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_1574621
_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         'C59 H99 Al F K N2 O7 Si2'
_chemical_formula_sum            'C59 H99 Al F K N2 O7 Si2'
_chemical_formula_weight         1089.66
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2025-03-10
_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                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.3496(2)
_cell_length_b                   23.9758(6)
_cell_length_c                   20.1328(3)
_cell_measurement_reflns_used    8101
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      75.2850
_cell_measurement_theta_min      2.8500
_cell_volume                     6443.9(2)
_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_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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     -5.00  30.00   0.50    3.00    --   46.57 -35.00  30.00   70
  2  \w     82.00 108.00   0.50   16.00    --  107.75-131.00 167.00   52
  3  \w    104.00 178.00   0.50   16.00    --  107.75  86.00  -7.00  148
  4  \w     37.00  63.00   0.50   16.00    --  107.75 -35.00  30.00   52
  5  \w     70.00 107.00   0.50   16.00    --  107.75-139.00  -7.00   74
  6  \w     38.00  68.00   0.50   16.00    --  107.75-131.00 167.00   60
  7  \w    -20.00  24.00   0.50    3.00    --  -46.57  38.00 150.00   88
  8  \w    -20.00   5.00   0.50    3.00    --  -46.57  38.00 -90.00   50
  9  \w     -6.00  29.00   0.50    3.00    --  -46.57  19.00  60.00   70
 10  \w      1.00  27.00   0.50    3.00    --  -46.57  19.00-150.00   52
 11  \w   -118.00 -79.00   0.50    3.00    --  -46.57-131.00 167.00   78
 12  \w     59.00  84.00   0.50    3.00    --   46.57-139.00  -7.00   50
 13  \w     36.00  65.00   0.50   16.00    --  107.75 -61.00  30.00   58
 14  \w     37.00  63.00   0.50   16.00    --  107.75 -45.00  30.00   52
 15  \w    146.00 176.00   0.50   16.00    --  107.75 125.00  30.00   60
 16  \w     32.00  57.00   0.50   16.00    --  107.75 -30.00  60.00   50
 17  \w     59.00  89.00   0.50   16.00    --  107.75 -61.00-150.00   60
 18  \w     94.00 140.00   0.50   16.00    --  107.75 125.00  30.00   92
 19  \w     36.00  66.00   0.50   16.00    --  107.75 -45.00-150.00   60
 20  \w    131.00 175.00   0.50   16.00    --  107.75  77.00  60.00   88
 21  \w     32.00  57.00   0.50   16.00    --  107.75 -30.00   0.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0414747000
_diffrn_orient_matrix_UB_12      -0.0591995000
_diffrn_orient_matrix_UB_13      -0.0111067000
_diffrn_orient_matrix_UB_21      -0.0945563000
_diffrn_orient_matrix_UB_22      -0.0248069000
_diffrn_orient_matrix_UB_23      0.0324995000
_diffrn_orient_matrix_UB_31      -0.0516096000
_diffrn_orient_matrix_UB_32      -0.0021709000
_diffrn_orient_matrix_UB_33      -0.0683977000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0612
_diffrn_reflns_av_unetI/netI     0.0526
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            28412
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        66.499
_diffrn_reflns_theta_max         66.499
_diffrn_reflns_theta_min         2.866
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.608
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89913
_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_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.123
_exptl_crystal_description       needle
_exptl_crystal_F_000             2368
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.883
_refine_diff_density_min         -0.679
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     558
_refine_ls_number_reflns         5824
_refine_ls_number_restraints     348
_refine_ls_restrained_S_all      1.120
_refine_ls_R_factor_all          0.1109
_refine_ls_R_factor_gt           0.0945
_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^)+(0.1580P)^2^+10.6721P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2662
_refine_ls_wR_factor_ref         0.2831
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4593
_reflns_number_total             5824
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02682b2.cif
_cod_data_source_block           compound-9
_cod_depositor_comments
'Adding full bibliography for 1574617--1574626.cif.'
_cod_database_code               1574621
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C48H100AlFKN2OSi2
_shelx_estimated_absorpt_t_max   0.938
_shelx_estimated_absorpt_t_min   0.603
_diffrn_oxdiff_digest_hkl
;
01fd824257d63a1d08cef04de0c1bf2944f7bd
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{F1, H}
3. Restrained distances
 C22A-C20A = C21-C20 = C21A-C20A = C22-C20
 1.53 with sigma of 0.008
 C18A-C17A = C17-C19 = C19A-C17A
 1.53 with sigma of 0.008
 C18A-C17A = C19-C17 = C19A-C17A = C18-C17
 1.53 with sigma of 0.008
 C16A-C14A = C15A-C14A = C15-C14 = C16-C14
 1.53 with sigma of 0.008
 O3-C31 = O3-C30 = O2-C29 = O2-C40 = O7-C39 = O7-C38 = O6-C37 = O6-C36 = O5-
 C35 = O5-C34 = O4-C33 = O4-C32
 1.4 with sigma of 0.008
 C29-C30 = C32-C31 = C33-C34 = C35-C36 = C37-C38 = C39-C40
 1.53 with sigma of 0.008
 Al1-C23A
 2.05 with sigma of 0.02
 H9C-H8A
 2.4 with sigma of 0.002
 Si1-C20A
 1.9 with sigma of 0.008
 C18A-C19A = C19-C18 = C15A-C16A = C15-C16 = C22-C21 = C21A-C22A
 2.5 with sigma of 0.008
 C30-C31 = C32-C33 = C34-C35 = C36-C37 = C38-C39 = C40-C29
 2.2 with sigma of 0.008
4. Uiso/Uaniso restraints and constraints
C17 \\sim C18 \\sim C19A \\sim C17A \\sim C18A \\sim C19: within 2A with sigma
of 0.005 and sigma for terminal atoms of 0.01 within 2A
C16A \\sim C14A \\sim C15A \\sim C15 \\sim C14 \\sim C16: within 2A with sigma
of 0.005 and sigma for terminal atoms of 0.01 within 2A
C31 \\sim O3 \\sim C30 \\sim C29 \\sim O2 \\sim C40 \\sim C39 \\sim O7 \\sim
C38 \\sim C37 \\sim O6 \\sim C36 \\sim C35 \\sim O5 \\sim C34 \\sim C33 \\sim
O4 \\sim C32: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim F1A: within 2A with
sigma of 0.003 and sigma for terminal atoms of 0.006 within 2A
C23A \\sim C24A \\sim C25A \\sim C26A \\sim C27A \\sim C28A: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
Uanis(C23) = Uanis(Al1)
Uanis(C23A) = Uanis(Al1)
5. Others
 Fixed Sof: H8A(0.5) H8B(0.5) H8C(0.5) C23(0.33) C24(0.33) H24(0.33) C25(0.33)
 H25(0.33) C26(0.33) H26(0.33) C27(0.33) C28(0.33) H28(0.33) H9A(0.5) H9C(0.5)
 H9B(0.5) O5(0.5) C20(0.6) H20(0.6) C15A(0.5) H15A(0.5) H15B(0.5) H15C(0.5)
 C34(0.5) H34A(0.5) H34B(0.5) O3(0.5) C38(0.5) H38A(0.5) H38B(0.5) C14A(0.5)
 H14A(0.5) C22(0.6) H22A(0.6) H22B(0.6) H22C(0.6) O6(0.5) O2(0.5) O4(0.5)
 O7(0.5) C17A(0.5) H17A(0.5) C21(0.6) H21B(0.6) H21C(0.6) H21A(0.6) C30(0.5)
 H30A(0.5) H30B(0.5) C16A(0.5) H16A(0.5) H16B(0.5) H16C(0.5) C18A(0.5)
 H18A(0.5) H18B(0.5) H18C(0.5) C22A(0.4) H22D(0.4) H22E(0.4) H22F(0.4)
 C20A(0.4) H20A(0.4) C21A(0.4) H21D(0.4) H21E(0.4) H21F(0.4) C19(0.5) H19A(0.5)
 H19B(0.5) H19C(0.5) C19A(0.5) H19D(0.5) H19E(0.5) H19F(0.5) C17(0.5) H17(0.5)
 C18(0.5) H18D(0.5) H18E(0.5) H18F(0.5) C16(0.5) H16D(0.5) H16E(0.5) H16F(0.5)
 C14(0.5) H14(0.5) C15(0.5) H15D(0.5) H15E(0.5) H15F(0.5) F1A(0.33) C35(0.5)
 H35A(0.5) H35B(0.5) C29(0.5) H29A(0.5) H29B(0.5) C40(0.5) H40A(0.5) H40B(0.5)
 C39(0.5) H39A(0.5) H39B(0.5) C37(0.5) H37A(0.5) H37B(0.5) C33(0.5) H33A(0.5)
 H33B(0.5) C31(0.5) H31A(0.5) H31B(0.5) C36(0.5) H36A(0.5) H36B(0.5) C32(0.5)
 H32A(0.5) H32B(0.5) C23A(0.17) C24A(0.17) H24A(0.17) C25A(0.17) H25A(0.17)
 C26A(0.17) H26A(0.17) C27A(0.17) H27A(0.17) C28A(0.17) H28A(0.17) F1(0.17)
 H(0.33)
 Fixed Uiso: H(0.05)
6.a Ternary CH refined with riding coordinates:
 C20(H20), C14A(H14A), C17A(H17A), C20A(H20A), C17(H17), C14(H14)
6.b Secondary CH2 refined with riding coordinates:
 C34(H34A,H34B), C38(H38A,H38B), C30(H30A,H30B), C35(H35A,H35B), C29(H29A,
 H29B), C40(H40A,H40B), C39(H39A,H39B), C37(H37A,H37B), C33(H33A,H33B),
 C31(H31A,H31B), C36(H36A,H36B), C32(H32A,H32B)
6.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C3(H3), C24(H24), C25(H25), C26(H26), C28(H28), C24A(H24A),
 C25A(H25A), C26A(H26A), C27A(H27A), C28A(H28A)
6.d Fitted hexagon refined as free rotating group:
 C23(C24,C25,C26,C27,C28), C23A(C24A,C25A,C26A,C27A,C28A)
6.e Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C13(H13A,H13B,H13C), C9(H9A,H9C,H9B), C11(H11A,H11B,H11C),
 C12(H12A,H12B,H12C), C15A(H15A,H15B,H15C), C22(H22A,H22B,H22C), C21(H21B,H21C,
 H21A), C16A(H16A,H16B,H16C), C18A(H18A,H18B,H18C), C22A(H22D,H22E,H22F),
 C21A(H21D,H21E,H21F), C19(H19A,H19B,H19C), C19A(H19D,H19E,H19F), C18(H18D,H18E,
 H18F), C16(H16D,H16E,H16F), C15(H15D,H15E,H15F)
;
_shelx_res_checksum              13192
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.232
_oxdiff_exptl_absorpt_empirical_full_min 0.598