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_1574620
_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         'C48 H78 Al N2 O Si2, C12 H24 K O6'
_chemical_formula_sum            'C60 H102 Al K N2 O7 Si2'
_chemical_formula_weight         1085.69
_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             2025-04-04
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.06 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-04-04 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                   13.52700(10)
_cell_length_b                   23.84830(10)
_cell_length_c                   20.00370(10)
_cell_measurement_reflns_used    71184
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      77.7510
_cell_measurement_theta_min      2.8690
_cell_volume                     6453.11(6)
_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    'solved using X-ray data'
_diffrn_ambient_temperature      150.15(10)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'Laue image-plate'
_diffrn_measured_fraction_theta_full 0.800
_diffrn_measured_fraction_theta_max 0.800
_diffrn_measurement_details      '12 images, exposure time 6000s'
_diffrn_measurement_device       'KOALA2, ANSTO'
_diffrn_measurement_device_type  'Laue image-plate diffractometer'
_diffrn_measurement_method       Laue
_diffrn_radiation_probe          neutron
_diffrn_radiation_type           neutron
_diffrn_radiation_wavelength     1.003
_diffrn_reflns_av_R_equivalents  0.066
_diffrn_reflns_av_unetI/netI     0.1159
_diffrn_reflns_Laue_measured_fraction_full 0.800
_diffrn_reflns_Laue_measured_fraction_max 0.800
_diffrn_reflns_number            2762
_diffrn_reflns_point_group_measured_fraction_full 0.800
_diffrn_reflns_point_group_measured_fraction_max 0.800
_diffrn_reflns_reduction_process 'LaueG (Piltz, 2018a)'
_diffrn_reflns_theta_full        29.996
_diffrn_reflns_theta_max         29.996
_diffrn_reflns_theta_min         3.521
_diffrn_source                   'nuclear reactor'
_diffrn_source_details           'thermal neutrons, supermirror guides'
_exptl_absorpt_coefficient_mu    0.497
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74784
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.117
_exptl_crystal_description       block
_exptl_crystal_F_000             2368
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.062
_refine_diff_density_min         -0.778
_refine_diff_density_rms         0.142
_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     701
_refine_ls_number_reflns         2762
_refine_ls_number_restraints     232
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.1732
_refine_ls_R_factor_gt           0.1061
_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^)+(0.0762P)^2^+279.7317P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2347
_refine_ls_wR_factor_ref         0.2837
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1777
_reflns_number_total             2762
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02682b2.cif
_cod_data_source_block           compound-6_neut
_cod_depositor_comments
'Adding full bibliography for 1574617--1574626.cif.'
_cod_database_code               1574620
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.898
_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
 C15-C14 = C14-C16 = C14A-C16A = C15A-C14A
 1.53 with sigma of 0.008
 C27A-C29A = C29-C27
 1.53 with sigma of 0.008
 Si1-C14 = Si1-C14A
 1.9 with sigma of 0.008
 C22-C20 = C20A-C21A = C22A-C20A = C20A-C21A = C21-C20
 1.53 with sigma of 0.008
 C13-H13A = C13-H13B = C13-H13C
 1.1 with sigma of 0.008
 O3A-C31A = O3A-C32A = O4A-C33A = O4A-C34A = O5A-C35A = O5A-C36A = O6A-C37A =
 O6A-C38A = O7A-C39A = O7A-C40A = O2A-C41A = O2A-C30A
 1.42 with sigma of 0.008
 C33A-C32A = C35A-C34A = C37A-C36A = C39A-C38A = C41A-C40A = C31A-C30A
 1.5 with sigma of 0.008
 O3-C32 = O4-C33 = O4-C34 = O5-C35 = O5-C36 = O6-C37 = O6-C38 = O7-C39 = O7-
 C40 = O2-C41 = O2-C30 = O3-C31
 1.42 with sigma of 0.008
 C31-C30 = C33-C32 = C35-C34 = C37-C36 = C39-C38 = C41-C40
 1.5 with sigma of 0.008
 C15-C16 = C18-C19 = C15A-C16A = C18A-C19A
 2.5 with sigma of 0.008
 C19A-Si1
 2.95 with sigma of 0.008
 C21A-C22A
 2.5 with sigma of 0.008
3. Uiso/Uaniso restraints and constraints
C23A \\sim C24A \\sim C25A \\sim C26A \\sim C27A \\sim C28A \\sim C29A: 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 C29: 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 C30A \\sim C31A
\\sim C32A \\sim C33A \\sim C34A \\sim C35A \\sim C36A \\sim C37A \\sim C38A
\\sim C39A \\sim C40A \\sim C41A: 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 C30 \\sim C31 \\sim C32
\\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40
\\sim C41: within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
within 2A
Uanis(Si1) \\sim Ueq, Uanis(C20A) \\sim Ueq, Uanis(C16A) \\sim Ueq, Uanis(C18)
\\sim Ueq: with sigma of 0.008 and sigma for terminal atoms of 0.016
Uanis(C16) = Uanis(C16A)
Uanis(Si1A) = Uanis(Si1)
Uanis(C22A) = Uanis(C22)
4. Rigid body (RIGU) restrains
 C14, C14A, C15, C15A, C16, C16A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C20, C20A, C21, C21A, C22, C22A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C17A, C18A, C19A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: Si1(0.5) Si1A(0.5) O2(0.25) O2A(0.25) O3(0.25) O3A(0.25) O4(0.25)
 O4A(0.25) O5(0.25) O5A(0.25) O6(0.25) O6A(0.25) O7(0.25) O7A(0.25) C14(0.5)
 H14(0.5) C14A(0.5) H14A(0.5) C15(0.5) H15A(0.5) H15B(0.5) H15C(0.5) C15A(0.5)
 H15D(0.5) H15E(0.5) H15F(0.5) C16(0.5) H16A(0.5) H16B(0.5) H16C(0.5) C16A(0.5)
 H16D(0.5) H16E(0.5) H16F(0.5) C17(0.5) H17(0.5) C17A(0.5) H17A(0.5) C18(0.5)
 H18A(0.5) H18B(0.5) H18C(0.5) C18A(0.5) H18D(0.5) H18E(0.5) H18F(0.5) C19(0.5)
 H19A(0.5) H19B(0.5) H19C(0.5) C19A(0.5) H19D(0.5) H19E(0.5) H19F(0.5) C20(0.5)
 H20(0.5) C20A(0.5) H20A(0.5) C21(0.5) H21A(0.5) H21B(0.5) H21C(0.5) C21A(0.5)
 H21D(0.5) H21E(0.5) H21F(0.5) C22(0.5) H22A(0.5) H22B(0.5) H22C(0.5) C22A(0.5)
 H22D(0.5) H22E(0.5) H22F(0.5) C23(0.2) C24(0.2) H24(0.2) C25(0.2) H25(0.2)
 C26(0.2) H26(0.2) C27(0.2) C28(0.2) H28(0.2) C23A(0.3) C24A(0.3) H24A(0.3)
 C25A(0.3) H25A(0.3) C26A(0.3) H26A(0.3) C27A(0.3) C28A(0.3) H28A(0.3) C29(0.2)
 H29A(0.2) H29B(0.2) H29C(0.2) C29A(0.3) H29D(0.3) H29E(0.3) H29F(0.3)
 C30(0.25) H30A(0.25) H30B(0.25) C30A(0.25) H30C(0.25) H30D(0.25) C31(0.25)
 H31B(0.25) H31A(0.25) C31A(0.25) H31C(0.25) H31D(0.25) C32(0.25) H32B(0.25)
 H32A(0.25) C32A(0.25) H32C(0.25) H32D(0.25) C33(0.25) H33A(0.25) H33B(0.25)
 C33A(0.25) H33C(0.25) H33D(0.25) C34(0.25) H34A(0.25) H34B(0.25) C34A(0.25)
 H34C(0.25) H34D(0.25) C35(0.25) H35A(0.25) H35B(0.25) C35A(0.25) H35D(0.25)
 H35C(0.25) C36(0.25) H36A(0.25) H36B(0.25) C36A(0.25) H36C(0.25) H36D(0.25)
 C37(0.25) H37A(0.25) H37B(0.25) C37A(0.25) H37C(0.25) H37D(0.25) C38(0.25)
 H38A(0.25) H38B(0.25) C38A(0.25) H38C(0.25) H38D(0.25) C39(0.25) H39A(0.25)
 H39B(0.25) C39A(0.25) H39C(0.25) H39D(0.25) C40(0.25) H40B(0.25) H40A(0.25)
 C40A(0.25) H40D(0.25) H40C(0.25) C41(0.25) H41A(0.25) H41B(0.25) C41A(0.25)
 H41D(0.25) H41C(0.25)
 Fixed Uiso: H22A(0.1) H22B(0.1) H22C(0.1)
6.a Ternary CH refined with riding coordinates:
 C14(H14), C14A(H14A), C17(H17), C17A(H17A), C20(H20), C20A(H20A)
6.b Secondary CH2 refined with riding coordinates:
 C30(H30A,H30B), C30A(H30C,H30D), C31(H31B,H31A), C31A(H31C,H31D), C32(H32B,
 H32A), C32A(H32C,H32D), C33(H33A,H33B), C33A(H33C,H33D), C34(H34A,H34B),
 C34A(H34C,H34D), C35(H35A,H35B), C35A(H35D,H35C), C36(H36A,H36B), C36A(H36C,
 H36D), C37(H37A,H37B), C37A(H37C,H37D), C38(H38A,H38B), C38A(H38C,H38D),
 C39(H39A,H39B), C39A(H39C,H39D), C40(H40B,H40A), C40A(H40D,H40C), C41(H41A,
 H41B), C41A(H41D,H41C)
6.c Aromatic/amide H refined with riding coordinates:
 C24(H24), C25(H25), C26(H26), C28(H28), C24A(H24A), C25A(H25A), C26A(H26A),
 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:
 C15(H15A,H15B,H15C), C15A(H15D,H15E,H15F), C16(H16A,H16B,H16C), C16A(H16D,
 H16E,H16F), C18(H18A,H18B,H18C), C18A(H18D,H18E,H18F), C19(H19A,H19B,H19C),
 C19A(H19D,H19E,H19F), C21(H21A,H21B,H21C), C21A(H21D,H21E,H21F), C22(H22A,H22B,
 H22C), C22A(H22D,H22E,H22F), C29(H29A,H29B,H29C), C29A(H29D,H29E,H29F)
;
_shelx_res_checksum              44283
_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
;