SUPPORTING INFORMATION Probing M C NHC bond and its effect on the synthesis, structure and reactivity of R 2 MOR(NHC) (M = Al, Ga, In) complexes.

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1 SUPPORTING INFORMATION Probing M C NHC bond and its effect on the synthesis, structure and reactivity of R 2 MOR(NHC) (M = Al, Ga, In) complexes. Rafał Zaremba,, Maciej Dranka, Bartosz Trzaskowski, Lilianna Chęcińska*, and Paweł Horeglad*, Centre of New Technologies, University of Warsaw, Banacha 2c, , Warsaw, Poland. Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, , Warsaw, Poland. Faculty of Chemistry, University of Lodz, Pomorska 163/165, , Lodz, Poland Table of contents Table/Fig. Title Page Figs. S1-S46 1D, 2D NMR data for selected aluminum and gallium complexes 2-28 Figs. S47-S52 1 H and 13 C NMR spectra of PLA obtained with 4a, 4b and 1a Figs. S53-S55 Table S1 Gel Permation Chromatography (GPC) data for PLA obtained with 1a, 4a and 4b Crystal data and structure refinement details for 1a, 1b, 2a, 3a, 4a, SI1 and SI Figs. S56 and S57 Molecular structures of SI1 and SI Fig. S58 Resultant bond valence vector and bond valencies for 3a 39 Table S2 RSBIs for O M of selected Me 2MOR(NHC) and Me 2MOAr(NHC). 40 Table S3 RSBIs for C Me M of selected Me 2MOR(NHC) and Me 2MOAr(NHC). 41 Table S4 QTAIM atomic charges of Al/Ga/In, O and C Me 42 Figs. S59, S62, S65, S68, S71 Figs. S60, S63, S66, S69, S72 Figs. S61, S64, S67, S70, S73 Molecular graphs of Me 2MOMe(IMes) (M = Al (1a) Ga, In), Me 2MOMe(SIMes) (M = Al (1b) Ga, In), Me 2M(OCPh 2Me)(IMes) (M = Al (3a) Ga, In), Me 2M(OCPh 2Me)(6-Mes) (M = Ga, In) and Me 2M(OC 6H 4OMe)(IMes) (M = Al (4a) Ga, In). Isosurface representations of the localization domains of the ELI-D of Me 2MOMe(IMes) (M = Al (1a) Ga, In), Me 2MOMe(SIMes) (M = Al (1b) Ga, In), Me 2M(OCPh 2Me)(IMes) (M = Al (3a) Ga, In), Me 2M(OCPh 2Me)(6-Mes) (M = Ga, In) and Me 2M(OC 6H 4OMe)(IMes) (M = Al (4a) Ga, In). ELI-D distributions onto V 2(M, C NHC) bonding (disynaptic valence) basins of Me 2MOMe(IMes) (M = Al (1a) Ga, In), Me 2MOMe(SIMes) (M = Al (1b) Ga, In), Me 2M(OCPh 2Me)(IMes) (M = Al (3a) Ga, In), Me 2M(OCPh 2Me)(6-Mes) (M = Ga, In) and Me 2M(OC 6H 4OMe)(IMes) (M = Al (4a) Ga, In)

2 Figure S1. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OMe)] 3 with IMes in toluened 8 (400 MHz). 2

3 Figure S2. 13 C NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OMe)] 3 with IMes in toluened 8 (100 MHz). Figure S3. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OMe)] 3 with IMes in toluened 8 (400 MHz) 24 h after mixing. 3

4 Figure S4. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OMe)] 3 with IMes in toluened 8 (400 MHz) 8 days after mixing 4

5 Figure S5. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OMe)] 3 with IMes after essentially complete disproportionation (15 days) and addition of Me 3Al(IMes) in toluene-d 8 (400 MHz). Figure S6. 1 H NMR spectrum of Me 2Al(OMe)(IMes) (1a) in toluene-d 8 (400 MHz). 5

6 Figure S7. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OMe)] 3 with SIMes in toluene-d 8 (400 MHz). Figure S8. 1 H NMR spectrum of Me 2Al(OMe)(SIMes) (1b) in THF-d 8 (400 MHz). 6

7 Figure S9. 13 C NMR spectrum of Me 2Al(OMe)(SIMes) (1b) in THF-d 8 (100 MHz). Figure S10. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OCH 2CH 2OMe)] 2 with 2 equiv. of IMes in toluene-d 8 (400 MHz). 7

8 Figure S11. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OCH 2CH 2OMe)] 2 with 4 equiv. of IMes (2a/IMes) in toluene-d 8 (400 MHz). Figure S C NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OCH 2CH 2OMe)] 2 with 4 equiv. of IMes (2a/IMes) in toluene-d 8 (100 MHz). 8

9 Figure S13. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OCH 2CH 2OMe)] 2 with 4 equiv. of IMes (2a/IMes) in toluene-d 8 (400 MHz) 3 days after mixing. Figure S14. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OCH 2CH 2OMe)] 2 with 4 equiv. of IMes (2a/IMes) in toluene-d 8 (400 MHz) 7 days after mixing. 9

10 Figure S15. 1 H- 1 H ROESY NMR spectrum of the post-reaction mixture of [Me 2Al(μ- OCH 2CH 2OMe)] 2 with 4 equiv. of IMes (2a/IMes) in toluene-d 8 (400 MHz). Crosspeaks of signals corresponding to CH Ar of free and coordinated IMes, are marked with green circle. 10

11 Figure S16. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OCH 2CH 2OMe)] 2 with 4 equiv. of SIMes in toluene-d 8 (400 MHz). Figure S C NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OCH 2CH 2OMe)] 2 with 4 equiv. of SIMes in toluene-d 8 (100 MHz). 11

12 Figure S18. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al((S)-melac)] 2 with IMes in toluene-d 8 (400 MHz). 12

13 Figure S C NMR spectrum of the post-reaction mixture of [Me 2Al((S)-melac)] 2 with IMes in toluene-d 8 (100 MHz). Figure S20. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al((S)-melac)] 2 with IMes in toluene-d 8 (400 MHz) 2 days after mixing. 13

14 Figure S21. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al((S)-melac)] 2 with IMes in toluene-d 8 (400 MHz) 6 days after mixing. 14

15 Figure S22. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al((S)-melac)] 2 with SIMes in toluene-d 8 (400 MHz). Figure S C NMR spectrum of the post-reaction mixture of [Me 2Al((S)-melac)] 2 with SIMes in toluene-d 8 (100 MHz). 15

16 Figure S24. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al((S)-melac)] 2 with SIMes in toluene-d 8 (400 MHz) 1 day after mixing. 16

17 Figure S25. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al((S)-melac)] 2 with SIMes in toluene-d 8 (400 MHz) 4 days after mixing. Figure S26. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OCPh 2Me)] 2 with IMes in toluene-d 8 (400 MHz). 17

18 Figure S27. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OCPh 2Me)] 2 with IMes in toluene-d 8 (400 MHz) 3 days after mixing. Figure S28. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OCPh 2Me)] 2 with IMes in toluene-d 8 (400 MHz) 11 days after mixing. 18

19 Figure S29. 1 H NMR spectrum of Me 2Al(OCPh 2Me)(IMes) (3a) in toluene-d 8 (400 MHz). Figure S C NMR spectrum of Me 2Al(OCPh 2Me)(IMes) (3a) in toluene-d 8 (100 MHz). 19

20 Figure S31. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OCPh 2Me)] 2 with SIMes in toluene-d 8 (400 MHz). Figure S C NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OCPh 2Me)] 2 with SIMes in toluene-d 8 (100 MHz). 20

21 Figure S33. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OCPh 2Me)] 2 with SIMes in toluene-d 8 (400 MHz) 14 days after mixing. 21

22 Figure S34. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OCPh 2Me)] 2 with SIMes in toluene-d 8 (400 MHz) 35 days after mixing. Figure S35. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OCPh 2Me)] 2 with SIMes in toluene-d 8 (400 MHz) 77 days after mixing. 22

23 Figure S36. 1 H NMR spectrum of crystals of Me 2Al(OCPh 2Me)(SIMes), with cocrystallized SIMes, in toluene-d 8 (400 MHz). 23

24 Figure S C NMR spectrum of Me 2Al(OCPh 2Me)(SIMes) with cocrystallized SIMes in toluene-d 8 (100 MHz). Figure S38. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OCPhMeH)] 2 with IMes in toluene-d 8 (400 MHz). 24

25 Figure S39. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OCPhMeH)] 2 with IMes in toluene-d 8 (400 MHz) 27 hours after mixing. Figure S40. 1 H NMR spectrum of the post-reaction mixture of [Me 2Al(μ-OCPhMeH)] 2 with IMes in toluene-d 8 (400 MHz) 75 hours after mixing. 25

26 Figure S41. 1 H NMR spectrum of Me 2Al(OC 6H 4OMe)(IMes) (4a) in toluene-d 8 (400 MHz). Figure S C NMR spectrum of Me 2Al(OC 6H 4OMe)(IMes) (4a) in toluene-d 8 (100 MHz). 26

27 Figure S43. 1 H NMR spectrum of Me 2Al(OC 6H 4OMe)(SIMes) (4b) in toluene-d 8 (400 MHz). Figure S C NMR spectrum of Me 2Al(OC 6H 4OMe)(SIMes) (4b) in toluene-d 8 (100 MHz). 27

28 Figure S45. 1 H NMR spectrum of Me 2Ga(OCH 2CH 2OMe)(IMes) in toluene-d 8 (400 MHz). Figure S C NMR spectrum of Me 2Ga(OCH 2CH 2OMe)(IMes) in toluene-d 8 (100 MHz). 28

29 Figure S47. 1 H NMR (CDCl 3, 400 MHz) spectrum of PLA (precipitated from CH 2Cl 2 solution with MeOH), prepared by polymerization of 50 equiv. of rac-la with Me 2Al(OC 6H 4OMe)(IMes) (4a) as initiator, in CH 2Cl 2, -20⁰C, 2h. 29

30 Figure S C NMR (CDCl 3, 100 MHz) spectrum of PLA, P m = 0.78 (precipitated from CH 2Cl 2 solution with MeOH) prepared by polymerization of 50 equiv. of rac-la with Me 2Al(OC 6H 4OMe)(IMes) (4a) as initiator, in CH 2Cl 2, -20⁰C, 2h. Figure S49. 1 H NMR (CDCl 3, 400 MHz) spectrum of PLA (precipitated from CH 2Cl 2 solution with MeOH) prepared by polymerization of 50 equiv. of rac-la with Me 2Al(OC 6H 4OMe)(SIMes) (4b) as initiator, in CH 2Cl 2, -20⁰C, 2h. 30

31 Figure S C NMR (CDCl 3, 100 MHz) spectrum of PLA, P m = 0.80 (precipitated from CH 2Cl 2 solution with MeOH) prepared by polymerization of 50 equiv. of rac-la with Me 2Al(OC 6H 4OMe)(SIMes) (4b) as initiator, in CH 2Cl 2, -20⁰C, 2h. 31

32 Figure S51. 1 H NMR (CDCl 3, 400 MHz) spectrum of PLA (precipitated from CH 2Cl 2 solution with MeOH) prepared by polymerization of 50 equiv. of rac-la with reaction mixture of IMes and [Me 2Al(μ-OMe)] 3 as initiator, in CH 2Cl 2, -20⁰C, 2h. Figure S C NMR (CDCl 3, 100 MHz) spectrum of PLA, P m = 0.76 (precipitated from CH 2Cl 2 solution with MeOH) prepared by polymerization of 50 equiv. of rac-la with reaction mixture of IMes and [Me 2Al(μ-OMe)] 3 as initiator, in CH 2Cl 2, -20⁰C, 2h. 32

33 Figure S53. GPC data for PLA obtained by polymerization of 50 equiv. of rac-la with 1a as initiator, in CH 2Cl 2, -20 C, 2h. 33

34 Figure S54. GPC data for PLA obtained by polymerization of 50 equiv. of rac-la with 4a as initiator, in CH 2Cl 2, -20 C, 2h. 34

35 Figure S55. GPC data for PLA obtained by polymerization of 50 equiv. of rac-la with 4b as initiator, in CH 2Cl 2, -20 C, 2h. 35

36 E Table S1. Crystal data and structure refinement details. Compound 1a 1b 2a 3a 4a Chemical formula C 24H 33N 2OAl C 24H 35AlN 2O C 26H 37N 2O 2Al C 37H 43N 2OAl C 30H 37AlN 2O 2 M /g mol T /K 120.0(1) 293.0(1) 120.0(1) 293.1(2) 120.0(1) Crystal system monoclinic orthorhombic triclinic triclinic triclinic Space group P2 1/n Pna2 1 P1 PA1 E PA1 E a /Å (2) (11) (4) (8) (3) b /Å (5) (4) (4) (7) (3) c /Å (4) (10) (7) (13) (7) α/ (4) (6) (2) β / (2) (4) (7) (3) γ/ (4) (7) (4) V /Å (11) (2) (10) (2) (9) Z D calc /g cm μ /mm F(000) Crystal size /mm Θ Range / to to to to to Reflections collected Independent refln [R int = , R sigma = ] 4667 [R int = , R sigma = ] [R int = , R sigma = ] 6638 [R int = , R sigma = ] 5997 [R int = , R sigma = ] Data/restraints/param eters 4886/0/ /1/ /0/ /0/ /0/325 S (F 2 ) [a] R1, wr2 (I>2σ(I)) [b] R 1 = , wr 2 = R 1 = , wr 2 = R 1 = , wr 2 = R 1 = , wr 2 = R 1 = , wr 2 = R1, wr2 (all data) R 1 = , R 1 = , R 1 = , wr 2 R 1 = , R 1 = , wr 2 = wr 2 = = wr 2 = wr 2 = Δρ min/max/eå / / / / /-0.27 Flack parameter (11) CCD number Compound SI1 SI2 Chemical formula C 26H 37GaN 2O 2 C 31H 41InN 2O M /g mol T /K 293.0(1) 100.(2) Crystal system triclinic monoclinic Space group PA1 E P21/c a /Å (3) (6) b /Å (3) (7) c /Å (5) (10) α/ (2) 90 β / (2) (12) γ/ (3) 90 V /Å (8) (3) Z 2 4 D calc /g cm μ /mm F(000) Crystal size /mm Θ Range / 6.76 to to 52 Reflections collected

37 Independent refln [R int = , R sigma = ] 5718 [R int = , R sigma = ] Data/restraints/param eters 5840/0/ /0/325 S (F 2 ) [a] R1, wr2 (I>2σ(I)) [b] R 1 = , wr 2 = R 1 = , wr 2 = R1, wr2 (all data) R 1 = , R 1 = , wr 2 = wr 2 = Δρ min/max/eå / /-0.37 Flack parameter - - CCD number [a] Goodness-of-fit S={Σ[w(F o2 F c2 ) 2 ]/(n p)} 1/2 where n is the reflections number and p is the parameters number; [b] R1=Σ F o F c /Σ F o, wr2={σ[w(f o2 F c2 ) 2 ]/Σ[w(F o2 ) 2 ]} 1/2. Figure S56. Molecular structure of Me 2Ga(OCH 2CH 2OMe)(IMes) (SI1) with thermal ellipsoids at the 50% probability level. Hydrogen atoms are omitted for clarity. Selected bond lengths (Å) and angles (deg): Ga(1) C(4) 1.970(3), Ga(1) C(5) 1.985(3), Ga(1) C(1) 2.076(2), Ga(1) O(1) (17), C(4) Ga(1) C(1) (10), C(5) Ga(1) C(1) (14), O(1) Ga(1) C(1) 96.93(7), N(2) C(1) N(1) (16), C(5) Ga(1) C(1) N(1) (16), C(4) Ga(1) C(1) N(1) (17), O(1) Ga(1) C(1) N(1) 90.66(13), NHC tilt 2.7(1). 37

38 Figure S57. Molecular structure of Me 2In(OMe)(IMes) (SI2) with thermal ellipsoids at the 50% probability level. Selected bond lengths (Å) and angles (deg): In(1) C(4) (18), In(1) C(5) (19), In(1) C(1) (18), In(1) O(1) (13), C(4) In(1) C(1) (7), C(5) In(1) C(1) (7), O(1) In(1) C(1) (6), N(2) C(1) N(1) (15), C(5) In(1) C(1) N(1) (12), C(4) In(1) C(1) N(1) 10.56(10), O(1) In(1) C(1) N(1) (11), NHC tilt 2.4(1). 38

39 Figure S58. Resultant bond valence vector at the gallium center (in red) for 3a (0.049 vu), and Al O and Al C bond valencies, calculated according to the methodology described by J. Zachara, 1 which had been previously used for the characterization of e.g. gallium complexes. 2 For the graphical presentation it was assumed that 1 vu is equal to 10 Å. 39

40 Table S2. Calculated Bond Topological a and Integrated b Bond Descriptors for O M of selected Me 2MOR(NHC) and Me 2MOAr(NHC) (M = Al, Ga, In; NHC = IMes, SIMes and 6-Mes). bond d ρbcp 2 ρbcp ε G/ρbcp H/ρbcp Me2AlOMe(IMes) (1a) O Al Me2GaOMe(IMes) O Ga Me2InOMe(IMes) O In Me2AlOMe(SIMes) (1b) O Al Me2GaOMe(SIMes) O Ga Me2InOMe(SIMes) O In Me2Al(OCPh2Me)(IMes) (3a) O Al Me2Ga(OCPh2Me)(IMes) O Ga Me2Ga(OCPh2Me)(6-Mes) O Ga Me2In(OCPh2Me)(IMes) O In Me2In(OCPh2Me)(6-Mes) O In Me2Al(OC6H4OMe)(IMes) (4a) O Al Me2Ga(OC6H4OMe)(IMes) O Ga Me2In(OC6H4OMe)(IMes) O In basin δ V001 ELI ELIpop ELImax ELI RJI (e) RJI (%) Me2AlOMe(IMes) (1a) O Al (0.09 c ) 95.0 (5.0 c ) Me2GaOMe(IMes) O Ga 0.55 Me2InOMe(IMes) O In 0.56 Me2AlOMe(SIMes) (1b) O Al (0.10 c ) 95.0 (5.0 c ) Me2GaOMe(SIMes) O Ga 0.55 Me2InOMe(SIMes) O In 0.58 Me2Al(OCPh2Me)(IMes) (3a) O Al (0.69 c ) 95.8 (4.1 c ) Me2Ga(OCPh2Me)(IMes) O Ga 0.52 Me2Ga(OCPh2Me)(6-Mes) O Ga 0.51 Me2In(OCPh2Me)(IMes) O In 0.53 Me2In(OCPh2Me)(6-Mes) O In 0.53 Me2Al(OC6H4OMe)(IMes) (4a) O Al (0.08 c ) 96.8 (3.1 c ) Me2Ga(OC6H4OMe)(IMes) O Ga Me2In(OC6H4OMe)(IMes) O In 0.45 a Definitions and units: Bond lengths (d) in Å and bond topological properties: electron density ρbcp in e Å 3 and its corresponding Laplacian 2 ρbcp, in e Å 5 ; ε, bond ellipticity; G/ρbcp and H/ρbcp, kinetic and total energy density over ρbcp ratios in he 1 ). b Definitions and units: δ the delocalization index; V001 ELI, volume of the ELI-D basin in Å 3 cut at 0.001au; ELIpop, electron population within the ELI-D basin in e, ELImax, ELI-D value at the attractor position; ELI, the distance in Å of the attractor position perpendicular to the atom-atom axis; RJI, Raub-Jansen index in e and %. c Raub-Jansen index value for contribution of aluminum atom. 40

41 Table S3. Calculated Bond Topological a and Integrated b Bond Descriptors for C Me M of selected Me 2MOR(NHC) and Me 2MOAr(NHC) (M = Al, Ga, In; NHC = IMes, SIMes and 6-Mes). bond d ρbcp 2 ρbcp ε G/ρbcp H/ρbcp Me2AlOMe(IMes) (1a) CMe Al Me2GaOMe(IMes) CMe Ga Me2InOMe(IMes) CMe In Me2AlOMe(SIMes) (1b) CMe Al Me2GaOMe(SIMes) CMe Ga Me2InOMe(SIMes) CMe In Me2Al(OCPh2Me)(IMes) (3a) CMe Al Me2Ga(OCPh2Me)(IMes) CMe Ga Me2Ga(OCPh2Me)(6-Mes) CMe Ga Me2In(OCPh2Me)(IMes) CMe In Me2In(OCPh2Me)(6-Mes) CMe In Me2Al(OC6H4OMe)(IMes) (4a) CMe Al Me2Ga(OC6H4OMe)(IMes) CMe Ga Me2In(OC6H4OMe)(IMes) CMe In basin δ V001 ELI ELIpop ELImax ELI RJI (e) RJI (%) Me2AlOMe(IMes) (1a) CMe Al Me2GaOMe(IMes) CMe Ga Me2InOMe(IMes) CMe In Me2AlOMe(SIMes) (1b) CMe Al Me2GaOMe(SIMes) CMe Ga Me2InOMe(SIMes) CMe In Me2Al(OCPh2Me)(IMes) (3a) CMe Al Me2Ga(OCPh2Me)(IMes) CMe Ga Me2Ga(OCPh2Me)(6-Mes) CMe Ga Me2In(OCPh2Me)(IMes) CMe In Me2In(OCPh2Me)(6-Mes) CMe In Me2Al(OC6H4OMe)(IMes) (4a) CMe Al Me2Ga(OC6H4OMe)(IMes) CMe Ga Me2In(OC6H4OMe)(IMes) CMe In a Definitions and units: Bond lengths (d) in Å and bond topological properties: electron density ρbcp in e Å 3 and its corresponding Laplacian 2 ρbcp, in e Å 5 ; ε, bond ellipticity; G/ρbcp and H/ρbcp, kinetic and total energy density over ρbcp ratios in he 1 ). b Definitions and units: δ the delocalization index; V001 ELI, volume of the ELI-D basin in Å 3 cut at 0.001au; ELIpop, electron population within the ELI-D basin in e, ELImax, ELI-D value at the attractor position; ELI, the distance in Å of the attractor position perpendicular to the atom-atom axis; RJI, Raub-Jansen index in e and %. 41

42 Table S4. QTAIM Atomic Charges for selected Me 2MOR(NHC) and Me 2MOAr(NHC) (M = Al, Ga, In; NHC = IMes, SIMes and 6-Mes). Al/Ga/In CNHC O CMe Me2AlOMe(IMes) (1a) Me2GaOMe(IMes) Me2InOMe(IMes) Me2AlOMe(SIMes) (1b) Me2GaOMe(SIMes) Me2InOMe(SIMes) Me2Al(OCPh2Me)(IMes) (3a) Me2Ga(OCPh2Me)(IMes) Me2Ga(OCPh2Me)(6-Mes) Me2In(OCPh2Me)(IMes) Me2In(OCPh2Me)(6-Mes) Me2Al(OC6H4OMe)(IMes) (4a) Me2Ga(OC6H4OMe)(IMes) Me2In(OC6H4OMe)(IMes)

43 Figure S59. Molecular graphs of Me 2MOMe(IMes) (M = Al (1a) Ga, In). Figure S60. Isosurface representations of the localization domains of the ELI-D of Me 2MOMe(IMes) (M = Al (1a) Ga, In) (an isovalue of Y=1.45). Figure S61. ELI-D distributions onto V 2(M, C NHC) bonding (disynaptic valence) basins of Me 2MOMe(IMes) (M = Al (1a) Ga, In). 43

44 Figure S62. Molecular graphs of Me 2MOMe(SIMes) (M = Al (1b) Ga, In). Figure S63. Isosurface representations of the localization domains of the ELI-D of Me 2MOMe(SIMes) (M = Al (1b) Ga, In) (an isovalue of Y=1.45). Figure S64. ELI-D distributions onto V 2(M, C NHC) bonding (disynaptic valence) basins of Me 2MOMe(SIMes) (M = Al (1b) Ga, In). 44

45 Figure S65. Molecular graphs of Me 2M(OCPh 2Me)(IMes) (M = Al (3a) Ga, In). Figure S66. Isosurface representations of the localization domains of the ELI-D of Me 2M(OCPh 2Me)(IMes) (M = Al (3a) Ga, In) (an isovalue of Y=1.45). Figure S67. ELI-D distributions onto V 2(M, C NHC) bonding (disynaptic valence) basins of Me 2M(OCPh 2Me)(IMes) (M = Al (3a) Ga, In). 45

46 Figure S68. Molecular graphs of Me 2M(OCPh 2Me)(6-Mes) (M = Ga, In). Figure S69. Isosurface representations of the localization domains of the ELI-D of Me 2M(OCPh 2Me)(6-Mes) (M = Ga, In) (an isovalue of Y=1.45). 46

47 Figure S70. ELI-D distributions onto V 2(M, C NHC) bonding (disynaptic valence) basins of Me 2M(OCPh 2Me)(6- Mes) (M = Ga, In). 47

48 Figure S71. Molecular graphs of Me 2M(OC 6H 4OMe)(IMes) (M = Al (4a) Ga, In). Figure S72. Isosurface representations of the localization domains of the ELI-D of Me 2M(OC 6H 4OMe)(IMes) (M = Al (4a) Ga, In) (an isovalue of Y=1.45). Figure S73. ELI-D distributions onto V 2(M, C NHC) bonding (disynaptic valence) basins of Me 2M(OC 6H 4OMe)(IMes) (M = Al (4a) Ga, In). 48

49 1 Zachara, J. Inorg. Chem. 2007, 46, (a) Horeglad, P.; Ablialimov, O.; Szczepaniak, G.; Dąbrowska, A. M.; Dranka, M.; Zachara, J. Organometallics 2014, 33, ; (b) Cybularczyk, M.; Dranka, M.; Zachara, J.; Horeglad, P. Organometallics 2016, 35,