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_1574626
_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(C53 H80 Al N2 O2 Si2), 2(C12 H24 K O6), 7.5(C6 H6)'
_chemical_formula_sum            'C175 H253 Al2 K2 N4 O16 Si4'
_chemical_formula_weight         2913.32
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2025-03-09
_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                88.4050(10)
_cell_angle_beta                 79.7730(10)
_cell_angle_gamma                89.7800(10)
_cell_formula_units_Z            2
_cell_length_a                   11.57270(10)
_cell_length_b                   26.0715(4)
_cell_length_c                   28.9632(4)
_cell_measurement_reflns_used    49751
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      77.7850
_cell_measurement_theta_min      3.1330
_cell_volume                     8596.53(19)
_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 0.998
_diffrn_measured_fraction_theta_max 0.975
_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    -63.00  27.00   0.50    0.50    --  -46.57  90.00 164.00  180
  2  \w     32.00  72.00   0.50    0.50    --   46.57 -90.00  49.00   80
  3  \w    105.00 131.00   0.50    2.50    --  107.75  90.00 164.00   52
  4  \w     50.00  76.00   0.50    2.50    --  107.75 -90.00  49.00   52
  5  \w     -5.00  28.00   0.50    0.50    --  -46.57  19.00 -90.00   66
  6  \w   -123.00 -36.00   0.50    0.50    --  -46.57 -19.00 -30.00  174
  7  \w    -13.00  27.00   0.50    0.50    --  -46.57  38.00 150.00   80
  8  \w    -22.00  27.00   0.50    0.50    --  -46.57  38.00 -60.00   98
  9  \w     -8.00  27.00   0.50    0.50    --  -46.57  19.00  60.00   70
 10  \w     -2.00  23.00   0.50    0.50    --  -46.57  19.00  90.00   50
 11  \w    -83.00 -56.00   0.50    0.50    --  -46.57 125.00-180.00   54
 12  \w    -47.00 -21.00   0.50    0.50    --  -46.57 125.00-180.00   52
 13  \w     33.00  90.00   0.50    0.50    --   46.57-125.00  30.00  114
 14  \w     81.00 106.00   0.50    2.50    --  107.75 -95.00 150.00   50
 15  \w     32.00  59.00   0.50    2.50    --  107.75 -30.00  30.00   54
 16  \w    122.00 152.00   0.50    2.50    --  107.75 125.00   0.00   60
 17  \w     35.00  60.00   0.50    2.50    --  107.75 -45.00 150.00   50
 18  \w     32.00  57.00   0.50    2.50    --  107.75 -30.00 -30.00   50
 19  \w     40.00  66.00   0.50    2.50    --  107.75 -61.00 -90.00   52
 20  \w     79.00 109.00   0.50    2.50    --  107.75 -77.00  60.00   60
 21  \w     36.00 107.00   0.50    2.50    --  107.75-101.00  76.77  142
 22  \w     33.00  58.00   0.50    2.50    --  107.75 -30.00 120.00   50
 23  \w     49.00  76.00   0.50    2.50    --  107.75 -77.00  60.00   54
 24  \w     39.00 119.00   0.50    2.50    --  107.75-133.00 -31.54  160
 25  \w     43.00  79.00   0.50    2.50    --  107.75-125.00 150.00   72
 26  \w     32.00  57.00   0.50    2.50    --  107.75 -30.00 150.00   50
 27  \w     96.00 176.00   0.50    2.50    --  107.75  45.00  30.00  160
 28  \w     37.00 112.00   0.50    2.50    --  107.75-125.00  30.00  150
 29  \w     40.00  86.00   0.50    2.50    --  107.75 -61.00-180.00   92
 30  \w     44.00  69.00   0.50    2.50    --  107.75 -95.00 150.00   50
 31  \w    125.00 171.00   0.50    2.50    --  107.75  30.00-150.00   92
 32  \w     67.00 107.00   0.50    2.50    --  107.75-100.00-174.89   80
 33  \w     47.00 105.00   0.50    2.50    --  107.75-102.00  52.89  116
 34  \w     40.00  73.00   0.50    2.50    --  107.75 -45.00 -90.00   66
 35  \w    105.00 162.00   0.50    2.50    --  107.75  15.00 -30.00  114
 36  \w     95.00 175.00   0.50    2.50    --  107.75  30.00 -90.00  160
 37  \w    103.00 178.00   0.50    2.50    --  107.75  45.00 120.00  150
 38  \w     53.00  79.00   0.50    2.50    --  107.75 -95.00-150.00   52
 39  \w     43.00 108.00   0.50    2.50    --  107.75-102.00 -51.84  130
 40  \w     99.00 172.00   0.50    2.50    --  107.75 125.00 120.00  146
 41  \w     50.00 111.00   0.50    2.50    --  107.75-125.00 -60.00  122
 42  \w     56.00  93.00   0.50    2.50    --  107.75 -61.00  60.00   74
 43  \w     39.00  73.00   0.50    2.50    --  107.75 -45.00 120.00   68
 44  \w     37.00 104.00   0.50    2.50    --  107.75 -95.00-120.00  134
 45  \w     48.00  73.00   0.50    2.50    --  107.75 -95.00 -30.00   50
 46  \w     81.00 106.00   0.50    2.50    --  107.75 -95.00 -30.00   50
 47  \w     78.00 106.00   0.50    2.50    --  107.75 -95.00 120.00   56
 48  \w     41.00  66.00   0.50    2.50    --  107.75-125.00-180.00   50
 49  \w     73.00 111.00   0.50    2.50    --  107.75-125.00-180.00   76
 50  \w     99.00 136.00   0.50    2.50    --  107.75  45.00  90.00   74
;
_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  0.0604
_diffrn_reflns_av_unetI/netI     0.0577
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            131178
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.297
_diffrn_reflns_theta_min         3.102
_exptl_absorpt_coefficient_mu    1.316
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80382
_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    1.125
_exptl_crystal_description       block
_exptl_crystal_F_000             3158
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.286
_refine_diff_density_min         -0.602
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1899
_refine_ls_number_reflns         35979
_refine_ls_number_restraints     253
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0852
_refine_ls_R_factor_gt           0.0745
_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^)+(0.1221P)^2^+5.2336P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2061
_refine_ls_wR_factor_ref         0.2170
_reflns_Friedel_coverage         0.000
_reflns_number_gt                29802
_reflns_number_total             35979
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02682b2.cif
_cod_data_source_block           compound-7
_cod_depositor_comments
'Adding full bibliography for 1574617--1574626.cif.'
_cod_database_code               1574626
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C163H230Al2K2N4O16Si4
_shelx_estimated_absorpt_t_max   0.827
_shelx_estimated_absorpt_t_min   0.694
_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
 C99-C98 = C100-C98
 1.53 with sigma of 0.008
 C79-C81 = C82-C79 = C80-C79 = C80A-C79A = C81A-C79A = C82A-C79A
 1.53 with sigma of 0.008
 C99-C100
 2.53 with sigma of 0.008
 C81-C82
 2.53 with sigma of 0.008
 C82-C80
 2.53 with sigma of 0.008
 C80-C81
 2.53 with sigma of 0.008
 C81A-C82A
 2.53 with sigma of 0.008
 C82A-C80A
 2.53 with sigma of 0.008
 C80A-C81A
 2.53 with sigma of 0.008
 C69-C79A \\sim C69-C79
 with sigma of 0.02
 C79A-C82A \\sim C79-C82
 with sigma of 0.02
 C79A-C80A \\sim C79-C80
 with sigma of 0.02
 C79A-C81A \\sim C79-C81
 with sigma of 0.02
 C69-C82A \\sim C69-C82
 with sigma of 0.04
 C69-C80A \\sim C69-C80
 with sigma of 0.04
 C69-C81A \\sim C69-C81
 with sigma of 0.04
 C82A-C80A \\sim C82-C80
 with sigma of 0.04
 C82A-C81A \\sim C82-C81
 with sigma of 0.04
 C80A-C81A \\sim C80-C81
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C176 \\sim C181 \\sim C180 \\sim C179 \\sim C178 \\sim C177: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C166 \\sim C165 \\sim C164 \\sim C169 \\sim C168 \\sim C167: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C186 \\sim C185 \\sim C184 \\sim C183 \\sim C182 \\sim C187: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C170 \\sim C175 \\sim C174 \\sim C173 \\sim C172 \\sim C171: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C161 \\sim C162 \\sim C163 \\sim C158 \\sim C159 \\sim C160: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C146 \\sim C145 \\sim C144 \\sim C143 \\sim C148 \\sim C147: within 2A with
sigma of 0.05 and sigma for terminal atoms of 0.1 within 2A
C79 \\sim C80 \\sim C81 \\sim C82: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
C79A \\sim C80A \\sim C81A \\sim C82A: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01 within 2A
Uanis(C79A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Others
 Sof(C170)=Sof(H170)=Sof(C175)=Sof(H175)=Sof(C174)=Sof(H174)=Sof(C173)=
 Sof(H173)=Sof(C172)=Sof(H172)=Sof(C171)=Sof(H171)=Sof(C176)=Sof(H176)=
 Sof(C181)=Sof(H181)=Sof(C180)=Sof(H180)=Sof(C179)=Sof(H179)=Sof(C178)=
 Sof(H178)=Sof(C177)=Sof(H177)=1-FVAR(1)
 Sof(C166)=Sof(H166)=Sof(C165)=Sof(H165)=Sof(C164)=Sof(H164)=Sof(C169)=
 Sof(H169)=Sof(C168)=Sof(H168)=Sof(C167)=Sof(H167)=Sof(C186)=Sof(H186)=
 Sof(C185)=Sof(H185)=Sof(C184)=Sof(H184)=Sof(C183)=Sof(H183)=Sof(C182)=
 Sof(H182)=Sof(C187)=Sof(H187)=FVAR(1)
 Sof(C79)=Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(H80C)=Sof(C81)=Sof(H81A)=Sof(H81B)=
 Sof(H81C)=Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(H82C)=1-FVAR(2)
 Sof(C79A)=Sof(C80A)=Sof(H80D)=Sof(H80E)=Sof(H80F)=Sof(C81A)=Sof(H81D)=
 Sof(H81E)=Sof(H81F)=Sof(C82A)=Sof(H82D)=Sof(H82E)=Sof(H82F)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C24(H24), C27(H27), C30(H30), C33(H33), C36(H36), C39(H39), C89(H89),
 C92(H92), C95(H95), C98(H98), C101(H101), C104(H104)
5.b Secondary CH2 refined with riding coordinates:
 C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B), C58(H58A,
 H58B), C59(H59A,H59B), C60(H60A,H60B), C61(H61A,H61B), C62(H62A,H62B),
 C63(H63A,H63B), C64(H64A,H64B), C65(H65A,H65B), C119(H11A,H11B), C120(H12A,
 H12B), C121(H12C,H12D), C122(H12E,H12F), C123(H12G,H12H), C124(H12I,H12J),
 C125(H12K,H12L), C126(H12M,H12N), C127(H12O,H12P), C128(H12Q,H12R), C129(H12S,
 H12T), C130(H13A,H13B)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C9(H9), C11(H11), C43(H43), C45(H45), C46(H46), C47(H47),
 C49(H49), C50(H50), C51(H51), C52(H52), C53(H53), C68(H68), C70(H70), C74(H74),
  C76(H76), C108(H108), C110(H110), C111(H111), C112(H112), C114(H114),
 C115(H115), C116(H116), C117(H117), C118(H118), C136(H136), C131(H131),
 C132(H132), C133(H133), C134(H134), C135(H135), C137(H137), C138(H138),
 C139(H139), C140(H140), C141(H141), C142(H142), C146(H146), C145(H145),
 C144(H144), C143(H143), C148(H148), C147(H147), C154(H154), C153(H153),
 C152(H152), C151(H151), C150(H150), C149(H149), C155(H155), C156(H156),
 C157(H157), C161(H161), C162(H162), C163(H163), C158(H158), C159(H159),
 C160(H160), C166(H166), C165(H165), C164(H164), C169(H169), C168(H168),
 C167(H167), C170(H170), C175(H175), C174(H174), C173(H173), C172(H172),
 C171(H171), C176(H176), C181(H181), C180(H180), C179(H179), C178(H178),
 C177(H177), C186(H186), C185(H185), C184(H184), C183(H183), C182(H182),
 C187(H187)
5.d Fitted hexagon refined as free rotating group:
 C136(C131,C132,C133,C134,C135), C146(C145,C144,C143,C148,C147), C154(C153,
 C152,C151,C150,C149), C161(C162,C163,C158,C159,C160), C166(C165,C164,C169,C168,
 C167), C170(C175,C174,C173,C172,C171), C176(C181,C180,C179,C178,C177),
 C186(C185,C184,C183,C182,C187)
5.e 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),
 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), C80(H80A,H80B,H80C), C80A(H80D,H80E,H80F),
 C81(H81A,H81B,H81C), C81A(H81D,H81E,H81F), C82(H82A,H82B,H82C), C82A(H82D,H82E,
 H82F), C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C86(H86A,H86B,H86C), C87(H87A,
 H87B,H87C), C88(H88A,H88B,H88C), C90(H90A,H90B,H90C), C91(H91A,H91B,H91C),
 C93(H93A,H93B,H93C), C94(H94A,H94B,H94C), C96(H96A,H96B,H96C), C97(H97A,H97B,
 H97C), C99(H99A,H99B,H99C), C100(H10A,H10B,H10C), C102(H10D,H10E,H10F),
 C103(H10G,H10H,H10I), C105(H10J,H10K,H10L), C106(H10M,H10N,H10O)
;
_shelx_res_checksum              73390
_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 2.164
_oxdiff_exptl_absorpt_empirical_full_min 0.461