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_1574623
_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 H100 Al K N2 O7 Si2, 2.5(C6 H12)'
_chemical_formula_sum            'C74 H130 Al K N2 O7 Si2'
_chemical_formula_weight         1282.05
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-20
_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                 98.984(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.8101(4)
_cell_length_b                   24.0778(3)
_cell_length_c                   22.5799(4)
_cell_measurement_reflns_used    10875
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.8520
_cell_measurement_theta_min      3.3540
_cell_volume                     7953.1(3)
_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 0.996
_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    -77.00  27.00   0.50    5.00    --  -46.45  91.00-170.00  208
  2  \w     13.00  62.00   0.50    5.00    --   46.45 -91.00  76.00   98
  3  \w    107.00 167.00   0.50   37.00    --  107.75  91.00-170.00  120
  4  \w     60.00 102.00   0.50   37.00    --  107.75 -91.00  76.00   84
  5  \w      2.00  30.00   0.50    5.00    --  -46.45  19.00 -90.00   56
  6  \w     -8.00  29.00   0.50    5.00    --  -46.45  19.00 -60.00   74
  7  \w     -8.00  30.00   0.50    5.00    --  -46.45  19.00 -30.00   76
  8  \w    -21.00   7.00   0.50    5.00    --  -46.45  38.00 -60.00   56
  9  \w    -25.00  42.00   0.50    5.00    --   46.45 -19.00  60.00  134
 10  \w     47.00  92.00   0.50   37.00    --  107.75 -61.00 120.00   90
 11  \w     36.00  65.00   0.50   37.00    --  107.75 -45.00 -60.00   58
 12  \w     42.00  70.00   0.50   37.00    --  107.75 -45.00 150.00   56
 13  \w     42.00  69.00   0.50   37.00    --  107.75 -45.00  60.00   54
 14  \w     36.00  61.00   0.50   37.00    --  107.75 -45.00-180.00   50
 15  \w     46.00  73.00   0.50   37.00    --  107.75 -45.00 120.00   54
 16  \w     32.00  57.00   0.50   37.00    --  107.75 -30.00-120.00   50
 17  \w     32.00  57.00   0.50   37.00    --  107.75 -30.00 150.00   50
 18  \w    101.00 131.00   0.50   37.00    --  107.75  30.00 150.00   60
 19  \w     32.00  57.00   0.50   37.00    --  107.75 -30.00  60.00   50
 20  \w     33.00  59.00   0.50   37.00    --  107.75 -30.00 -30.00   52
 21  \w     34.00 120.00   0.50   37.00    --  107.75 -77.00  90.00  172
 22  \w     36.00  73.00   0.50   37.00    --  107.75 -45.00 -30.00   74
 23  \w    133.00 172.00   0.50   37.00    --  107.75  30.00 150.00   78
 24  \w     41.00  73.00   0.50   37.00    --  107.75 -45.00   0.00   64
 25  \w     32.00  57.00   0.50   37.00    --  107.75 -30.00 -90.00   50
 26  \w     34.00  59.00   0.50   37.00    --  107.75 -30.00  90.00   50
 27  \w     45.00  93.00   0.50   37.00    --  107.75 -61.00 -90.00   96
 28  \w     37.00  70.00   0.50   37.00    --  107.75 -45.00-150.00   66
;
_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      -0.0462918000
_diffrn_orient_matrix_UB_12      -0.0401026000
_diffrn_orient_matrix_UB_13      0.0392559000
_diffrn_orient_matrix_UB_21      -0.0762800000
_diffrn_orient_matrix_UB_22      0.0429431000
_diffrn_orient_matrix_UB_23      0.0028602000
_diffrn_orient_matrix_UB_31      -0.0559185000
_diffrn_orient_matrix_UB_32      -0.0254575000
_diffrn_orient_matrix_UB_33      -0.0567083000
_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  0.0634
_diffrn_reflns_av_unetI/netI     0.0502
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            50158
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        66.500
_diffrn_reflns_theta_max         66.500
_diffrn_reflns_theta_min         2.701
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.346
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57144
_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    1.071
_exptl_crystal_description       block
_exptl_crystal_F_000             2816
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.690
_refine_diff_density_min         -0.507
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1041
_refine_ls_number_reflns         13965
_refine_ls_number_restraints     512
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.1463
_refine_ls_R_factor_gt           0.1124
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1744P)^2^+9.0557P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2972
_refine_ls_wR_factor_ref         0.3242
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9520
_reflns_number_total             13965
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02682b2.cif
_cod_data_source_block           compound-5
_cod_depositor_comments
'Adding full bibliography for 1574617--1574626.cif.'
_cod_database_code               1574623
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C71 H105 Al K N2 O7 Si2'
_chemical_oxdiff_usercomment     'cyclohexane layer'
_shelx_estimated_absorpt_t_max   0.924
_shelx_estimated_absorpt_t_min   0.803
_diffrn_oxdiff_ac3_digest_hkl    01c1126c29670f79939cff5cee0ee9e154b761
_diffrn_oxdiff_digest_hkl
;
019fafc6c829d1d2470d588199b9dddaadcaff
;
_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. Restrained distances
 C65-C60 = C61-C60 = C62-C61 = C63-C62 = C64-C63 = C65-C64
 1.53 with sigma of 0.008
 C73A-C72A = C77A-C72A = C77A-C76A = C76A-C75A = C75A-C74A = C74A-C73A
 1.53 with sigma of 0.008
 C72-C73 = C73-C74 = C74-C75 = C75-C76 = C76-C77 = C77-C72
 1.53 with sigma of 0.008
 C56A-C57A = C59A-C58A = C49A-C48A = C51A-C50A = C53A-C52A
 1.53 with sigma of 0.008
 C49-C48 = C51-C50 = C53-C52 = C55-C54 = C57-C56 = C59-C58
 1.53 with sigma of 0.008
 O5A-C53A = O4A-C52A = O4A-C51A = O3A-C50A = O3A-C49A = O2A-C48A = O2A-C59A =
 O7A-C58A = O7A-C57A = O6A-C56A
 1.4 with sigma of 0.008
 O5A-C54A
 1.4 with sigma of 0.008
 O2-C48 = O3-C49 = O3-C50 = O4-C51 = O4-C52 = O5-C53 = O5-C54 = O6-C55 = O6-
 C56 = O7-C57 = O7-C58 = O2-C59
 1.4 with sigma of 0.008
 C54A-C55A
 1.53 with sigma of 0.008
 C32-C30 = C32A-C30A = C31A-C30A = C31-C30
 1.53 with sigma of 0.008
 C61A-C60A = C62A-C61A = C63A-C62A = C64A-C63A = C65A-C64A = C65A-C60A
 1.53 with sigma of 0.008
 C70A-C69A = C71A-C70A = C71A-C66A = C67A-C66A = C68A-C67A = C69A-C68A
 1.53 with sigma of 0.008
 C27-C28 = C27-C29 = C27A-C28A = C27A-C29A
 1.53 with sigma of 0.008
 C71-C66 = C67-C66 = C68-C67 = C69-C68 = C70-C69 = C71-C70
 1.53 with sigma of 0.008
 C72A-C74A = C73A-C75A = C74A-C76A = C75A-C77A = C76A-C72A = C77A-C73A
 2.5 with sigma of 0.008
 C72-C74 = C73-C75 = C74-C76 = C75-C77 = C76-C72 = C73-C77
 2.5 with sigma of 0.008
 K1-C56
 3.45 with sigma of 0.008
 O2-C49 = O3-C48 = O3-C51 = O4-C50 = O4-C53 = O5-C52 = O5-C55 = O6-C54 = O6-
 C57 = O7-C56 = O7-C59 = O2-C58
 2.35 with sigma of 0.008
 C66A-C68A = C67A-C69A = C68A-C70A = C69A-C71A = C70A-C66A = C71A-C67A
 2.48 with sigma of 0.008
 C66-C68 = C67-C69 = C68-C70 = C69-C71 = C70-C66 = C71-C67
 2.5 with sigma of 0.008
3. Uiso/Uaniso restraints and constraints
C72 \\sim C73 \\sim C74 \\sim C75 \\sim C76 \\sim C77: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01 within 2A
O2A \\sim O3A \\sim O4A \\sim O5A \\sim O6A \\sim O7A \\sim C48A \\sim C49A
\\sim C50A \\sim C51A \\sim C52A \\sim C53A \\sim C54A \\sim C55A \\sim C56A
\\sim C57A \\sim C58A \\sim C59A: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
O2 \\sim O3 \\sim O4 \\sim O5 \\sim O6 \\sim O7 \\sim C48 \\sim C49 \\sim C50
\\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58
\\sim C59: within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
within 2A
C30 \\sim C30A \\sim C31 \\sim C31A \\sim C32 \\sim C32A: within 2A with sigma
of 0.005 and sigma for terminal atoms of 0.01 within 2A
C60A \\sim C61A \\sim C62A \\sim C63A \\sim C64A \\sim C65A: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C66A \\sim C67A \\sim C68A \\sim C69A \\sim C70A \\sim C71A: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01 within 2A
C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01 within 2A
C27 \\sim C27A \\sim C28 \\sim C28A \\sim C29 \\sim C29A: within 2A with sigma
of 0.005 and sigma for terminal atoms of 0.01 within 2A
Uanis(C27A) \\sim Ueq, Uanis(C27) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
4. Others
 Sof(O2A)=Sof(O3A)=Sof(O4A)=Sof(O5A)=Sof(O6A)=Sof(O7A)=Sof(C48A)=Sof(H48C)=
 Sof(H48D)=Sof(C49A)=Sof(H49C)=Sof(H49D)=Sof(C50A)=Sof(H50C)=Sof(H50D)=
 Sof(C51A)=Sof(H51C)=Sof(H51D)=Sof(C52A)=Sof(H52C)=Sof(H52D)=Sof(C53A)=
 Sof(H53C)=Sof(H53D)=Sof(C54A)=Sof(H54C)=Sof(H54D)=Sof(C55A)=Sof(H55C)=
 Sof(H55D)=Sof(C56A)=Sof(H56C)=Sof(H56D)=Sof(C57A)=Sof(H57C)=Sof(H57D)=
 Sof(C58A)=Sof(H58C)=Sof(H58D)=Sof(C59A)=Sof(H59C)=Sof(H59D)=1-FVAR(1)
 Sof(O2)=Sof(O3)=Sof(O4)=Sof(O5)=Sof(O6)=Sof(O7)=Sof(C48)=Sof(H48A)=Sof(H48B)=
 Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(C51)=Sof(H51A)=
 Sof(H51B)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(C54)=
 Sof(H54A)=Sof(H54B)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(C56)=Sof(H56A)=Sof(H56B)=
 Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(C59)=Sof(H59A)=
 Sof(H59B)=FVAR(1)
 Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31D)=Sof(H31E)=Sof(H31F)=Sof(C32A)=
 Sof(H32D)=Sof(H32E)=Sof(H32F)=1-FVAR(2)
 Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C32)=Sof(H32A)=
 Sof(H32B)=Sof(H32C)=FVAR(2)
 Sof(C60A)=Sof(H60C)=Sof(H60D)=Sof(C61A)=Sof(H61C)=Sof(H61D)=Sof(C62A)=
 Sof(H62C)=Sof(H62D)=Sof(C63A)=Sof(H63C)=Sof(H63D)=Sof(C64A)=Sof(H64C)=
 Sof(H64D)=Sof(C65A)=Sof(H65C)=Sof(H65D)=1-FVAR(3)
 Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C62)=Sof(H62A)=
 Sof(H62B)=Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(C65)=
 Sof(H65A)=Sof(H65B)=FVAR(3)
 Sof(C66A)=Sof(H66C)=Sof(H66D)=Sof(C67A)=Sof(H67C)=Sof(H67D)=Sof(C68A)=
 Sof(H68C)=Sof(H68D)=Sof(C69A)=Sof(H69C)=Sof(H69D)=Sof(C70A)=Sof(H70C)=
 Sof(H70D)=Sof(C71A)=Sof(H71C)=Sof(H71D)=1-FVAR(4)
 Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(C68)=Sof(H68A)=
 Sof(H68B)=Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(C71)=
 Sof(H71A)=Sof(H71B)=FVAR(4)
 Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29A)=
 Sof(H29D)=Sof(H29E)=Sof(H29F)=1-FVAR(5)
 Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29)=Sof(H29A)=
 Sof(H29B)=Sof(H29C)=FVAR(5)
 Fixed Sof: C72(0.25) H72A(0.25) H72B(0.25) C72A(0.25) H72C(0.25) H72D(0.25)
 C73(0.25) H73A(0.25) H73B(0.25) C73A(0.25) H73C(0.25) H73D(0.25) C74(0.25)
 H74A(0.25) H74B(0.25) C74A(0.25) H74C(0.25) H74D(0.25) C75(0.25) H75A(0.25)
 H75B(0.25) C75A(0.25) H75C(0.25) H75D(0.25) C76(0.25) H76A(0.25) H76B(0.25)
 C76A(0.25) H76C(0.25) H76D(0.25) C77(0.25) H77A(0.25) H77B(0.25) C77A(0.25)
 H77C(0.25) H77D(0.25)
 Fixed Uiso: H(0.06)
5.a Ternary CH refined with riding coordinates:
 C24(H24), C27(H27), C27A(H27A), C30(H30), C30A(H30A), C33(H33), C36(H36),
 C39(H39)
5.b Secondary CH2 refined with riding coordinates:
 C48(H48A,H48B), C48A(H48C,H48D), C49(H49A,H49B), C49A(H49C,H49D), C50(H50A,
 H50B), C50A(H50C,H50D), C51(H51A,H51B), C51A(H51C,H51D), C52(H52A,H52B),
 C52A(H52C,H52D), C53(H53A,H53B), C53A(H53C,H53D), C54(H54A,H54B), C54A(H54C,
 H54D), C55(H55A,H55B), C55A(H55C,H55D), C56(H56A,H56B), C56A(H56C,H56D),
 C57(H57A,H57B), C57A(H57C,H57D), C58(H58A,H58B), C58A(H58C,H58D), C59(H59A,
 H59B), C59A(H59C,H59D), C60(H60A,H60B), C60A(H60C,H60D), C61(H61A,H61B),
 C61A(H61C,H61D), C62(H62A,H62B), C62A(H62C,H62D), C63(H63A,H63B), C63A(H63C,
 H63D), C64(H64A,H64B), C64A(H64C,H64D), C65(H65A,H65B), C65A(H65C,H65D),
 C66(H66A,H66B), C66A(H66C,H66D), C67(H67A,H67B), C67A(H67C,H67D), C68(H68A,
 H68B), C68A(H68C,H68D), C69(H69A,H69B), C69A(H69C,H69D), C70(H70A,H70B),
 C70A(H70C,H70D), C71(H71A,H71B), C71A(H71C,H71D), C72(H72A,H72B), C72A(H72C,
 H72D), C73(H73A,H73B), C73A(H73C,H73D), C74(H74A,H74B), C74A(H74C,H74D),
 C75(H75A,H75B), C75A(H75C,H75D), C76(H76A,H76B), C76A(H76C,H76D), C77(H77A,
 H77B), C77A(H77C,H77D)
5.c 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)
5.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), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C),
 C28A(H28D,H28E,H28F), C29(H29A,H29B,H29C), C29A(H29D,H29E,H29F), C31(H31A,H31B,
 H31C), C31A(H31D,H31E,H31F), C32(H32A,H32B,H32C), C32A(H32D,H32E,H32F),
 C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C37(H37A,H37B,H37C), C38(H38A,H38B,
 H38C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C)
;
_shelx_res_checksum              51812
_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 1.740
_oxdiff_exptl_absorpt_empirical_full_min 0.621