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_1574624
_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         'C60 H102 Al K N2 O7 Si2'
_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
_atom_sites_solution_primary     dual
_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                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    '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 1.000
_diffrn_measured_fraction_theta_max 0.999
_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    -47.00  26.00   0.50    1.00    --  -46.45  60.00  47.00  146
  2  \w    -18.00  62.00   0.50    1.00    --   46.45 -60.00 -91.00  160
  3  \w     48.00 118.00   0.50    1.00    --   46.45  60.00  47.00  140
  4  \w    143.00 176.00   0.50    4.00    --  107.75  60.00  47.00   66
  5  \w     37.00  71.00   0.50    4.00    --  107.75 -60.00 -91.00   68
  6  \w     98.00 126.00   0.50    4.00    --  107.75  60.00  47.00   56
  7  \w     -7.00  23.00   0.50    1.00    --  -46.45  19.00 -30.00   60
  8  \w   -115.00 -40.00   0.50    1.00    --  -46.45 -60.00 -91.00  150
  9  \w      1.00  27.00   0.50    1.00    --  -46.45  38.00-180.00   52
 10  \w    -18.00  25.00   0.50    1.00    --  -46.45  38.00   0.00   86
 11  \w    -87.00 -57.00   0.50    1.00    --  -46.45 125.00  90.00   60
 12  \w    -53.00 -12.00   0.50    1.00    --  -46.45 125.00  90.00   82
 13  \w     33.00  81.00   0.50    1.00    --   46.45-125.00 150.00   96
 14  \w     33.00  58.00   0.50    4.00    --  107.75 -30.00  30.00   50
 15  \w     43.00 105.00   0.50    4.00    --  107.75-125.00 -90.00  124
 16  \w     35.00  60.00   0.50    4.00    --  107.75 -95.00  30.00   50
 17  \w     78.00 106.00   0.50    4.00    --  107.75 -95.00 -90.00   56
 18  \w     35.00  82.00   0.50    4.00    --  107.75 -95.00  90.00   94
 19  \w    125.00 172.00   0.50    4.00    --  107.75  45.00  30.00   94
 20  \w     63.00  89.00   0.50    4.00    --  107.75-140.00-158.49   52
 21  \w     90.00 128.00   0.50    4.00    --  107.75  77.00  60.00   76
 22  \w     35.00  61.00   0.50    4.00    --  107.75 -45.00 -60.00   52
 23  \w    104.00 132.00   0.50    4.00    --  107.75  15.00 -30.00   56
 24  \w     96.00 137.00   0.50    4.00    --  107.75 125.00 -30.00   82
 25  \w     45.00  77.00   0.50    4.00    --  107.75 -77.00 -90.00   64
 26  \w     88.00 114.00   0.50    4.00    --  107.75 -77.00 -90.00   52
 27  \w    139.00 177.00   0.50    4.00    --  107.75  77.00  60.00   76
 28  \w    107.00 133.00   0.50    4.00    --  107.75 125.00-180.00   52
 29  \w     36.00  62.00   0.50    4.00    --  107.75 -95.00  60.00   52
 30  \w     65.00 102.00   0.50    4.00    --  107.75 -95.00  60.00   74
 31  \w     35.00  75.00   0.50    4.00    --  107.75   0.00-180.00   80
 32  \w     85.00 158.00   0.50    4.00    --  107.75   0.00-180.00  146
 33  \w     38.00  93.00   0.50    4.00    --  107.75 -95.00 150.00  110
 34  \w     44.00  76.00   0.50    4.00    --  107.75-125.00 -60.00   64
 35  \w     86.00 112.00   0.50    4.00    --  107.75 -77.00  60.00   52
 36  \w     99.00 124.00   0.50    4.00    --  107.75-140.00-158.49   50
 37  \w     33.00  59.00   0.50    4.00    --  107.75 -30.00 -60.00   52
 38  \w     33.00  59.00   0.50    4.00    --  107.75 -30.00  60.00   52
 39  \w     33.00  58.00   0.50    4.00    --  107.75 -30.00-180.00   50
 40  \w     58.00 112.00   0.50    4.00    --  107.75-125.00-150.00  108
 41  \w     63.00 119.00   0.50    4.00    --  107.75-133.00  -7.58  112
 42  \w     38.00  88.00   0.50    4.00    --  107.75 -61.00-150.00  100
 43  \w     55.00  97.00   0.50    4.00    --  107.75 -77.00 150.00   84
 44  \w     93.00 168.00   0.50    4.00    --  107.75  15.00-150.00  150
 45  \w     49.00  75.00   0.50    4.00    --  107.75 -61.00 -60.00   52
 46  \w     60.00 105.00   0.50    4.00    --  107.75-121.00  73.12   90
 47  \w     39.00  93.00   0.50    4.00    --  107.75-125.00 -30.00  108
 48  \w     42.00 110.00   0.50    4.00    --  107.75-125.00 150.00  136
 49  \w    137.00 175.00   0.50    4.00    --  107.75 125.00-150.00   76
 50  \w     63.00 108.00   0.50    4.00    --  107.75-110.00-119.35   90
 51  \w     65.00 109.00   0.50    4.00    --  107.75-112.00 142.49   88
 52  \w    139.00 169.00   0.50    4.00    --  107.75 125.00-180.00   60
 53  \w     45.00  71.00   0.50    4.00    --  107.75-108.00  -8.22   52
 54  \w     83.00 108.00   0.50    4.00    --  107.75-108.00  -8.22   50
 55  \w     39.00  64.00   0.50    4.00    --  107.75-125.00   0.00   50
 56  \w     71.00 112.00   0.50    4.00    --  107.75-125.00   0.00   82
 57  \w    123.00 165.00   0.50    4.00    --  107.75 125.00 -90.00   84
 58  \w    132.00 165.00   0.50    4.00    --  107.75 125.00   0.00   66
 59  \w     63.00 107.00   0.50    4.00    --  107.75 -99.00-118.97   88
 60  \w     41.00  72.00   0.50    4.00    --  107.75 -45.00   0.00   62
 61  \w    103.00 156.00   0.50    4.00    --  107.75  45.00 -30.00  106
 62  \w     34.00  79.00   0.50    4.00    --  107.75 -77.00-180.00   90
 63  \w     98.00 123.00   0.50    4.00    --  107.75 -77.00-180.00   50
 64  \w     45.00  80.00   0.50    4.00    --  107.75 -77.00   0.00   70
 65  \w     41.00 106.00   0.50    4.00    --  107.75 -95.00   0.00  130
 66  \w     90.00 115.00   0.50    4.00    --  107.75  77.00 -30.00   50
 67  \w    120.00 177.00   0.50    4.00    --  107.75  77.00 -30.00  114
 68  \w     37.00  72.00   0.50    4.00    --  107.75 -61.00-120.00   70
 69  \w     95.00 164.00   0.50    4.00    --  107.75 125.00-120.00  138
 70  \w     32.00  59.00   0.50    4.00    --  107.75 -30.00 -30.00   54
 71  \w     46.00  72.00   0.50    4.00    --  107.75-106.00-161.12   52
 72  \w     82.00 107.00   0.50    4.00    --  107.75-106.00-161.12   50
 73  \w     76.00 106.00   0.50    4.00    --  107.75 -95.00  30.00   60
 74  \w     45.00  70.00   0.50    4.00    --  107.75-125.00  90.00   50
 75  \w    151.00 176.00   0.50    4.00    --  107.75  45.00-120.00   50
 76  \w    144.00 173.00   0.50    4.00    --  107.75  77.00 150.00   58
 77  \w     44.00  72.00   0.50    4.00    --  107.75 -45.00 150.00   56
;
_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      -0.0853012000
_diffrn_orient_matrix_UB_12      0.0427223000
_diffrn_orient_matrix_UB_13      0.0033054000
_diffrn_orient_matrix_UB_21      -0.0327471000
_diffrn_orient_matrix_UB_22      -0.0171770000
_diffrn_orient_matrix_UB_23      -0.0708982000
_diffrn_orient_matrix_UB_31      -0.0679737000
_diffrn_orient_matrix_UB_32      -0.0452816000
_diffrn_orient_matrix_UB_33      0.0299593000
_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  0.0375
_diffrn_reflns_av_unetI/netI     0.0160
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            140124
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.104
_diffrn_reflns_theta_min         2.883
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.580
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74784
_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    1.117
_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         0.664
_refine_diff_density_min         -0.608
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     543
_refine_ls_number_reflns         7075
_refine_ls_number_restraints     315
_refine_ls_restrained_S_all      1.210
_refine_ls_R_factor_all          0.0795
_refine_ls_R_factor_gt           0.0772
_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^)+(0.1257P)^2^+4.9123P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2240
_refine_ls_wR_factor_ref         0.2269
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6677
_reflns_number_total             7075
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02682b2.cif
_cod_data_source_block           compound-6
_cod_depositor_comments
'Adding full bibliography for 1574617--1574626.cif.'
_cod_database_code               1574624
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C69H65K2N3OSi2
_shelx_estimated_absorpt_t_max   0.833
_shelx_estimated_absorpt_t_min   0.722
_diffrn_oxdiff_ac3_digest_hkl    0188d2ed5a25d843f5146caff4571f91c24af3
_diffrn_oxdiff_digest_hkl
;
011b38d6f59c113ce7c3f9e69a34a33d3a3305
;
_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
 O5-C36 = O5-C35 = O4-C34 = O4-C33 = O3-C32 = O3-C31 = O2-C30 = O2-C41 = O7-
 C40 = O7-C39 = O6-C38 = O6-C37
 1.4 with sigma of 0.008
 C39-C38 = C36-C37 = C35-C34 = C33-C32 = C30-C31 = C40-C41
 1.5 with sigma of 0.008
 C15-C14 = C14-C16 = C14A-C16A = C15A-C14A = C21-C20 = C22-C20 = C22A-C20A =
 C21A-C20A = C18A-C17A = C19A-C17A = C19-C17 = C18-C17
 1.53 with sigma of 0.008
 C31-C30 = C41-C40 = C39-C38 = C37-C36 = C35-C34 = C33-C32
 1.53 with sigma of 0.008
 Si1-C17 = Si1-C17A = Si1-C14 = Si1-C14A = Si1-C20 = Si1-C20A
 1.9 with sigma of 0.008
 C15-C16 = C18-C19 = C21A-C22A = C15A-C16A = C18A-C19A = C21-C22
 2.5 with sigma of 0.008
 C15-C16 = C15A-C16A = C18-C19 = C18A-C19A = C21-C22 = C21A-C22A
 2.5 with sigma of 0.008
 Si1-C21 = Si1-C22
 2.9 with sigma of 0.008
 H8A-H9A
 2.35 with sigma of 0.003
3. Uiso/Uaniso restraints and constraints
K1 \\sim 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
C20 \\sim C20A \\sim C21 \\sim C21A \\sim C22 \\sim C22A: within 2A with sigma
of 0.008 and sigma for terminal atoms of 0.016 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
C14 \\sim C15 \\sim C16: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
C20 \\sim C21 \\sim C22: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
C17 \\sim C18 \\sim C19: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
Uanis(C21) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C17) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C29) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
4. Others
 Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C19A)=
 Sof(H19D)=Sof(H19E)=Sof(H19F)=1-FVAR(1)
 Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19A)=
 Sof(H19B)=Sof(H19C)=FVAR(1)
 Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16A)=
 Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(2)
 Sof(C14)=Sof(H14)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16)=Sof(H16A)=
 Sof(H16B)=Sof(H16C)=FVAR(2)
 Sof(C20A)=Sof(H20A)=Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C22A)=
 Sof(H22D)=Sof(H22E)=Sof(H22F)=1-FVAR(3)
 Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22)=Sof(H22A)=
 Sof(H22B)=Sof(H22C)=FVAR(3)
 Fixed Sof: O2(0.5) O3(0.5) O4(0.5) O5(0.5) O6(0.5) O7(0.5) H8A(0.5) H8B(0.5)
 H8C(0.5) H9A(0.5) H9B(0.5) H9C(0.5) C23(0.5) C24(0.5) H24(0.5) C25(0.5)
 H25(0.5) C26(0.5) H26(0.5) C27(0.5) C28(0.5) H28(0.5) C29(0.5) H29A(0.5)
 H29B(0.5) H29C(0.5) C30(0.5) H30A(0.5) H30B(0.5) C31(0.5) H31A(0.5) H31B(0.5)
 C32(0.5) H32A(0.5) H32B(0.5) C33(0.5) H33A(0.5) H33B(0.5) C34(0.5) H34A(0.5)
 H34B(0.5) C35(0.5) H35A(0.5) H35B(0.5) C36(0.5) H36A(0.5) H36B(0.5) C37(0.5)
 H37A(0.5) H37B(0.5) C38(0.5) H38A(0.5) H38B(0.5) C39(0.5) H39A(0.5) H39B(0.5)
 C40(0.5) H40A(0.5) H40B(0.5) C41(0.5) H41A(0.5) H41B(0.5)
 Fixed Uiso: H(0.045)
5.a Ternary CH refined with riding coordinates:
 C14(H14), C14A(H14A), C17(H17), C17A(H17A), C20(H20), C20A(H20A)
5.b Secondary CH2 refined with riding coordinates:
 C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B), C34(H34A,
 H34B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B),
 C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C24(H24), C25(H25), C26(H26), C28(H28)
5.d Fitted hexagon refined as free rotating group:
 C23(C24,C25,C26,C27,C28)
5.e Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), 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)
;
_shelx_res_checksum              68112
_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 1.629
_oxdiff_exptl_absorpt_empirical_full_min 0.588