Enhancing the nucleophilicity of aluminyl anions: targeting selective C–H activation
Kallmeier, Fabian; Nelmes, Gareth R.; McMullin, Claire L.; Edwards, Alison J.; Hicks, Jamie; Chemical Science 16 (2025) 10750–10758; doi:10.1039/D5SC02682B

data_1574617
_publ_section_title
;
 Enhancing the nucleophilicity of aluminyl anions: targeting selective
 C--H activation
;
_journal_issue                   24
_journal_name_full               'Chemical Science'
_journal_page_first              10750
_journal_page_last               10758
_journal_paper_doi               10.1039/D5SC02682B
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         '0.25(C188 H304 Al4 K3 N8 O4 Si8), 0.25(K)'
_chemical_formula_sum            'C47 H76 Al K N2 O Si2'
_chemical_formula_weight         807.35
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2025-03-08
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.06 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-03-20 deposited with the CCDC.	2025-05-12 downloaded from the CCDC.
;
_cell_angle_alpha                101.4380(10)
_cell_angle_beta                 105.3220(10)
_cell_angle_gamma                103.9550(10)
_cell_formula_units_Z            4
_cell_length_a                   14.41060(10)
_cell_length_b                   15.42140(10)
_cell_length_c                   24.1204(2)
_cell_measurement_reflns_used    74826
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      77.9290
_cell_measurement_theta_min      3.0630
_cell_volume                     4816.59(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -115.00 -40.00   0.50    0.50    --  -46.45 -50.00 -86.00  150
  2  \w    -14.00  46.00   0.50    0.50    --   46.45 -50.00 -86.00  120
  3  \w     47.00 119.00   0.50    0.50    --   46.45  50.00  59.00  144
  4  \w     48.00  74.00   0.50    0.75    --  107.75 -50.00 -86.00   52
  5  \w    153.00 178.00   0.50    0.75    --  107.75  50.00  59.00   50
  6  \w    123.00 149.00   0.50    0.75    --  107.75  50.00  59.00   52
  7  \w     -8.00  17.00   0.50    0.50    --  -46.45  19.00-180.00   50
  8  \w     -7.00  22.00   0.50    0.50    --  -46.45  19.00  90.00   58
  9  \w     -5.00  21.00   0.50    0.50    --  -46.45  19.00   0.00   52
 10  \w    -27.00  25.00   0.50    0.50    --  -46.45  50.00  59.00  104
 11  \w     -7.00  22.00   0.50    0.50    --  -46.45  19.00 -30.00   58
 12  \w     -8.00  30.00   0.50    0.50    --  -46.45  19.00-150.00   76
 13  \w     36.00  90.00   0.50    0.50    --   46.45-125.00 150.00  108
 14  \w     35.00  77.00   0.50    0.50    --   46.45-125.00  90.00   84
 15  \w     40.00  80.00   0.50    0.50    --   46.45 -99.00-180.00   80
 16  \w     -1.00  25.00   0.50    0.50    --   46.45 -99.00-180.00   52
 17  \w     32.00  57.00   0.50    0.75    --  107.75 -30.00 -60.00   50
 18  \w     86.00 120.00   0.50    0.75    --  107.75 -77.00  90.00   68
 19  \w     95.00 168.00   0.50    0.75    --  107.75  45.00 -90.00  146
 20  \w     70.00 119.00   0.50    0.75    --  107.75-133.00  55.19   98
 21  \w     40.00  77.00   0.50    0.75    --  107.75 -77.00  90.00   74
 22  \w     32.00  57.00   0.50    0.75    --  107.75 -30.00  90.00   50
 23  \w     54.00  99.00   0.50    0.75    --  107.75 -95.00  30.00   90
 24  \w     55.00 106.00   0.50    0.75    --  107.75 -95.00 -60.00  102
 25  \w     42.00  80.00   0.50    0.75    --  107.75-141.00-112.46   76
 26  \w     34.00  92.00   0.50    0.75    --  107.75 -61.00-150.00  116
 27  \w     86.00 125.00   0.50    0.75    --  107.75-141.00-112.46   78
 28  \w    113.00 140.00   0.50    0.75    --  107.75  30.00-150.00   54
 29  \w    149.00 178.00   0.50    0.75    --  107.75  30.00-150.00   58
 30  \w     78.00 104.00   0.50    0.75    --  107.75 -95.00 -90.00   52
 31  \w     34.00  73.00   0.50    0.75    --  107.75 -77.00  30.00   78
 32  \w    114.00 165.00   0.50    0.75    --  107.75 125.00 -30.00  102
 33  \w     33.00  58.00   0.50    0.75    --  107.75 -30.00   0.00   50
 34  \w     61.00 116.00   0.50    0.75    --  107.75   0.00-180.00  110
 35  \w    137.00 168.00   0.50    0.75    --  107.75   0.00-180.00   62
 36  \w     44.00  73.00   0.50    0.75    --  107.75-100.00 148.39   58
 37  \w     96.00 140.00   0.50    0.75    --  107.75 125.00 -90.00   88
 38  \w     52.00 109.00   0.50    0.75    --  107.75-109.00 -96.94  114
 39  \w     50.00  80.00   0.50    0.75    --  107.75 -77.00 150.00   60
 40  \w     80.00 112.00   0.50    0.75    --  107.75-125.00 150.00   64
 41  \w     34.00  68.00   0.50    0.75    --  107.75 -61.00  60.00   68
 42  \w     67.00 124.00   0.50    0.75    --  107.75-140.00 125.27  114
 43  \w     56.00  82.00   0.50    0.75    --  107.75 -77.00-150.00   52
 44  \w     85.00 111.00   0.50    0.75    --  107.75 -77.00 150.00   52
 45  \w     32.00  57.00   0.50    0.75    --  107.75 -30.00 -30.00   50
 46  \w     36.00  92.00   0.50    0.75    --  107.75 -61.00 150.00  112
 47  \w     69.00  94.00   0.50    0.75    --  107.75 -77.00 -90.00   50
 48  \w     95.00 120.00   0.50    0.75    --  107.75  30.00-120.00   50
 49  \w    130.00 176.00   0.50    0.75    --  107.75  30.00-120.00   92
 50  \w     99.00 160.00   0.50    0.75    --  107.75  15.00 -30.00  122
 51  \w    106.00 170.00   0.50    0.75    --  107.75  15.00  30.00  128
 52  \w     48.00  74.00   0.50    0.75    --  107.75-115.00 -37.62   52
 53  \w     84.00 109.00   0.50    0.75    --  107.75-115.00 -37.62   50
 54  \w     40.00  66.00   0.50    0.75    --  107.75-103.00 143.02   52
 55  \w     82.00 107.00   0.50    0.75    --  107.75-103.00 143.02   50
 56  \w     95.00 120.00   0.50    0.75    --  107.75 -76.00 -42.02   50
 57  \w     35.00  81.00   0.50    0.75    --  107.75 -77.00  60.00   92
 58  \w     36.00  61.00   0.50    0.75    --  107.75 -45.00-120.00   50
 59  \w     66.00 109.00   0.50    0.75    --  107.75-125.00 -90.00   86
 60  \w     87.00 112.00   0.50    0.75    --  107.75-125.00 -60.00   50
 61  \w     85.00 110.00   0.50    0.75    --  107.75-125.00-120.00   50
 62  \w     94.00 127.00   0.50    0.75    --  107.75 125.00 120.00   66
 63  \w    137.00 175.00   0.50    0.75    --  107.75 125.00 120.00   76
 64  \w    101.00 152.00   0.50    0.75    --  107.75  45.00-120.00  102
 65  \w     35.00 104.00   0.50    0.75    --  107.75 -95.00 -30.00  138
 66  \w     34.00  80.00   0.50    0.75    --  107.75 -95.00   0.00   92
 67  \w     34.00  59.00   0.50    0.75    --  107.75 -95.00 120.00   50
 68  \w     66.00  92.00   0.50    0.75    --  107.75 -95.00 120.00   52
 69  \w     58.00  83.00   0.50    0.75    --  107.75 -76.00 -42.02   50
 70  \w     81.00 112.00   0.50    0.75    --  107.75-125.00-180.00   62
 71  \w     46.00  72.00   0.50    0.75    --  107.75-125.00-180.00   52
 72  \w     82.00 107.00   0.50    0.75    --  107.75-100.00 148.39   50
 73  \w     39.00  72.00   0.50    0.75    --  107.75 -45.00 -30.00   66
 74  \w     51.00  93.00   0.50    0.75    --  107.75 -61.00-120.00   84
 75  \w     78.00 104.00   0.50    0.75    --  107.75 -95.00-150.00   52
 76  \w     71.00 105.00   0.50    0.75    --  107.75 -95.00  60.00   68
 77  \w     38.00  64.00   0.50    0.75    --  107.75-125.00   0.00   52
 78  \w     45.00  70.00   0.50    0.75    --  107.75-125.00 150.00   50
 79  \w     34.00  59.00   0.50    0.75    --  107.75 -30.00  30.00   50
 80  \w    124.00 150.00   0.50    0.75    --  107.75 125.00 150.00   52
 81  \w     32.00  58.00   0.50    0.75    --  107.75 -30.00 120.00   52
 82  \w     42.00  67.00   0.50    0.75    --  107.75 -77.00-120.00   50
 83  \w     34.00  60.00   0.50    0.75    --  107.75 -77.00 -60.00   52
 84  \w     60.00  92.00   0.50    0.75    --  107.75 -61.00  90.00   64
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0445
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            108037
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.151
_diffrn_reflns_theta_min         3.076
_exptl_absorpt_coefficient_mu    1.867
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71632
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.85a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.113
_exptl_crystal_description       block
_exptl_crystal_F_000             1760
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.487
_refine_diff_density_min         -0.711
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1071
_refine_ls_number_reflns         20375
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0385
_refine_ls_R_factor_gt           0.0356
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0481P)^2^+1.2843P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0946
_refine_ls_wR_factor_ref         0.0965
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18603
_reflns_number_total             20375
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02682b2.cif
_cod_data_source_block           compound-2
_cod_depositor_comments
'Adding full bibliography for 1574617--1574626.cif.'
_cod_original_cell_volume        4816.58(7)
_cod_database_code               1574617
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.912
_shelx_estimated_absorpt_t_min   0.835
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C17A-C14 = C15A-C14 = C16A-C14
 1.53 with sigma of 0.008
3. Others
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=1-FVAR(1)
 Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C22A)=Sof(H22D)=Sof(H22E)=
 Sof(H22F)=Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=FVAR(1)
 Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16A)=Sof(H16D)=Sof(H16E)=
 Sof(H16F)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=1-FVAR(2)
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=
 Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 C24(H24), C27(H27), C30(H30), C33(H33), C36(H36), C39(H39), C71(H71),
 C74(H74), C77(H77), C80(H80), C83(H83), C86(H86)
4.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C9(H9), C11(H11), C43(H43), C44(H44), C45(H45), C46(H46),
 C47(H47), C50(H50), C52(H52), C56(H56), C58(H58), C90(H90), C91(H91), C92(H92),
  C93(H93), C94(H94)
4.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C15A(H15D,H15E,H15F), C16(H16A,H16B,H16C), C16A(H16D,
 H16E,H16F), C17(H17A,H17B,H17C), C17A(H17D,H17E,H17F), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C21A(H21D,H21E,H21F), C22(H22A,H22B,
 H22C), C22A(H22D,H22E,H22F), C23(H23A,H23B,H23C), C23A(H23D,H23E,H23F),
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C35(H35A,
 H35B,H35C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C40(H40A,H40B,H40C),
 C41(H41A,H41B,H41C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C64(H64A,H64B,
 H64C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C68(H68A,H68B,H68C), C69(H69A,
 H69B,H69C), C70(H70A,H70B,H70C), C72(H72A,H72B,H72C), C73(H73A,H73B,H73C),
 C75(H75A,H75B,H75C), C76(H76A,H76B,H76C), C78(H78A,H78B,H78C), C79(H79A,H79B,
 H79C), C81(H81A,H81B,H81C), C82(H82A,H82B,H82C), C84(H84A,H84B,H84C), C85(H85A,
 H85B,H85C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C)
;
_shelx_res_checksum              30816
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;