Metallation of sensitive fluoroarenes using a potassium TMP-zincate supported by a silyl(bis)amido ligand
Mastropierro, Pasquale; Kennedy, Alan R.; Hevia, Eva; Chemical Communications  (2022) –; doi:10.1039/D2CC00979J

data_7129965
_publ_section_title
;
 Metallation of sensitive fluoroarenes using a potassium TMP-zincate
 supported by a silyl(bis)amido ligand
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC00979J
_journal_year                    2022
_chemical_formula_moiety
'C42 H47 F N3 O2 Si Zn, 2(C12 H24 K0.5 O3), C4 H8 O'
_chemical_formula_sum            'C70 H103 F K N3 O9 Si Zn'
_chemical_formula_weight         1282.11
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2022-02-04T17:44:01-00:00
_audit_update_record
;
2022-02-14 deposited with the CCDC.	2022-03-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.879(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.630(3)
_cell_length_b                   15.7650(10)
_cell_length_c                   20.4853(17)
_cell_measurement_reflns_used    9771
_cell_measurement_temperature    84.8(6)
_cell_measurement_theta_max      68.084
_cell_measurement_theta_min      3.487
_cell_volume                     6915.2(13)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      84.8(6)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_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    -32.00  55.00   0.50    5.00    --  -21.00  22.00-163.00  174
  2  \w    -96.00  -9.00   0.50    5.00    --  -21.00 -22.00  31.00  174
  3  \w    -27.00  25.00   0.50    5.00    --   47.66 -22.00  31.00  104
  4  \w     36.00 123.00   0.50    5.00    --   47.66  22.00-163.00  174
  5  \w     99.00 177.00   0.50   12.00    --  110.58  22.00-163.00  156
  6  \w    -94.00   2.00   0.50    5.00    --  -21.00 -77.00-180.00  192
  7  \w    -69.00 -13.00   0.50    5.00    --  -21.00 125.00 -60.00  112
  8  \w    -27.00  23.00   0.50    5.00    --   47.66 -19.00 -30.00  100
  9  \w     34.00  95.00   0.50    5.00    --   47.66-125.00  30.00  122
 10  \w     39.00  68.00   0.50   12.00    --  110.58 -61.00 150.00   58
 11  \w     97.00 177.00   0.50   12.00    --  110.58  15.00 -90.00  160
 12  \w     39.00  68.00   0.50   12.00    --  110.58 -61.00  60.00   58
 13  \w     39.00  68.00   0.50   12.00    --  110.58 -61.00 120.00   58
 14  \w     39.00  68.00   0.50   12.00    --  110.58 -61.00  90.00   58
 15  \w     39.00  68.00   0.50   12.00    --  110.58 -61.00-120.00   58
 16  \w     39.00  68.00   0.50   12.00    --  110.58 -61.00 -90.00   58
 17  \w     39.00 102.00   0.50   12.00    --  110.58 -77.00 -90.00  126
 18  \w     98.00 177.00   0.50   12.00    --  110.58  30.00 150.00  158
 19  \w     97.00 177.00   0.50   12.00    --  110.58  15.00-120.00  160
 20  \w     39.00 105.00   0.50   12.00    --  110.58 -94.00-150.00  132
 21  \w     39.00 102.00   0.50   12.00    --  110.58 -77.00-150.00  126
 22  \w     39.00 111.00   0.50   12.00    --  110.58-125.00   0.00  144
 23  \w     39.00  68.00   0.50   12.00    --  110.58 -61.00-180.00   58
 24  \w     39.00 102.00   0.50   12.00    --  110.58 -77.00  90.00  126
 25  \w     39.00  68.00   0.50   12.00    --  110.58 -61.00 -30.00   58
 26  \w     39.00  68.00   0.50   12.00    --  110.58 -61.00  30.00   58
 27  \w     25.00  54.00   0.50    5.00    --   47.66  77.00  30.00   58
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.068806
_diffrn_orient_matrix_UB_12      0.010589
_diffrn_orient_matrix_UB_13      0.004502
_diffrn_orient_matrix_UB_21      -0.0162078
_diffrn_orient_matrix_UB_22      -0.0258501
_diffrn_orient_matrix_UB_23      -0.0762348
_diffrn_orient_matrix_UB_31      -0.0132398
_diffrn_orient_matrix_UB_32      0.0936493
_diffrn_orient_matrix_UB_33      -0.0218774
_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  0.1321
_diffrn_reflns_av_unetI/netI     0.0636
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            38045
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        47.838
_diffrn_reflns_theta_max         47.838
_diffrn_reflns_theta_min         3.481
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.664
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.77749
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
        Empirical absorption correction using spherical harmonics,
        implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark orange'
_exptl_crystal_density_diffrn    1.231
_exptl_crystal_description       plate
_exptl_crystal_F_000             2752
_exptl_crystal_size_max          0.304
_exptl_crystal_size_mid          0.217
_exptl_crystal_size_min          0.122
_refine_diff_density_max         1.153
_refine_diff_density_min         -0.622
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     778
_refine_ls_number_reflns         6426
_refine_ls_number_restraints     515
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.151
_refine_ls_R_factor_gt           0.1316
_refine_ls_shift/su_max          0
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1816P)^2^+38.7967P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3393
_refine_ls_wR_factor_ref         0.358
_reflns_Friedel_coverage         0
_reflns_number_gt                4966
_reflns_number_total             6426
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 13.2282\% 
around [0.35 -0.36 -0.87] (reciprocal) or [0.04 -0.58 -0.81] (direct)
;
_cod_data_source_file            d2cc00979j2.cif
_cod_data_source_block           20EH218_PM683
_cod_database_code               7129965
_oxdiff_exptl_absorpt_empirical_details
;
        Empirical correction (ABSPACK) includes:
        - Absorption correction using spherical harmonics
        - Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.706
_oxdiff_exptl_absorpt_empirical_full_min 0.517
_shelx_shelxl_version_number     2018/3
_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
 C62-C63 = C64-C65
 1.53 with sigma of 0.02
 O9-C62 = O9-C65
 1.44 with sigma of 0.02
 C63-C64
 1.54 with sigma of 0.02
 O6-C50 = O6-C53
 1.44 with sigma of 0.02
 C50-C51 = C52-C53
 1.53 with sigma of 0.02
 C51-C52
 1.54 with sigma of 0.02
 C60-C59
 1.54 with sigma of 0.02
 O8-C61 = O8-C58
 1.44 with sigma of 0.02
 C61-C60 = C59-C58
 1.53 with sigma of 0.02
 O9-C63 = O9-C64 = C62-C64 = C63-C65
 2.38 with sigma of 0.04
 O6-C51 = O6-C52 = C50-C52 = C51-C53
 2.38 with sigma of 0.04
 O8-C60 = O8-C59 = C61-C59 = C60-C58
 2.38 with sigma of 0.04
 C63-C65 \\sim C62-C64
 with sigma of 0.04
 O9-C62 \\sim O9-C65
 with sigma of 0.02
 C62-C63 \\sim C63-C64 \\sim C64-C65
 with sigma of 0.02
 O9-C63 \\sim O9-C64
 with sigma of 0.04
 C51-C53 \\sim C50-C52
 with sigma of 0.04
 O6-C51 \\sim O6-C52
 with sigma of 0.04
 C50-C51 \\sim C51-C52 \\sim C52-C53
 with sigma of 0.02
 O6-C50 \\sim O6-C53
 with sigma of 0.02
 C60-C58 \\sim C61-C59
 with sigma of 0.04
 C61-C60 \\sim C60-C59 \\sim C59-C58
 with sigma of 0.02
 O8-C61 \\sim O8-C58
 with sigma of 0.02
 O8-C60 \\sim O8-C59
 with sigma of 0.04
        3. Rigid bond restraints
 Zn1, C13, C32, C34, C35, C33, C17, C36, C37, C22, F1, C24, C23, O1, N3, O2,
 C18, C20, C16, C15, C14, C19, C21, Si1, N2, N1, C1, C2, C3, C4, C5, C6, C12,
 C11, C10, C9, C7, C8, C27, C67, C31, C30, C29, C28, C25, C26, C66, C69, C70,
 C68
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O5, C46, C49, C48, C47
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C56, C57, C55, C54, O7
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
        4. Uiso/Uaniso restraints and constraints
O9 \\sim C62 \\sim C63 \\sim C64 \\sim C65: within 2A with sigma of 0.04 and
        sigma for terminal atoms of 0.08 within 2A
O6 \\sim C50 \\sim C51 \\sim C52 \\sim C53: within 2A with sigma of 0.04 and
        sigma for terminal atoms of 0.08 within 2A
O8 \\sim C61 \\sim C60 \\sim C59 \\sim C58: within 2A with sigma of 0.04 and
        sigma for terminal atoms of 0.08 within 2A
Uanis(C49) \\sim Ueq, Uanis(O5) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C38)
\\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C44) \\sim Ueq,
Uanis(K2) \\sim Ueq, Uanis(C55) \\sim Ueq: with sigma of 0.01 and sigma for
        terminal atoms of 0.02
Uanis(C5) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C70)
\\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(O7) \\sim Ueq,
Uanis(C57) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(K2) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.02
Uanis(F1) \\sim Ueq, Uanis(C8) \\sim Ueq: with sigma of 0.01 and sigma for
        terminal atoms of 0.01
Uanis(C46) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.02
Uanis(C48) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
        5. Rigid body (RIGU) restrains
 O9, C62, C63, C64, C65
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O6, C50, C51, C52, C53
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O8, C61, C60, C59, C58
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
        6.a Ternary CH refined with riding coordinates:
 C19(H19), C22(H22), C10(H10), C7(H7)
        6.b Secondary CH2 refined with riding coordinates:
 C41(H41A,H41B), C40(H40A,H40B), C42(H42A,H42B), C43(H43A,H43B), C46(H46A,
 H46B), C39(H39A,H39B), C45(H45A,H45B), C44(H44A,H44B), C38(H38A,H38B),
 C47(H47A,H47B), C57(H57A,H57B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B),
  C49(H49A,H49B), C48(H48A,H48B), C62(H62A,H62B), C63(H63A,H63B), C64(H64A,
 H64B), C65(H65A,H65B), C50(H50A,H50B), C51(H51A,H51B), C52(H52A,H52B),
 C53(H53A,H53B), C61(H61A,H61B), C60(H60A,H60B), C59(H59A,H59B), C58(H58B,H58A)
        6.c Me refined with riding coordinates:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C24(H24A,H24B,H24C), C11(H11A,H11B,
 H11C), C9(H9A,H9B,H9C), C12(H12A,H12B,H12C), C23(H23A,H23B,H23C), C8(H8A,H8B,
 H8C)
        6.d Aromatic/amide H refined with riding coordinates:
 C17(H17), C68(H68), C5(H5), C16(H16), C15(H15), C28(H28), C3(H3), C66(H66),
 C36(H36), C4(H4), C70(H70), C26(H26), C67(H67), C30(H30), C35(H35), C31(H31),
 C69(H69), C29(H29), C34(H34)
;
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
_shelx_res_checksum              48718
_shelx_hkl_checksum              36611