lewis acid-base adducts of group 13 elements: …1 -supporting information- lewis acid-base adducts...
TRANSCRIPT
1
-Supporting Information-
Lewis Acid-Base Adducts of Group 13 Elements: Synthesis, Structure and Reactivity
toward Benzaldehyde
Chelladurai Ganesamoorthy, Marcel Matthias, Dieter Bläser, Christoph Wölper and Stephan
Schulz*
Content
A) Fig. S1 - S25: NMR (1H,
13C,
19F) and IR spectra of 2 - 7
B) Figure S26. Temperature-dependant 1H NMR study of 2.
C) Fig. S27, S28: In situ 1H NMR experiment of B(C6F5)3 and Al(C6F5)3(Tol)0.5 with benzaldehyde and
LGa.
D) Table S1: Crystallographic details of 2, 3, 4 and 7
E) Crystallographic details of 5
Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2016
Figure S1. 1H NMR spectrum of [LGa
Figure S2. 13
C{1H} NMR spectrum of
LGa-Al(C6F5)3] 2 in C6D6 at room temperature
spectrum of [LGa-Al(C6F5)3] 2 in C6D6 at room temperature.
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at room temperature.
at room temperature.
Figure S3. 13
C{1H} dept-135 NMR spectrum of [LGa
Figure S4. 19
F NMR spectrum of [LGa
135 NMR spectrum of [LGa-Al(C6F5)3] 2 in C6D6 at room temperature.
[LGa-Al(C6F5)3] 2 in C6D6 at room temperature.
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at room temperature.
at room temperature.
Figure S5. ATR-IR spectrum of [LGa
Figure S6. 1H NMR spectrum of [LGa
IR spectrum of [LGa-Al(C6F5)3] 2.
H NMR spectrum of [LGa-Ga(C6F5)3] 3 in C6D6 at room temperature.
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at room temperature.
Figure S7. 13
C{1H} NMR spectrum of [LGa
Figure S8. 13
C{1H} dept135 NMR spectrum of [LGa
H} NMR spectrum of [LGa-Ga(C6F5)3] 3 in C6D6 at room temperature.
H} dept135 NMR spectrum of [LGa-Ga(C6F5)3] 3 in C6D6 at room temperature.
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at room temperature.
at room temperature.
Figure S9. 19
F NMR spectrum of [LGa
Figure S10. ATR-IR spectrum of [LGa
F NMR spectrum of [LGa-Ga(C6F5)3] 3 in C6D6 at room temperature.
IR spectrum of [LGa-Ga(C6F5)3] 3.
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at room temperature.
Figure S11. 1H NMR spectrum of [LGa
Figure S12. 13
C{1H} NMR spectrum of
temperature.
H NMR spectrum of [LGa(C6F5){CH(Ph)(OB(C6F5)2)}] 4 in C6D6
H} NMR spectrum of [LGa(C6F5){CH(Ph)(OB(C6F5)2)}]
7
at room temperature.
)}] 4 in C6D6 at room
Figure S13. 13
C{1H} dept-135 NMR spectrum of [LGa(
temperature.
135 NMR spectrum of [LGa(C6F5){CH(Ph)(OB(C6F
8
F5)2)}] 4 in C6D6 at room
Figure S14. 19
F NMR spectrum of [LGa(C
Figure S15. ATR-IR spectrum of [LGa(C
[LGa(C6F5){CH(Ph)(OB(C6F5)2)}] 4 in C6D6
[LGa(C6F5){CH(Ph)(OB(C6F5)2)}] 4.
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at room temperature.
Figure S16. 1H NMR spectrum of [LGa(CH NMR spectrum of [LGa(C6F5){CH(Ph)(OAl(C6F5)2)}] 5 in C6D6
10
6 at room temperature.
Figure S17. 13
C{1H} NMR spectrum of [LGa(C
temperature.
H} NMR spectrum of [LGa(C6F5){CH(Ph)(OAl(C6F5)2)}]
11
)}] 5 in C6D6 at room
Figure S18. 19
F NMR spectrum of [LGa(CF NMR spectrum of [LGa(C6F5){CH(Ph)(OAl(C6F5)2)}] 5 in C6D6
12
6 at room temperature.
Figure S19. ATR-IR spectrum of [LGa(C
Figure S20. 1H NMR spectrum of {(C
Figure S21. 19
F NMR spectrum of {(C
IR spectrum of [LGa(C6F5){CH(Ph)(OAl(C6F5)2)}] 5.
H NMR spectrum of {(C6F5)2Al(OCH2Ph)}2 6 in C6D6 at room temperature.
F NMR spectrum of {(C6F5)2Al(OCH2Ph)}2 6 in C6D6 at room temperature.
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at room temperature.
at room temperature.
Figure S22. ATR-IR spectrum of {(C
Figure S23. 1H NMR spectrum of {(C
IR spectrum of {(C6F5)2Al(OCH2Ph)}2 6.
H NMR spectrum of {(C6F5)2Ga(OCH2Ph)}2 7 in C6D6 at room temperature.
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at room temperature.
Figure S24. 19
F NMR spectrum of {(C
Figure S25. ATR-IR spectrum of {(C
F NMR spectrum of {(C6F5)2Ga(OCH2Ph)}2 7 in C6D6 at room temperature.
IR spectrum of {(C6F5)2Ga(OCH2Ph)}2 7.
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at room temperature.
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Figure S26. Temperature-dependant 1H NMR study of 2.
Figure S27. In situ 1H NMR experiment of B(C6F5)3 with benzaldehyde and LGa in C6D6 at room
temperature. Equimolar amounts of benzaldehyde and LGa were stepwise added to B(C6F5)3 and
monitored after each additions via 1H NMR.
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Figure S28. In situ 1H NMR experiment of Al(C6F5)3(Tol)0.5 with benzaldehyde and LGa in C6D6 at
room temperature. Equimolar amounts of benzaldehyde and LGa were stepwise added to
Al(C6F5)3(Tol)0.5 and monitored after each additions via 1H NMR.
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Crystallographic data of 2 – 4, and 7.
Table S1. Crystallographic data of 2 – 4, and 7.
2 3 4 7
Empirical formula C47H41AlF15GaN2 C47H41F15Ga2N2 C54H47BF15GaN2O C38H14F20Ga2O2 M 1015.52 1058.26 1105.46 1021.93
Crystal size [mm] 0.385 × 0.324 × 0.277 0.323 × 0.244 × 0.172 0.170 × 0.150 × 0.130 0.088 × 0.059 ×
0.053 T [K] 100(1) 100(1) 100(1) 100(1)
Crystal system monoclinic monoclinic monoclinic triclinic Space group P21/n P21/n P21/c P -1
a [Å] 12.1325(11) 12.1241(9) 12.2876(8) 7.4230(5) b [Å] 21.616(2) 21.6245(16) 20.8316(13) 11.1300(8) c [Å] 17.5035(15) 17.4652(13) 20.7404(12) 11.2132(8) α [°] 90 90 90 104.138(4) β [°] 102.705(4) 103.146(3) 107.336(3) 106.229(4) γ [°] 90 90 90 93.986(4)
V [Å3] 4477.9(7) 4459.0(6) 5067.8(5) 853.06(11) Z 4 4 4 1
Dcalc [g⋅cm-1] 1.506 1.576 1.449 1.989 μ(MoKα [mm-1]) 0.733 1.308 0.639 1.728 Transmissions 0.75/0.68 0.75/0.65 0.75/0.57 0.75/0.64
F(000) 2064 2136 2256 500 Index ranges -17 ≤ h ≤ 17 -17 ≤ h ≤ 18 -16 ≤ h ≤ 16 -10 ≤ h ≤ 10
-29 ≤ k ≤ 30 -30 ≤ k ≤ 33 -28 ≤ k ≤ 28 -14 ≤ k ≤ 14 -24 ≤ l ≤ 24 -26 ≤ l ≤ 26 -28 ≤ l ≤ 28 0 ≤ l ≤ 16
θmax [°] 30.033 33.210 28.821 30.654 Reflections collected 88675 126920 113502 4685
Independent reflections 13096 16118 13086 4685 Rint 0.0280 0.0253 0.0873 0.0389
Refined parameters 605 605 667 281 R1 [I > 2σ(I)][a] 0.0282 0.0266 0.0502 0.0399 wR2 [all data][b] 0.0770 0.0691 0.1512 0.0980
GooF[c] 1.034 1.023 1.102 1.065 Δρfinal (max/min) [e⋅Å-3] 0.522/-0.284 0.507/-0.280 1.540/-0.832 0.651/-0.655
[a] R1 = Σ(||Fo| - |Fc||)/Σ|Fo| (for I > 2σ(I)). - [b]wR2 = {Σ[w(Fo2 - Fc2)2]/Σ[w(Fo2)2]}1/2. - [c] Goodness of fit = {Σ[w(|Fo2| -
|Fc2|)2]/(Nobservns - Nparams)}1/2. w–1 = σ2(Fo2) + (aP)2 + bP with P = [Fo2 + 2Fc2]/3, a and b are constants chosen by the
program.
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Crystallographic details of 5
RIGU restraints were applied to all ADP.
Treatment of hydrogen atoms
Riding model on idealized geometries with the 1.2 fold isotropic displacement parameters of the
equivalent Uij of the corresponding carbon atom. The methyl groups are idealized with tetrahedral angles
in a combined rotating and rigid group re_nement with the 1.5 fold isotropic displacement parameters of
the equivalent Uij of the corresponding carbon atom.
Disorder
The positions of carbon atoms of the benzene molecules were constrained to form a regular hexagon
(AFIX 66) and were disordered over two position.
Twinning
Appearantly the crystal was a non-merohedral twinned but since the two components strongly overlapp
they could not be separated and the twinning was not accounted for in the refinement. Consequently only
qualitative results from the model should be regarded meaningful.
Table S2: Crystal structure data of 5.
Identification code mm_002am_a
Empirical formula C78.05 H71.05 Al F15 Ga N2 O
Formula weight 1434.71
Density (calculated) 1.378 g⋅cm-1
F(000) 5923
Temperature 100(1) K
Crystal size 0.361 × 0.257 × 0.237 mm
Crystal colour colourless
Crystal description block
Wavelength 0.71073 Å
Crystal system orthorhombic
Space group Pnna
Unit cell dimensions
a [Å] 18.3614(10)
b [Å] 49.880(2)
c [Å] 15.0992(8)
α [°] 90
β [°] 90
γ [°] 90
Volume 13829.0(12) Å3
Z 8
20
Cell measurement reflections used 9350
Cell measurement θ min/max 2.45°/31.19°
Diffractometer control software BRUKER D8 KAPPA APEX 2 (3.0-2009)
Diffractometer measurement device Bruker D8 KAPPA series II with APEX II area detector system
Diffractometer measurement method Data collection strategy APEX 2/COSMO
θ range for data collection 1.793°- 32.330°
Completeness to θ = 25.242° 100.0%
Completeness to θmax = 32.330° 89.9%
Index ranges -26 ≤ h ≤ 19
-71 ≤ k ≤ 73
-21 ≤ l ≤ 19
Computing data reduction BRUKER D8 KAPPA APEX 2 (3.0-2009)
Absorption coefficient 0.498 mm-1
Absorption correction Semi-empirical from equivalents
Computation absorption correction BRUKER AXS SMART APEX 2 Vers. 3.0-2009
Max./min. Transmission 0.75/0.61
Rmerg before/after correction 0.0900/0.0718
Computing structure solution BRUKER D8 KAPPA APEX 2 (3.0-2009)
Computing structure refinement SHELXL-2014/7 (Sheldrick, 2014)
Refinement method Full-matrix least-squares on F2
Reflections collected 205887
Independent reflections 22189
Rint 0.0484
Reflections with I > 2σ(I) 19226
Restraints 918
Parameter 1018
GooF 1.270
Weighting details w = 1/[σ2(Fobs2) + 144.2076P]
where P = (Fobs2 + 2Fcalc
2)/3
R1 [I > 2σ(I)] 0.1246
wR2 [I > 2σ(I)] 0.2735
R1 [all data] 0.1356
wR2 [all data] 0.2776
Largest diff. peak and hole 0.883/-2.881
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Table S3: Atomic coordinates ( × 104) and equivalent isotropic displacement parameters (Å2 × 103) for mm_002am_a. Ueq is defined as one third of the trace of the orthogonalized Uij tensor.
x y z Ueq
Ga(1) 6460(1) 3918(1) 6859(1) 15(1)
Al(1) 6237(1) 3677(1) 4585(1) 16(1)
F(1) 7679(2) 3721(1) 8023(2) 27(1)
F(2) 8102(2) 3825(1) 9685(3) 51(1)
F(3) 7364(3) 4193(1) 10672(3) 68(2)
F(4) 6225(2) 4464(1) 9940(3) 50(1)
F(5) 5796(2) 4359(1) 8294(2) 31(1)
F(6) 7937(2) 3571(1) 4375(2) 29(1)
F(7) 8682(2) 3156(1) 3742(3) 48(1)
F(8) 7982(3) 2696(1) 3280(3) 52(1)
F(9) 6512(3) 2664(1) 3441(3) 53(1)
F(10) 5752(2) 3083(1) 4063(3) 38(1)
F(11) 4818(2) 3473(1) 3562(3) 39(1)
F(12) 4228(3) 3624(1) 2023(3) 60(1)
F(13) 4765(3) 4050(2) 1132(3) 83(2)
F(14) 5933(3) 4327(2) 1804(5) 102(3)
F(15) 6564(3) 4166(1) 3298(3) 56(1)
O(1) 6762(2) 3922(1) 5041(2) 19(1)
N(1) 6176(2) 3523(1) 6917(3) 16(1)
N(2) 5478(2) 4025(1) 6399(3) 15(1)
C(1) 5762(3) 3427(1) 6296(3) 16(1)
C(2) 5459(3) 3599(1) 5595(3) 15(1)
H(2) 5049 3498 5315 18
C(3) 5181(3) 3867(1) 5811(3) 14(1)
C(4) 5566(3) 3136(1) 6231(4) 20(1)
H(4A) 5738 3042 6762 30
H(4B) 5796 3058 5705 30
H(4C) 5036 3118 6185 30
C(5) 4524(3) 3951(1) 5284(3) 22(1)
H(5A) 4529 3860 4708 32
H(5B) 4534 4145 5195 32
H(5C) 4081 3901 5607 32
C(6) 6490(3) 3348(1) 7590(3) 18(1)
C(7) 6190(3) 3359(1) 8451(3) 22(1)
C(8) 6533(4) 3205(1) 9106(4) 29(1)
H(8) 6349 3207 9694 34
C(9) 7136(4) 3049(1) 8908(4) 30(1)
H(9) 7366 2948 9364 36
C(10) 7403(3) 3038(1) 8065(4) 26(1)
H(10) 7811 2927 7941 31
C(11) 7088(3) 3187(1) 7379(3) 19(1)
22
C(12) 5502(3) 3514(1) 8662(4) 25(1)
H(12) 5492 3676 8271 30
C(13) 4830(4) 3347(1) 8450(5) 35(1)
H(13A) 4839 3182 8802 53
H(13B) 4828 3302 7819 53
H(13C) 4391 3450 8594 53
C(14) 5479(4) 3612(2) 9626(4) 42(2)
H(14A) 5438 3458 10025 63
H(14B) 5058 3730 9708 63
H(14C) 5927 3711 9760 63
C(15) 7425(3) 3167(1) 6467(3) 22(1)
H(15) 7131 3280 6055 27
C(16) 7408(4) 2877(1) 6111(4) 28(1)
H(16A) 6902 2818 6050 42
H(16B) 7664 2758 6526 42
H(16C) 7649 2870 5532 42
C(17) 8212(3) 3272(1) 6454(4) 28(1)
H(17A) 8516 3161 6842 42
H(17B) 8220 3458 6663 42
H(17C) 8403 3265 5848 42
C(18) 5110(3) 4281(1) 6600(3) 17(1)
C(19) 5424(3) 4518(1) 6277(4) 22(1)
C(20) 5062(3) 4760(1) 6463(5) 30(1)
H(20) 5263 4923 6253 36
C(21) 4421(3) 4766(1) 6944(5) 32(1)
H(21) 4178 4931 7051 38
C(22) 4142(3) 4528(1) 7265(4) 27(1)
H(22) 3708 4533 7608 33
C(23) 4470(3) 4281(1) 7107(3) 20(1)
C(24) 6140(3) 4534(1) 5789(4) 25(1)
H(24) 6333 4348 5721 30
C(25) 6696(3) 4696(1) 6325(5) 32(1)
H(25A) 6779 4608 6896 47
H(25B) 6509 4877 6424 47
H(25C) 7156 4705 5997 47
C(26) 6045(4) 4654(1) 4858(4) 33(1)
H(26A) 5872 4839 4907 50
H(26B) 5690 4548 4525 50
H(26C) 6514 4652 4547 50
C(27) 4124(3) 4034(1) 7512(4) 23(1)
H(27) 4404 3873 7315 28
C(28) 4169(3) 4053(1) 8525(4) 31(1)
H(28A) 3902 4212 8726 47
H(28B) 4680 4068 8705 47
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H(28C) 3954 3893 8789 47
C(29) 3326(3) 4001(1) 7231(4) 31(1)
H(29A) 3286 4023 6588 46
H(29B) 3027 4136 7529 46
H(29C) 3156 3821 7397 46
C(30) 6707(3) 4030(1) 8092(3) 19(1)
C(31) 7295(3) 3905(1) 8485(4) 25(1)
C(32) 7527(4) 3956(2) 9336(4) 36(2)
C(33) 7162(4) 4143(2) 9833(4) 43(2)
C(34) 6578(4) 4278(1) 9471(4) 37(2)
C(35) 6368(3) 4220(1) 8614(4) 25(1)
C(36) 6802(3) 3347(1) 4257(3) 19(1)
C(37) 7555(3) 3352(1) 4149(4) 23(1)
C(38) 7955(3) 3138(1) 3821(4) 30(1)
C(39) 7600(4) 2905(1) 3592(5) 36(1)
C(40) 6854(4) 2887(1) 3679(5) 36(1)
C(41) 6485(3) 3106(1) 4007(4) 28(1)
C(42) 5713(3) 3814(1) 3496(3) 24(1)
C(43) 5123(3) 3687(1) 3138(4) 30(1)
C(44) 4794(4) 3761(2) 2350(4) 43(2)
C(45) 5070(4) 3979(2) 1901(5) 55(2)
C(46) 5657(5) 4112(2) 2230(5) 59(2)
C(47) 5970(4) 4029(2) 3021(5) 39(2)
C(48) 7175(3) 3923(1) 5836(3) 16(1)
H(48) 7440 3748 5856 20
C(49) 7749(3) 4138(1) 5810(3) 18(1)
C(50) 7821(3) 4304(1) 5074(4) 22(1)
H(50) 7500 4282 4586 27
C(51) 8359(3) 4501(1) 5043(5) 30(1)
H(51) 8404 4612 4536 36
C(52) 8829(3) 4534(1) 5753(5) 31(1)
H(52) 9194 4669 5735 37
C(53) 8764(3) 4368(1) 6497(4) 30(1)
H(53) 9083 4391 6987 36
C(54) 8230(3) 4172(1) 6516(4) 24(1)
H(54) 8192 4059 7019 29
C(60) 2898(10) 5227(2) 7407(8) 50(4)
H(60) 3050 5385 7111 60
C(61) 2484(12) 5037(3) 6961(5) 39(3)
H(61) 2352 5065 6360 46
C(62) 2262(9) 4805(2) 7394(7) 46(4)
H(62) 1979 4675 7089 56
C(63) 2455(6) 4763(2) 8273(7) 51(3)
H(63) 2304 4604 8569 61
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C(64) 2870(7) 4953(3) 8719(6) 66(5)
H(64) 3002 4924 9320 79
C(65) 3091(7) 5185(2) 8286(8) 59(4)
H(65) 3375 5315 8591 71
C(70) 5449(7) 2402(3) 6718(9) 80(6)
H(70) 5572 2323 6166 96
C(71) 5993(6) 2463(2) 7325(10) 60(4)
H(71) 6488 2426 7187 72
C(75) 5814(5) 2579(2) 8133(9) 56(4)
H(75) 6185 2621 8548 67
C(72) 5090(6) 2633(3) 8334(9) 72(6)
H(72) 4967 2713 8887 86
C(74) 4546(5) 2572(5) 7728(12) 87(8)
H(74) 4051 2609 7865 104
C(73) 4725(7) 2456(4) 6919(11) 86(7)
H(73) 4354 2414 6505 104
C(80) 4802(6) 2941(2) 730(7) 42(3)
H(80) 4996 3112 876 51
C(81) 4053(5) 2907(2) 648(8) 46(4)
H(81) 3736 3055 739 55
C(82) 3769(4) 2657(2) 434(9) 52(4)
H(82) 3258 2634 378 62
C(83) 4234(6) 2441(2) 301(9) 59(5)
H(83) 4040 2270 154 71
C(84) 4982(5) 2475(2) 382(9) 53(4)
H(84) 5300 2327 291 63
C(85) 5266(4) 2725(2) 596(8) 47(3)
H(85) 5778 2748 652 57
C(80C) 4359(8) 2961(2) 1425(12) 75(5)
H(80C) 4322 3151 1443 90
C(80A) 4150(8) 2822(4) 668(10) 91(7)
H(80A) 3970 2917 169 110
C(80B) 4205(9) 2544(4) 642(11) 104(7)
H(80B) 4062 2449 125 125
C(80D) 4468(9) 2405(2) 1373(14) 100(7)
H(80D) 4505 2215 1355 120
C(80E) 4677(8) 2544(3) 2130(11) 94(6)
H(80E) 4857 2449 2629 113
C(80F) 4622(7) 2822(3) 2156(10) 81(5)
H(80F) 4765 2916 2673 98
C(90) 4221(7) 4817(3) 1543(6) 59(4)
H(90) 4444 4848 2101 70
C(91) 4648(5) 4753(2) 812(8) 47(3)
H(91) 5162 4741 871 56
25
C(92) 4322(6) 4707(2) -5(7) 53(4)
H(92) 4613 4663 -505 63
C(93) 3570(6) 4725(2) -91(6) 50(4)
H(93) 3347 4693 -650 60
C(94) 3143(5) 4789(2) 640(8) 52(4)
H(94) 2629 4801 581 63
C(95) 3469(7) 4835(3) 1457(6) 67(6)
H(95) 3178 4878 1956 80
C(90A) 4113(7) 4957(2) 1599(8) 54(4)
H(90A) 4242 5109 1944 65
C(91A) 4607(5) 4851(2) 995(10) 67(6)
H(91A) 5073 4931 926 80
C(92A) 4418(6) 4629(2) 490(9) 63(5)
H(92A) 4756 4557 77 75
C(93A) 3736(6) 4512(2) 590(7) 51(4)
H(93A) 3607 4360 245 61
C(94A) 3243(5) 4617(2) 1194(7) 47(3)
H(94A) 2776 4537 1263 56
C(95A) 3431(6) 4840(2) 1699(7) 53(4)
H(95A) 3094 4912 2112 64
C(100) 7749(4) 3163(2) 1227(7) 50(4)
H(100) 8241 3128 1070 60
C(101) 7255(5) 2953(1) 1295(7) 42(3)
H(101) 7408 2774 1185 50
C(102) 6535(5) 3004(2) 1524(6) 42(3)
H(102) 6197 2861 1571 50
C(103) 6310(4) 3266(2) 1685(6) 45(3)
H(103) 5818 3301 1842 54
C(104) 6804(6) 3476(1) 1617(7) 45(3)
H(104) 6651 3655 1727 54
C(105) 7524(6) 3424(2) 1387(7) 53(3)
H(105) 7862 3568 1341 64
C(10A) 7763(7) 3089(3) 1226(9) 37(4)
H(10A) 8177 2983 1086 44
C(10B) 7146(8) 2970(2) 1587(10) 37(4)
H(10B) 7139 2782 1695 45
C(10C) 6541(6) 3125(3) 1792(9) 42(4)
H(10C) 6120 3044 2039 50
C(10D) 6552(7) 3400(3) 1635(8) 33(4)
H(10D) 6138 3506 1775 39
C(10E) 7168(8) 3519(2) 1273(9) 38(4)
H(10E) 7175 3707 1166 46
C(10F) 7774(6) 3364(3) 1069(9) 39(4)
H(10F) 8195 3445 822 47
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Table S4: Anisotropic displacement parameters (Å2 × 103) for mm_002am_a. The anisotropic displacement factor exponent takes the form: -2π2[h2
a*2U11 + ... + 2hka*b*U12 ]
U11 U22 U33 U23 U13 U12
Ga(1) 19(1) 13(1) 14(1) -1(1) -2(1) 0(1)
Al(1) 20(1) 15(1) 12(1) 2(1) 0(1) 0(1)
F(1) 31(2) 25(2) 23(2) -6(1) -5(1) 7(1)
F(2) 48(2) 74(3) 31(2) -16(2) -23(2) 27(2)
F(3) 66(3) 108(4) 30(2) -41(2) -30(2) 35(3)
F(4) 51(3) 57(3) 43(2) -33(2) -11(2) 16(2)
F(5) 32(2) 29(2) 34(2) -10(1) -5(2) 10(1)
F(6) 26(2) 25(2) 35(2) -4(1) 5(1) -4(1)
F(7) 28(2) 51(2) 66(3) -14(2) 12(2) 11(2)
F(8) 59(3) 34(2) 64(3) -18(2) 11(2) 16(2)
F(9) 61(3) 27(2) 71(3) -27(2) 3(2) -6(2)
F(10) 28(2) 37(2) 49(2) -16(2) 0(2) -7(2)
F(11) 38(2) 49(2) 29(2) 5(2) -13(2) -12(2)
F(12) 45(2) 105(4) 31(2) 5(2) -15(2) 9(3)
F(13) 65(3) 150(6) 33(2) 43(3) 1(2) 47(4)
F(14) 68(4) 140(5) 97(5) 99(4) -3(3) 5(4)
F(15) 44(2) 65(3) 58(3) 42(2) -3(2) -11(2)
O(1) 23(2) 16(1) 18(2) 2(1) 0(1) -2(1)
N(1) 20(2) 12(2) 15(2) 2(1) -1(1) 3(1)
N(2) 16(2) 13(2) 16(2) 1(1) 1(1) 0(1)
C(1) 18(2) 14(2) 16(2) 4(1) 0(2) 0(2)
C(2) 19(2) 10(2) 15(2) 2(1) -1(2) 1(1)
C(3) 18(2) 11(2) 15(2) 5(1) 2(2) 0(1)
C(4) 26(2) 12(2) 24(2) 1(2) -4(2) -2(2)
C(5) 24(2) 21(2) 20(2) 0(2) -6(2) 6(2)
C(6) 24(2) 15(2) 16(2) 3(1) -7(2) 1(2)
C(7) 28(2) 19(2) 19(2) 6(2) -4(2) 0(2)
C(8) 40(3) 29(2) 17(2) 5(2) -4(2) 7(2)
C(9) 45(3) 26(2) 19(2) 8(2) -8(2) 10(2)
C(10) 33(3) 22(2) 22(2) 4(2) -7(2) 5(2)
C(11) 25(2) 18(2) 16(2) 1(2) -4(2) 1(2)
C(12) 28(2) 28(2) 18(2) 4(2) -1(2) 3(2)
C(13) 31(3) 39(3) 36(3) 5(3) 2(2) -1(2)
C(14) 54(4) 49(4) 23(3) -4(3) -3(3) 16(3)
C(15) 25(2) 22(2) 20(2) 2(2) -4(2) 4(2)
C(16) 37(3) 19(2) 27(3) -1(2) -2(2) 9(2)
C(17) 27(3) 29(3) 28(3) -2(2) -2(2) 3(2)
C(18) 22(2) 12(2) 18(2) -2(1) -2(2) 4(1)
C(19) 23(2) 12(2) 30(2) 1(2) 0(2) 3(2)
C(20) 26(3) 15(2) 48(3) 0(2) -2(2) 4(2)
C(21) 27(3) 18(2) 50(3) -4(2) -4(2) 5(2)
27
C(22) 22(2) 19(2) 40(3) -7(2) 1(2) 5(2)
C(23) 23(2) 17(2) 22(2) -1(2) -1(2) 5(2)
C(24) 25(2) 14(2) 36(3) 2(2) 5(2) 2(2)
C(25) 25(3) 24(2) 45(3) -4(2) 4(2) 1(2)
C(26) 38(3) 29(3) 32(3) 10(2) 8(2) 4(2)
C(27) 26(2) 20(2) 24(2) -4(2) 5(2) -1(2)
C(28) 30(3) 40(3) 24(2) -1(2) 3(2) 0(2)
C(29) 30(3) 33(3) 30(3) -5(2) 4(2) -5(2)
C(30) 24(2) 19(2) 15(2) -5(2) -4(2) 2(2)
C(31) 27(2) 25(2) 21(2) -5(2) -5(2) 0(2)
C(32) 35(3) 54(4) 20(2) -15(2) -13(2) 14(3)
C(33) 47(3) 55(4) 27(3) -22(3) -18(3) 17(3)
C(34) 41(3) 44(3) 26(2) -21(2) -11(2) 11(3)
C(35) 29(3) 26(2) 22(2) -9(2) -7(2) 3(2)
C(36) 23(2) 18(2) 16(2) -1(2) 2(2) 2(2)
C(37) 26(2) 21(2) 23(2) -4(2) 3(2) 1(2)
C(38) 28(2) 30(2) 32(3) -5(2) 5(2) 5(2)
C(39) 43(3) 27(2) 37(3) -9(2) 6(2) 9(2)
C(40) 43(3) 24(2) 40(3) -13(2) 3(2) -2(2)
C(41) 30(2) 25(2) 30(3) -8(2) 1(2) -6(2)
C(42) 21(2) 38(3) 12(2) 9(2) 5(2) 6(2)
C(43) 27(3) 46(3) 15(2) 4(2) 2(2) 8(2)
C(44) 33(3) 81(4) 15(2) 6(2) 0(2) 23(3)
C(45) 39(3) 99(5) 28(3) 33(3) 3(2) 27(3)
C(46) 45(4) 90(5) 41(3) 41(3) 7(3) 20(3)
C(47) 32(3) 50(3) 34(3) 30(3) 6(2) 9(2)
C(48) 21(2) 12(2) 16(2) 0(1) 1(2) 1(2)
C(49) 19(2) 13(2) 21(2) -4(2) 2(2) 1(2)
C(50) 22(2) 16(2) 30(2) 4(2) 6(2) 2(2)
C(51) 26(3) 16(2) 47(3) 2(2) 11(2) -1(2)
C(52) 25(3) 16(2) 51(3) -7(2) 7(2) -3(2)
C(53) 24(3) 26(2) 40(3) -11(2) 3(2) -6(2)
C(54) 25(2) 20(2) 28(2) -2(2) -3(2) 0(2)
C(60) 48(9) 47(7) 55(7) -6(6) 26(6) 5(6)
C(61) 36(5) 25(8) 54(6) 7(4) 9(6) 20(7)
C(62) 47(10) 27(6) 65(7) 5(5) 9(6) 14(5)
C(63) 52(8) 40(6) 60(7) 9(5) 16(6) 19(5)
C(64) 76(10) 70(8) 52(7) -1(6) 17(6) 0(7)
C(65) 64(9) 60(7) 52(7) -10(5) 15(6) 1(7)
C(70) 75(9) 49(11) 116(12) -5(9) 23(8) -4(10)
C(71) 65(8) 15(9) 100(12) 12(8) 31(7) 1(6)
C(75) 46(7) 16(6) 106(12) 4(7) 26(6) -4(5)
C(72) 44(7) 53(10) 119(12) -32(9) 22(7) -8(7)
C(74) 50(8) 86(17) 125(14) -31(12) 14(7) -16(7)
28
C(73) 70(9) 63(13) 126(14) -23(10) 20(8) -12(9)
C(80) 50(6) 34(5) 43(7) 5(5) 6(5) 0(4)
C(81) 46(6) 30(5) 61(10) 2(5) 10(6) 2(4)
C(82) 43(6) 31(5) 81(12) 1(6) 6(6) 4(4)
C(83) 50(6) 32(6) 95(15) -6(7) 3(7) 7(5)
C(84) 51(6) 40(6) 67(11) 2(6) 2(6) 4(5)
C(85) 49(6) 39(5) 53(9) 4(5) -1(6) 4(5)
C(80C) 44(9) 78(10) 104(11) 8(8) 31(8) 2(7)
C(80A) 75(14) 96(11) 103(12) 9(8) 25(9) -16(10)
C(80B) 97(17) 95(11) 122(13) 6(9) 27(11) -18(10)
C(80D) 87(15) 88(11) 125(14) 12(9) 31(11) -17(9)
C(80E) 67(12) 87(10) 128(14) 13(8) 21(10) 3(8)
C(80F) 47(9) 90(10) 107(12) 9(8) 25(8) 0(8)
C(90) 65(8) 63(11) 47(7) 3(7) -7(5) -2(7)
C(91) 62(7) 25(7) 54(7) 9(5) -7(5) -4(5)
C(92) 60(7) 47(9) 51(7) -2(6) -3(5) 7(6)
C(93) 60(7) 45(8) 45(6) -13(6) -5(5) 4(6)
C(94) 58(7) 50(9) 49(6) -14(6) -3(5) 3(6)
C(95) 66(8) 88(16) 46(7) -18(7) -4(6) 0(7)
C(90A) 66(8) 39(7) 56(8) 5(6) -14(6) 9(5)
C(91A) 66(8) 50(9) 85(11) -13(8) 1(7) -7(6)
C(92A) 54(7) 51(8) 83(11) -13(8) 9(7) -5(6)
C(93A) 56(7) 46(7) 50(8) -15(6) 4(6) -8(5)
C(94A) 53(7) 56(7) 31(6) -7(5) -7(5) 3(5)
C(95A) 67(8) 53(8) 40(7) -7(6) -11(6) 1(6)
C(100) 64(7) 37(5) 50(9) -9(5) 7(6) -8(4)
C(101) 65(6) 26(4) 34(7) -2(4) 9(5) -2(4)
C(102) 63(7) 31(5) 32(5) 1(4) 13(5) -3(4)
C(103) 70(7) 34(5) 31(5) -10(4) 3(5) 2(4)
C(104) 72(7) 32(5) 29(6) -8(4) -3(5) -4(4)
C(105) 72(7) 35(5) 53(8) -14(5) 5(6) -9(4)
C(10A) 44(8) 40(7) 28(9) 4(5) -3(6) 5(5)
C(10B) 51(8) 34(7) 27(9) 1(5) 3(6) 1(5)
C(10C) 49(8) 41(7) 36(9) 4(6) 5(6) 1(5)
C(10D) 44(8) 40(7) 14(6) -4(5) -6(5) 4(5)
C(10E) 44(7) 37(7) 33(8) 1(5) -8(6) 3(5)
C(10F) 43(7) 44(7) 31(8) 4(5) -7(6) 3(5)
29
Table S5: Bond lengths [Å] for mm_002am_a.
Ga(1)-C(30) 1.995(5) C(15)-C(16) 1.542(7) C(64)-C(65) 1.3900
Ga(1)-N(2) 2.005(4) C(18)-C(23) 1.402(7) C(70)-C(71) 1.3900
Ga(1)-C(48) 2.026(5) C(18)-C(19) 1.403(7) C(70)-C(73) 1.3900
Ga(1)-N(1) 2.042(4) C(19)-C(20) 1.406(7) C(71)-C(75) 1.3900
Al(1)-O(1) 1.702(4) C(19)-C(24) 1.510(8) C(75)-C(72) 1.3900
Al(1)-C(36) 2.008(5) C(20)-C(21) 1.383(9) C(72)-C(74) 1.3900
Al(1)-C(42) 2.024(5) C(21)-C(22) 1.381(8) C(74)-C(73) 1.3900
Al(1)-C(2) 2.127(5) C(22)-C(23) 1.391(7) C(80)-C(81) 1.3900
F(1)-C(31) 1.353(6) C(23)-C(27) 1.516(7) C(80)-C(85) 1.3900
F(2)-C(32) 1.350(7) C(24)-C(25) 1.531(8) C(81)-C(82) 1.3900
F(3)-C(33) 1.344(7) C(24)-C(26) 1.538(8) C(82)-C(83) 1.3900
F(4)-C(34) 1.334(7) C(27)-C(28) 1.534(8) C(83)-C(84) 1.3900
F(5)-C(35) 1.347(6) C(27)-C(29) 1.535(8) C(84)-C(85) 1.3900
F(6)-C(37) 1.342(6) C(30)-C(35) 1.381(7) C(80C)-C(80A) 1.3900
F(7)-C(38) 1.343(7) C(30)-C(31) 1.381(7) C(80C)-C(80F) 1.3900
F(8)-C(39) 1.341(7) C(31)-C(32) 1.378(7) C(80A)-C(80B) 1.3900
F(9)-C(40) 1.328(7) C(32)-C(33) 1.369(9) C(80B)-C(80D) 1.3900
F(10)-C(41) 1.354(7) C(33)-C(34) 1.382(9) C(80D)-C(80E) 1.3900
F(11)-C(43) 1.364(7) C(34)-C(35) 1.382(7) C(80E)-C(80F) 1.3900
F(12)-C(44) 1.340(9) C(36)-C(41) 1.388(7) C(90)-C(91) 1.3900
F(13)-C(45) 1.336(8) C(36)-C(37) 1.392(8) C(90)-C(95) 1.3900
F(14)-C(46) 1.347(10) C(37)-C(38) 1.387(8) C(91)-C(92) 1.3900
F(15)-C(47) 1.354(9) C(38)-C(39) 1.378(9) C(92)-C(93) 1.3900
O(1)-C(48) 1.421(6) C(39)-C(40) 1.378(10) C(93)-C(94) 1.3900
N(1)-C(1) 1.299(6) C(40)-C(41) 1.377(8) C(94)-C(95) 1.3900
N(1)-C(6) 1.458(6) C(42)-C(43) 1.366(9) C(90A)-C(91A) 1.3900
N(2)-C(3) 1.308(6) C(42)-C(47) 1.372(8) C(90A)-C(95A) 1.3900
N(2)-C(18) 1.474(6) C(43)-C(44) 1.384(8) C(91A)-C(92A) 1.3900
C(1)-C(2) 1.472(6) C(44)-C(45) 1.378(12) C(92A)-C(93A) 1.3900
C(1)-C(4) 1.498(6) C(45)-C(46) 1.360(14) C(93A)-C(94A) 1.3900
C(2)-C(3) 1.466(6) C(46)-C(47) 1.389(9) C(94A)-C(95A) 1.3900
C(3)-C(5) 1.505(7) C(48)-C(49) 1.502(7) C(100)-C(101) 1.3900
C(6)-C(11) 1.395(7) C(49)-C(50) 1.392(7) C(100)-C(105) 1.3900
C(6)-C(7) 1.414(7) C(49)-C(54) 1.395(7) C(101)-C(102) 1.3900
C(7)-C(8) 1.401(7) C(50)-C(51) 1.395(7) C(102)-C(103) 1.3900
C(7)-C(12) 1.515(8) C(51)-C(52) 1.386(9) C(103)-C(104) 1.3900
C(8)-C(9) 1.386(9) C(52)-C(53) 1.400(9) C(104)-C(105) 1.3900
C(9)-C(10) 1.365(8) C(53)-C(54) 1.386(8) C(10A)-C(10B) 1.3900
C(10)-C(11) 1.401(7) C(60)-C(61) 1.3900 C(10A)-C(10F) 1.3900
C(11)-C(15) 1.514(7) C(60)-C(65) 1.3900 C(10B)-C(10C) 1.3900
C(12)-C(13) 1.523(9) C(61)-C(62) 1.3900 C(10C)-C(10D) 1.3900
C(12)-C(14) 1.536(8) C(62)-C(63) 1.3900 C(10D)-C(10E) 1.3900
C(15)-C(17) 1.538(8) C(63)-C(64) 1.3900 C(10E)-C(10F) 1.3900
30
Table S6: Bond angles [°] for mm_002am_a.
C(30)-Ga(1)-N(2) 116.89(19) C(10)-C(11)-C(15) 117.8(5) C(33)-C(34)-C(35) 119.0(6)
C(30)-Ga(1)-C(48) 124.1(2) C(7)-C(12)-C(13) 110.6(5) F(5)-C(35)-C(30) 120.0(5)
N(2)-Ga(1)-C(48) 108.34(18) C(7)-C(12)-C(14) 112.6(5) F(5)-C(35)-C(34) 116.4(5)
C(30)-Ga(1)-N(1) 106.77(18) C(13)-C(12)-C(14) 110.6(6) C(30)-C(35)-C(34) 123.6(5)
N(2)-Ga(1)-N(1) 92.43(16) C(11)-C(15)-C(17) 111.9(5) C(41)-C(36)-C(37) 113.5(5)
C(48)-Ga(1)-N(1) 102.18(17) C(11)-C(15)-C(16) 111.9(4) C(41)-C(36)-Al(1) 124.1(4)
O(1)-Al(1)-C(36) 113.3(2) C(17)-C(15)-C(16) 109.6(5) C(37)-C(36)-Al(1) 121.9(4)
O(1)-Al(1)-C(42) 110.8(2) C(23)-C(18)-C(19) 122.2(4) F(6)-C(37)-C(38) 116.0(5)
C(36)-Al(1)-C(42) 108.8(2) C(23)-C(18)-N(2) 119.9(4) F(6)-C(37)-C(36) 120.2(5)
O(1)-Al(1)-C(2) 102.82(19) C(19)-C(18)-N(2) 117.9(4) C(38)-C(37)-C(36) 123.7(5)
C(36)-Al(1)-C(2) 111.95(19) C(18)-C(19)-C(20) 117.4(5) F(7)-C(38)-C(39) 120.4(6)
C(42)-Al(1)-C(2) 109.0(2) C(18)-C(19)-C(24) 125.0(4) F(7)-C(38)-C(37) 120.4(6)
C(48)-O(1)-Al(1) 130.3(3) C(20)-C(19)-C(24) 117.5(5) C(39)-C(38)-C(37) 119.1(6)
C(1)-N(1)-C(6) 121.0(4) C(21)-C(20)-C(19) 121.7(5) F(8)-C(39)-C(38) 119.7(6)
C(1)-N(1)-Ga(1) 118.3(3) C(22)-C(21)-C(20) 118.8(5) F(8)-C(39)-C(40) 120.2(6)
C(6)-N(1)-Ga(1) 120.5(3) C(21)-C(22)-C(23) 122.6(6) C(38)-C(39)-C(40) 120.1(6)
C(3)-N(2)-C(18) 118.1(4) C(22)-C(23)-C(18) 117.3(5) F(9)-C(40)-C(41) 121.9(6)
C(3)-N(2)-Ga(1) 116.7(3) C(22)-C(23)-C(27) 118.0(5) F(9)-C(40)-C(39) 119.9(6)
C(18)-N(2)-Ga(1) 124.9(3) C(18)-C(23)-C(27) 124.7(4) C(41)-C(40)-C(39) 118.2(6)
N(1)-C(1)-C(2) 121.8(4) C(19)-C(24)-C(25) 110.6(5) F(10)-C(41)-C(40) 116.3(5)
N(1)-C(1)-C(4) 122.9(4) C(19)-C(24)-C(26) 111.6(5) F(10)-C(41)-C(36) 118.3(5)
C(2)-C(1)-C(4) 115.3(4) C(25)-C(24)-C(26) 110.7(5) C(40)-C(41)-C(36) 125.3(6)
C(3)-C(2)-C(1) 120.2(4) C(23)-C(27)-C(28) 109.2(5) C(43)-C(42)-C(47) 115.4(5)
C(3)-C(2)-Al(1) 103.0(3) C(23)-C(27)-C(29) 112.1(5) C(43)-C(42)-Al(1) 122.8(4)
C(1)-C(2)-Al(1) 111.6(3) C(28)-C(27)-C(29) 109.5(5) C(47)-C(42)-Al(1) 121.6(5)
N(2)-C(3)-C(2) 123.8(4) C(35)-C(30)-C(31) 114.6(5) F(11)-C(43)-C(42) 120.1(5)
N(2)-C(3)-C(5) 121.7(4) C(35)-C(30)-Ga(1) 128.5(4) F(11)-C(43)-C(44) 115.7(6)
C(2)-C(3)-C(5) 114.5(4) C(31)-C(30)-Ga(1) 116.9(4) C(42)-C(43)-C(44) 124.2(6)
C(11)-C(6)-C(7) 122.6(4) F(1)-C(31)-C(32) 116.5(5) F(12)-C(44)-C(45) 120.6(6)
C(11)-C(6)-N(1) 119.7(4) F(1)-C(31)-C(30) 119.5(5) F(12)-C(44)-C(43) 121.2(7)
C(7)-C(6)-N(1) 117.6(4) C(32)-C(31)-C(30) 124.0(5) C(45)-C(44)-C(43) 118.3(7)
C(8)-C(7)-C(6) 116.9(5) F(2)-C(32)-C(33) 119.9(5) F(13)-C(45)-C(46) 121.3(8)
C(8)-C(7)-C(12) 120.5(5) F(2)-C(32)-C(31) 121.0(5) F(13)-C(45)-C(44) 118.9(9)
C(6)-C(7)-C(12) 122.6(4) C(33)-C(32)-C(31) 119.1(6) C(46)-C(45)-C(44) 119.8(6)
C(9)-C(8)-C(7) 121.0(5) F(3)-C(33)-C(32) 120.5(6) F(14)-C(46)-C(45) 120.7(7)
C(10)-C(9)-C(8) 120.6(5) F(3)-C(33)-C(34) 119.8(6) F(14)-C(46)-C(47) 119.6(9)
C(9)-C(10)-C(11) 121.3(5) C(32)-C(33)-C(34) 119.7(6) C(45)-C(46)-C(47) 119.7(8)
C(6)-C(11)-C(10) 117.5(5) F(4)-C(34)-C(33) 120.5(5) F(15)-C(47)-C(42) 120.7(5)
C(6)-C(11)-C(15) 124.7(4) F(4)-C(34)-C(35) 120.6(6) F(15)-C(47)-C(46) 116.6(6)
31
C(42)-C(47)-C(46) 122.7(8) C(71)-C(75)-C(72) 120.0 C(95)-C(94)-C(93) 120.0
O(1)-C(48)-C(49) 110.8(4) C(74)-C(72)-C(75) 120.0 C(94)-C(95)-C(90) 120.0
O(1)-C(48)-Ga(1) 107.4(3) C(72)-C(74)-C(73) 120.0 C(91A)-C(90A)-C(95A) 120.0
C(49)-C(48)-Ga(1) 118.9(3) C(74)-C(73)-C(70) 120.0 C(92A)-C(91A)-C(90A) 120.0
C(50)-C(49)-C(54) 118.5(5) C(81)-C(80)-C(85) 120.0 C(91A)-C(92A)-C(93A) 120.0
C(50)-C(49)-C(48) 120.7(5) C(80)-C(81)-C(82) 120.0 C(94A)-C(93A)-C(92A) 120.0
C(54)-C(49)-C(48) 120.8(5) C(83)-C(82)-C(81) 120.0 C(95A)-C(94A)-C(93A) 120.0
C(49)-C(50)-C(51) 120.8(6) C(82)-C(83)-C(84) 120.0 C(94A)-C(95A)-C(90A) 120.0
C(52)-C(51)-C(50) 120.0(6) C(83)-C(84)-C(85) 120.0 C(101)-C(100)-C(105) 120.0
C(51)-C(52)-C(53) 119.7(5) C(84)-C(85)-C(80) 120.0 C(102)-C(101)-C(100) 120.0
C(54)-C(53)-C(52) 119.6(6) C(80A)-C(80C)-C(80F) 120.0 C(103)-C(102)-C(101) 120.0
C(53)-C(54)-C(49) 121.3(5) C(80B)-C(80A)-C(80C) 120.0 C(102)-C(103)-C(104) 120.0
C(61)-C(60)-C(65) 120.0 C(80A)-C(80B)-C(80D) 120.0 C(105)-C(104)-C(103) 120.0
C(60)-C(61)-C(62) 120.0 C(80B)-C(80D)-C(80E) 120.0 C(104)-C(105)-C(100) 120.0
C(63)-C(62)-C(61) 120.0 C(80F)-C(80E)-C(80D) 120.0 C(10B)-C(10A)-C(10F) 120.0
C(64)-C(63)-C(62) 120.0 C(80E)-C(80F)-C(80C) 120.0 C(10A)-C(10B)-C(10C) 120.0
C(63)-C(64)-C(65) 120.0 C(91)-C(90)-C(95) 120.0 C(10D)-C(10C)-C(10B) 120.0
C(64)-C(65)-C(60) 120.0 C(92)-C(91)-C(90) 120.0 C(10C)-C(10D)-C(10E) 120.0
C(71)-C(70)-C(73) 120.0 C(91)-C(92)-C(93) 120.0 C(10F)-C(10E)-C(10D) 120.0
C(70)-C(71)-C(75) 120.0 C(92)-C(93)-C(94) 120.0 C(10E)-C(10F)-C(10A) 120.0