 6 D 5 Br S3

4 Figure S4: 11 B NMR spectrum of [( tbu BDI)Mg benzene] + [B(C 6 F 5 ) 4 ] in C 6 D 5 Br Figure S5: 1 H NMR spectrum of [( tbu BDI)Mg (THF)] + [B(C 6 F 5 ) 4 ] in C 6 D 5 Br. Resonances marked with a star can be assigned to a species with two coordinated THF ligands (as has been proven by subsequent addition of a second eq of THF) S4

5 Figure S6: 1 D Selective Gradient NOESY NMR spectrum of [( tbu BDI)Mg (THF)] + [B(C 6 F 5 ) 4 ] in C 6 D 5 Br. Irradiation at the THF OCH 2 signal (2.87 ppm) gave strong enlargement of the ipr CH signal at 3.02 ppm. Figure S5: 1 H NMR spectrum of [( tbu BDI)Mg] + [B(C 6 F 5 ) 4 ] in THF-d 8 S5

6 Spectra of [( tbu BDI)Mg toluene+ + [B(C 6 F 5 ) 4 ] Figure S8: 1 H NMR spectrum of [( tbu BDI)Mg toluene] + [B(C 6 F 5 ) 4 ] in C 6 D 5 Br Figure S9: 13 C{ 1 H} NMR spectrum of [( tbu BDI)Mg toluene] + [B(C 6 F 5 ) 4 ] in C 6 D 5 Br S6

7 Figure S10: 11 B NMR spectrum of [( tbu BDI)Mg toluene] + [B(C 6 F 5 ) 4 ] in C 6 D 5 Br Figure S11: 19 F NMR spectrum of [( tbu BDI)Mg toluene] + [B(C 6 F 5 ) 4 ] in C 6 D 5 Br S7

8 Spectra of [( tbu BDI)Mg m-xylene] + [B(C 6 F 5 ) 4 ] Figure S12: 1 H NMR spectrum of [( tbu BDI)Mg m-xylene] + [B(C 6 F 5 ) 4 ] in C 6 D 5 Br. Figure S13: 13 C{ 1 H} NMR spectrum of [( tbu BDI)Mg m-xylene] + [B(C 6 F 5 ) 4 ] in C 6 D 5 Br. S8

9 Figure S14: 19 F NMR spectrum of [( tbu BDI)Mg m-xylene] + [B(C 6 F 5 ) 4 ] in C 6 D 5 Br. Figure S15: 11 B NMR spectrum of [( tbu BDI)Mg m-xylene] + [B(C 6 F 5 ) 4 ] in C 6 D 5 Br. S9

10 Spectra of [( tbu BDI)Mg (PhCl)+ + [B(C 6 F 5 ) 4 ] Figure S16: 1 H NMR spectrum of [( tbu BDI)Mg (PhCl)] + [B(C 6 F 5 ) 4 ] in C 6 D 5 Br. Figure S17: 13 C{ 1 H} NMR spectrum of [( tbu BDI)Mg (PhCl)] + [B(C 6 F 5 ) 4 ] in C 6 D 5 Br. S10

11 Figure S18: 19 F NMR spectrum of [( tbu BDI)Mg (PhCl)] + [B(C 6 F 5 ) 4 ] in C 6 D 5 Br. Figure S19: 11 B NMR spectrum of [( tbu BDI)Mg (PhCl)] + [B(C 6 F 5 ) 4 ] in C 6 D 5 Br. S11

12 1.2 Single Crystal X-Ray Diffraction Single crystal X ray diffraction data for all compounds were collected on a SuperNova diffractometer (Rigaku Oxford diffraction) with Atlas S2 detector using a CuK α or MoK α microfocus source. All crystals were maintained at 100 K during data collection. Using Olex2 S1 the structures were solved by Direct Methods (ShelXT) S2 and refined with ShelXL S3 using Least Squares minimization. The hydrogen atoms have been placed on calculated positions and were refined isotropically in a riding model. All presented structures had the complete molecule in their respective asymmetric units without any cocrystallized solvents. For the solution of [( tbu BDI)Mg (PhCl)] + [B(C 6 F 5 ) 4 ] five reflexes were omitted for error minimization. The crystal structure of [( tbu BDI)Mg toluene] + [B(C 6 F 5 ) 4 ] was of poor quality but we give the cell parameters for identification: a = (2) Å, b = (3) Å, c = (3) Å, = (14), = (13), = (14), V = (16) Å 3, space group: P-1. S12

13 Table S1. Crystal data. Identification code [( tbu BDI)Mg benzene] + [( tbu BDI)Mg m xylene] + [( tbu BDI)Mg PhCl] + [B(C 6 F 5 ) 4 ] [B(C 6 F 5 ) 4 ] [B(C 6 F 5 ) 4 ] Empirical formula C 65 H 59 BF 20 MgN 2 C 67 H 63 BF 20 MgN 2 C 65 H 58 BClF 20 MgN 2 Formula weight Temperature/K (10) 99.98(16) 100 Crystal system monoclinic monoclinic monoclinic Space group P2 1 /c P2 1 /c P2 1 /c a/å (4) (3) (2) b/å (5) (3) (2) c/å (4) (3) (2) α/ β/ (2) (14) (10) γ/ Volume/Å (2) (16) (12) Z ρ calc g/cm μ/mm F(000) Crystal size/mm Crystal color colorless colorless colorless Radiation CuKα (λ = ) CuKα (λ = ) CuKα (λ = ) 2Θ range for data collection/ Index ranges to to h 21, -15 k 21, -23 l h 20, -21 k 19, -14 l to h 22, -21 k 21, - 22 l 22 Reflections collected Independent reflections [R int = , R sigma = ] [R int = , R sigma = ] [R int = , R sigma = ] Data/restraints/parameters 11638/0/ /0/ /0/829 Goodness-of-fit on F Final R indexes *I>=2σ (I)+ Final R indexes [all data] R 1 = , wr 2 = R 1 = , wr 2 = R 1 = , wr 2 = R 1 = , wr 2 = Largest diff. peak/hole / e Å / /-0.54 R 1 = , wr 2 = R 1 = , wr 2 = /-0.36 S13

14 Figure S20: ORTEP representation of [( tbu BDI)Mg benzene] + [B(C 6 F 5 ) 4 ] (probability level 50%). Hydrogen atoms were omitted for clarity. Figure S21: ORTEP representation of [( tbu BDI)Mg m-xylene] + [B(C 6 F 5 ) 4 ] (probability level 50%). Hydrogen atoms were omitted for clarity. S14

15 Figure S22: ORTEP representation of [( tbu BDI)Mg (PhCl)] + [B(C 6 F 5 ) 4 ] (probability level 50%). Hydrogen atoms were emitted for clarity. S15

16 2. DFT calculations General All calculations were carried out using Gaussian 16 A. [S4] All methods were used as implemented. All structures were fully optimized on a ωb97xd/6-31+g** level of theory. In order to determine zero point energies and to characterize the structures as minima frequency analysis has been applied. [S5-8] Energies were calculated on ωb97xd/6-311+g** level of theory. Charges were calculated via NBO analysis. [S9] Molecules were drawn and evaluated using Molecule V2.3. [S10] Topological analyses were carried out using AIMAll V17 using the wavefunctions of the geometry optimizations. [S11-12] Table S2. Complexation energies of cations with benzene calculated at the ωb97xd/6-311+g**//ωb97xd/6-31+g** level. H and G (298 K, 1 atm) given in kcal/mol. Reaction de dh dg (298K, 1 atm) ( Me BDI)Mg + + C 6 H 6 ( Me BDI)Mg + C 6 H ( tbu BDI)Mg + + C 6 H 6 ( tbu BDI)Mg + C 6 H [( Me BDI)Mg + ] + C 6 H 6 [( Me BDI)Mg + C 6 H 6 ] a a [B(C 6 F 5 ) 4 ] [B(C 6 F 5 ) 4 ] a Calculated at ωb97xd/6-311+g**//6-31g*. [S13] XYZ Coordinates 103 tbu C6H6 Mg N N C C C C C H C C C C C C H C S16

17 C H C H C H C H C H H H C H C H H H C H H H C H C H C H H H C H H H C H C H H H C H H H C H C H C H H H S17

18 C H H H C H C H H H C H C H H H C H C H C H C H H H C H H H C H H H tbu Mg N N C C C C C H C C C C C C S18

19 H C C H C H C H C H C H H H C H C H H H C H H H C H C H C H H H C H H H C H C H H H C H H H C H C H H H S19

20 C H H H C H H H C H H H C H H H C H H H C H H H BDI C6H6 C Mg N N C C C C C C C C C C C C C C C C C H H H H S20

21 H H H H C C H H H H C C H H C C C C C H H H H H C C H C H C C H C H C C H H H H H H H H H H H H H H H H S21

22 H H H H H H H H BDI Mg N N C C C C H C C C C H C C C H C H C H C H C H C H H H C H C H H H C H C H C H S22

23 H H C H H H C H C H H H C H H H C H H H C H H H C H H H C H H H S23

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