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_1574618
_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         'C53 H94 Al K N2 O7 Si2, C5 H12'
_chemical_formula_sum            'C58 H106 Al K N2 O7 Si2'
_chemical_formula_weight         1065.70
_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
_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                 104.568(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.7297(3)
_cell_length_b                   22.5628(2)
_cell_length_c                   17.7034(3)
_cell_measurement_reflns_used    18693
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      75.0150
_cell_measurement_theta_min      3.2220
_cell_volume                     6467.64(18)
_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 0.983
_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     -9.00  16.00   0.50    6.00    --  -46.57  22.00  39.00   50
  2  \w   -123.00 -36.00   0.50    6.00    --  -46.57 -22.00-126.00  174
  3  \w     35.00 109.00   0.50    6.00    --   46.57  22.00  39.00  148
  4  \w      1.00  51.00   0.50    6.00    --   46.57 -22.00-126.00  100
  5  \w     98.00 171.00   0.50   25.00    --  107.75  22.00  39.00  146
  6  \w     -2.00  23.00   0.50    6.00    --  -46.57  19.00-180.00   50
  7  \w    -86.00 -26.00   0.50    6.00    --  -46.57 125.00-180.00  120
  8  \w    -25.00  46.00   0.50    6.00    --   46.57 -19.00  90.00  142
  9  \w     42.00  87.00   0.50   25.00    --  107.75 -61.00   0.00   90
 10  \w     33.00  58.00   0.50   25.00    --  107.75 -30.00 -60.00   50
 11  \w     56.00 103.00   0.50   25.00    --  107.75 -95.00 150.00   94
 12  \w     32.00  59.00   0.50   25.00    --  107.75 -30.00-150.00   54
 13  \w     35.00  70.00   0.50   25.00    --  107.75 -45.00-150.00   70
 14  \w     41.00  69.00   0.50   25.00    --  107.75 -77.00   0.00   56
 15  \w     73.00  99.00   0.50   25.00    --  107.75 -77.00   0.00   52
 16  \w     38.00  70.00   0.50   25.00    --  107.75 -45.00-120.00   64
 17  \w     36.00  67.00   0.50   25.00    --  107.75 -45.00 -60.00   62
 18  \w     34.00  99.00   0.50   25.00    --  107.75 -95.00 120.00  130
 19  \w     69.00 107.00   0.50   25.00    --  107.75-125.00-120.00   76
 20  \w     32.00  57.00   0.50   25.00    --  107.75 -30.00-180.00   50
 21  \w     33.00  59.00   0.50   25.00    --  107.75 -30.00  90.00   52
 22  \w     32.00  57.00   0.50   25.00    --  107.75 -30.00-120.00   50
 23  \w     32.00  57.00   0.50   25.00    --  107.75 -30.00 120.00   50
 24  \w    113.00 166.00   0.50   25.00    --  107.75  45.00 120.00  106
 25  \w     47.00  73.00   0.50   25.00    --  107.75 -61.00  30.00   52
 26  \w     34.00  89.00   0.50   25.00    --  107.75 -61.00 120.00  110
 27  \w     40.00  66.00   0.50   25.00    --  107.75 -45.00   0.00   52
 28  \w     36.00  98.00   0.50   25.00    --  107.75 -95.00  90.00  124
 29  \w     41.00  68.00   0.50   25.00    --  107.75 -45.00 -90.00   54
 30  \w    100.00 132.00   0.50   25.00    --  107.75 125.00-150.00   64
 31  \w    139.00 165.00   0.50   25.00    --  107.75 125.00-150.00   52
 32  \w     41.00  73.00   0.50   25.00    --  107.75 -45.00 120.00   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  0.0461
_diffrn_reflns_av_unetI/netI     0.0415
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            58107
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.070
_diffrn_reflns_theta_min         3.239
_exptl_absorpt_coefficient_mu    1.566
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82003
_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    1.094
_exptl_crystal_description       needle
_exptl_crystal_F_000             2336
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.370
_refine_diff_density_min         -0.347
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     740
_refine_ls_number_reflns         13622
_refine_ls_number_restraints     114
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0719
_refine_ls_R_factor_gt           0.0581
_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^)+(0.0760P)^2^+2.7387P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1506
_refine_ls_wR_factor_ref         0.1598
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11095
_reflns_number_total             13622
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02682b2.cif
_cod_data_source_block           compound-10
_cod_depositor_comments
'Adding full bibliography for 1574617--1574626.cif.'
_cod_database_code               1574618
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H N O Al Si K'
_shelx_estimated_absorpt_t_max   0.969
_shelx_estimated_absorpt_t_min   0.799
_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
 C58-C57 = C57-C56 = C56-C55 = C55-C54
 1.53 with sigma of 0.008
 C54A-C55A = C55A-C56A = C56A-C57A = C58A-C57A
 1.53 with sigma of 0.008
 C26-C24 = C26A-C24A = C25-C24 = C25A-C24A
 1.53 with sigma of 0.008
 C61-C59 = C60-C59
 1.53 with sigma of 0.008
 C15-C14 = C16-C14 = C17-C14
 1.53 with sigma of 0.008
 C16A-C14 = C17A-C14 = C15A-C14
 1.53 with sigma of 0.008
 C54-C56 = C55-C57 = C56-C58
 2.5 with sigma of 0.008
 C54A-C56A = C55A-C57A = C56A-C58A
 2.5 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58: within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01 within 2A
C24A \\sim C25A \\sim C26A: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
C24 \\sim C25 \\sim C26: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
C14 \\sim C15 \\sim C15A \\sim C16 \\sim C16A \\sim C17 \\sim C17A: within 2A
with sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
4. Others
 Sof(C54A)=Sof(H54D)=Sof(H54E)=Sof(H54F)=Sof(C55A)=Sof(H55C)=Sof(H55D)=
 Sof(C56A)=Sof(H56C)=Sof(H56D)=Sof(C57A)=Sof(H57C)=Sof(H57D)=Sof(C58A)=
 Sof(H58D)=Sof(H58E)=Sof(H58F)=1-FVAR(1)
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=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(H58C)=FVAR(1)
 Sof(C24A)=Sof(C25A)=Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C26A)=Sof(H26D)=
 Sof(H26E)=Sof(H26F)=1-FVAR(2)
 Sof(C24)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C26)=Sof(H26A)=Sof(H26B)=
 Sof(H26C)=FVAR(2)
 Sof(C59)=Sof(H59)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=Sof(C61)=Sof(H61A)=
 Sof(H61B)=Sof(H61C)=1-FVAR(3)
 Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C32)=Sof(H32A)=
 Sof(H32B)=Sof(H32C)=FVAR(3)
 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(4)
 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(4)
5.a Ternary CH refined with riding coordinates:
 C27(H27), C30(H30), C33(H33), C36(H36), C39(H39), C59(H59)
5.b Secondary CH2 refined with riding coordinates:
 C42(H42A,H42B), C43(H43A,H43B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,
 H46B), C47(H47A,H47B), C48(H48A,H48B), C49(H49A,H49B), C50(H50A,H50B),
 C51(H51A,H51B), C52(H52A,H52B), C53(H53A,H53B), C55(H55A,H55B), C55A(H55C,
 H55D), C56(H56A,H56B), C56A(H56C,H56D), C57(H57A,H57B), C57A(H57C,H57D)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C9(H9), C11(H11)
5.d 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), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C25(H25A,H25B,H25C), C25A(H25D,H25E,H25F), C26(H26A,H26B,H26C),
 C26A(H26D,H26E,H26F), 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),
 C54(H54A,H54B,H54C), C54A(H54D,H54E,H54F), C58(H58A,H58B,H58C), C58A(H58D,H58E,
 H58F), C60(H60A,H60B,H60C), C61(H61A,H61B,H61C)
;
_shelx_res_checksum              76117
_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 1.430
_oxdiff_exptl_absorpt_empirical_full_min 0.689