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_1574625
_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         '2(C59 H72 Al N2 O2), 5.5(C6 H6), 2(K)'
_chemical_formula_sum            'C151 H177 Al2 K2 N4 O4'
_chemical_formula_weight         2244.12
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yac'
_space_group_name_H-M_alt        'P 1 2/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_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                 96.745(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.4545(3)
_cell_length_b                   14.2108(2)
_cell_length_c                   45.7301(8)
_cell_measurement_reflns_used    17822
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      74.0310
_cell_measurement_theta_min      3.1270
_cell_volume                     13200.6(4)
_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      150.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.956
_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    -28.00  27.00   0.50   15.00    --  -46.57  52.00-157.00  110
  2  \w   -120.00 -32.00   0.50   15.00    --  -46.57 -52.00  57.00  176
  3  \w     52.00  77.00   0.50   15.00    --   46.57  52.00-157.00   50
  4  \w     -7.00  18.00   0.50   15.00    --   46.57 -52.00  57.00   50
  5  \w     31.00  70.00   0.50   60.00    --  104.28 -52.00  57.00   78
  6  \w     92.00 178.00   0.50   60.00    --  104.28  52.00-157.00  172
  7  \w     -6.00  28.00   0.50   15.00    --  -46.57  19.00   0.00   68
  8  \w     -1.00  26.00   0.50   15.00    --  -46.57  19.00 150.00   54
  9  \w    -21.00  17.00   0.50   15.00    --  -46.57  38.00   0.00   76
 10  \w     -7.00  28.00   0.50   15.00    --  -46.57  19.00 -30.00   70
 11  \w     41.00 111.00   0.50   60.00    --  104.28-125.00  90.00  140
 12  \w     33.00  58.00   0.50   60.00    --  104.28 -30.00  60.00   50
 13  \w     29.00  59.00   0.50   60.00    --  104.28 -30.00 -90.00   60
 14  \w     28.00  53.00   0.50   60.00    --  104.28 -30.00 -60.00   50
 15  \w     95.00 176.00   0.50   60.00    --  104.28  45.00 150.00  162
 16  \w     32.00  62.00   0.50   60.00    --  104.28 -61.00 -30.00   60
 17  \w     32.00  57.00   0.50   60.00    --  104.28 -45.00 120.00   50
 18  \w     36.00  66.00   0.50   60.00    --  104.28 -45.00 -90.00   60
 19  \w     28.00  56.00   0.50   60.00    --  104.28 -30.00  90.00   56
 20  \w     28.00  56.00   0.50   60.00    --  104.28 -30.00-120.00   56
 21  \w     33.00  59.00   0.50   60.00    --  104.28 -30.00-150.00   52
 22  \w     39.00  92.00   0.50   60.00    --  104.28 -61.00 120.00  106
 23  \w     37.00  71.00   0.50   60.00    --  104.28 -45.00-150.00   68
;
_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      -0.0102324000
_diffrn_orient_matrix_UB_12      0.0441660000
_diffrn_orient_matrix_UB_13      0.0298894000
_diffrn_orient_matrix_UB_21      0.0610538000
_diffrn_orient_matrix_UB_22      -0.0527805000
_diffrn_orient_matrix_UB_23      0.0146317000
_diffrn_orient_matrix_UB_31      0.0437845000
_diffrn_orient_matrix_UB_32      0.0838423000
_diffrn_orient_matrix_UB_33      -0.0065190000
_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  0.0759
_diffrn_reflns_av_unetI/netI     0.0719
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       57
_diffrn_reflns_limit_l_min       -51
_diffrn_reflns_number            82810
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.669
_diffrn_reflns_theta_min         3.110
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.177
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77158
_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    1.129
_exptl_crystal_description       block
_exptl_crystal_F_000             4828
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.623
_refine_diff_density_min         -0.421
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1455
_refine_ls_number_reflns         26583
_refine_ls_number_restraints     72
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.1149
_refine_ls_R_factor_gt           0.0863
_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^)+(0.0953P)^2^+17.5985P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2152
_refine_ls_wR_factor_ref         0.2317
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19540
_reflns_number_total             26583
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02682b2.cif
_cod_data_source_block           compound-8
_cod_depositor_comments
'Adding full bibliography for 1574617--1574626.cif.'
_cod_database_code               1574625
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H N O Al K'
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.782
_diffrn_oxdiff_ac3_digest_hkl    01e809f63088ba9bef255c7e99d2773c038bfd
_diffrn_oxdiff_digest_hkl
;
01cd1e009e17ed336d3c5c4b5bca9cc4dab64a
;
_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. Uiso/Uaniso restraints and constraints
C149 \\sim C150 \\sim C151: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
C149 \\sim C150 \\sim C151 \\sim C152 \\sim C153 \\sim C154: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C123 \\sim C122 \\sim C121 \\sim C120 \\sim C119 \\sim C124: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
3. Others
 Fixed Sof: C149(0.5) H149(0.5) C150(0.5) H150(0.5) C151(0.5) H151(0.5)
 C152(0.5) H152(0.5) C153(0.5) H153(0.5) C154(0.5) H154(0.5)
4.a Ternary CH refined with riding coordinates:
 C30(H30), C33(H33), C42(H42), C45(H45), C89(H89), C92(H92), C101(H101),
 C104(H104)
4.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C9(H9), C11(H11), C26(H26), C27(H27), C28(H28), C38(H38),
 C39(H39), C40(H40), C49(H49), C50(H50), C51(H51), C52(H52), C53(H53), C55(H55),
  C56(H56), C57(H57), C58(H58), C59(H59), C62(H62), C64(H64), C68(H68),
 C70(H70), C85(H85), C86(H86), C87(H87), C97(H97), C98(H98), C99(H99),
 C108(H108), C109(H109), C110(H110), C111(H111), C112(H112), C114(H114),
 C115(H115), C116(H116), C117(H117), C118(H118), C123(H123), C122(H122),
 C121(H121), C120(H120), C119(H119), C124(H124), C129(H129), C128(H128),
 C127(H127), C126(H126), C125(H125), C130(H130), C136(H136), C135(H135),
 C134(H134), C133(H133), C132(H132), C131(H131), C141(H141), C140(H140),
 C139(H139), C138(H138), C137(H137), C142(H142), C148(H148), C147(H147),
 C146(H146), C145(H145), C144(H144), C143(H143), C149(H149), C150(H150),
 C151(H151), C152(H152), C153(H153), C154(H154)
4.c Fitted hexagon refined as free rotating group:
 C123(C122,C121,C120,C119,C124), C129(C128,C127,C126,C125,C130), C136(C135,
 C134,C133,C132,C131), C141(C140,C139,C138,C137,C142), C148(C147,C146,C145,C144,
 C143), C149(C150,C151,C152,C153,C154)
4.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C),
 C35(H35A,H35B,H35C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C46(H46A,H46B,
 H46C), C47(H47A,H47B,H47C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C76(H76A,
 H76B,H76C), C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C80(H80A,H80B,H80C),
 C81(H81A,H81B,H81C), C82(H82A,H82B,H82C), C90(H90A,H90B,H90C), C91(H91A,H91B,
 H91C), C93(H93A,H93B,H93C), C94(H94A,H94B,H94C), C102(H10A,H10B,H10C),
 C103(H10D,H10E,H10F), C105(H10G,H10H,H10I), C106(H10J,H10K,H10L)
;
_shelx_res_checksum              82270
_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 1.677
_oxdiff_exptl_absorpt_empirical_full_min 0.466