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_7129967
_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 H44 F5 N2 Si Zn, 2.122(C10.696 H21.393 K0.5 O2.674), 1.326(C4 H8 O)'
_chemical_formula_sum            'C70 H100 F5 K N2 O7 Si Zn'
_chemical_formula_weight         1309.07
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      15
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-10-27T19:50:40-00:00
_audit_update_record
;
2022-02-14 deposited with the CCDC.	2022-03-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.1052(7)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   35.1874(3)
_cell_length_b                   15.60249(10)
_cell_length_c                   25.53322(18)
_cell_measurement_reflns_used    56394
_cell_measurement_temperature    100.0(5)
_cell_measurement_theta_max      77.579
_cell_measurement_theta_min      3.098
_cell_volume                     13841.39(18)
_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    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(5)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1
_diffrn_measured_fraction_theta_max 0.998
_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    -39.00  50.00   0.50    0.70    --  -23.00  61.00 157.00  178
  2  \w     31.00 120.00   0.50    0.70    --   47.70  61.00 157.00  178
  3  \w    -24.00  64.00   0.50    0.70    --   47.70 -61.00  19.00  176
  4  \w     42.00  68.00   0.50    4.00    --  113.25 -61.00  19.00   52
  5  \w     97.00 177.00   0.50    4.00    --  113.25  61.00 157.00  160
  6  \w    -95.00  -6.00   0.50    0.70    --  -23.00 -61.00  19.00  178
  7  \w    -70.00 -12.00   0.50    0.70    --  -23.00 125.00-150.00  116
  8  \w    -94.00  -8.00   0.50    0.70    --  -23.00 -57.00-150.00  172
  9  \w     -1.00  81.00   0.50    0.70    --   47.70 -99.00 -30.00  164
 10  \w     -1.00  81.00   0.50    0.70    --   47.70 -99.00 -90.00  164
 11  \w    -27.00  23.00   0.50    0.70    --   47.70 -19.00 -30.00  100
 12  \w    -27.00  23.00   0.50    0.70    --   47.70 -19.00  60.00  100
 13  \w    -27.00  23.00   0.50    0.70    --   47.70 -19.00  30.00  100
 14  \w     97.00 177.00   0.50    4.00    --  113.25  61.00 -60.00  160
 15  \w     42.00 106.00   0.50    4.00    --  113.25 -94.00 120.00  128
 16  \w     42.00 106.00   0.50    4.00    --  113.25 -94.00   0.00  128
 17  \w     42.00 108.00   0.50    4.00    --  113.25-106.00 -56.01  132
 18  \w     42.00  68.00   0.50    4.00    --  113.25 -61.00  60.00   52
 19  \w     42.00 106.00   0.50    4.00    --  113.25 -94.00-180.00  128
 20  \w     42.00 106.00   0.50    4.00    --  113.25 -94.00  30.00  128
 21  \w     42.00 106.00   0.50    4.00    --  113.25 -94.00-120.00  128
 22  \w     42.00 107.00   0.50    4.00    --  113.25-104.00  -7.27  130
 23  \w     97.00 177.00   0.50    4.00    --  113.25  61.00 120.00  160
 24  \w     42.00 106.00   0.50    4.00    --  113.25 -94.00  90.00  128
 25  \w    100.00 177.00   0.50    4.00    --  113.25  47.00  53.66  154
 26  \w     42.00  68.00   0.50    4.00    --  113.25 -61.00-120.00   52
 27  \w     42.00 106.00   0.50    4.00    --  113.25 -94.00 150.00  128
 28  \w    101.00 177.00   0.50    4.00    --  113.25  79.00  70.23  152
 29  \w     42.00 102.00   0.50    4.00    --  113.25 -77.00-180.00  120
 30  \w     42.00  68.00   0.50    4.00    --  113.25 -61.00  30.00   52
 31  \w     42.00  68.00   0.50    4.00    --  113.25 -61.00 -68.64   52
 32  \w    101.00 177.00   0.50    4.00    --  113.25  30.00   0.00  152
 33  \w     97.00 177.00   0.50    4.00    --  113.25  61.00-150.00  160
 34  \w     93.00 177.00   0.50    4.00    --  113.25  71.00 133.04  168
 35  \w    101.00 177.00   0.50    4.00    --  113.25  45.00  90.00  152
 36  \w     42.00 106.00   0.50    4.00    --  113.25 -94.00  60.00  128
 37  \w     42.00  68.00   0.50    4.00    --  113.25 -61.00  90.00   52
 38  \w    100.00 177.00   0.50    4.00    --  113.25  15.00 -60.00  154
 39  \w     42.00 102.00   0.50    4.00    --  113.25 -77.00-120.00  120
 40  \w    101.00 177.00   0.50    4.00    --  113.25  45.00 -30.00  152
 41  \w     42.00  68.00   0.50    4.00    --  113.25 -61.00   0.00   52
 42  \w     42.00  68.00   0.50    4.00    --  113.25 -61.00 150.00   52
 43  \w     42.00 102.00   0.50    4.00    --  113.25 -77.00 -90.00  120
 44  \w     42.00 107.00   0.50    4.00    --  113.25-103.00-102.23  130
 45  \w     42.00 109.00   0.50    4.00    --  113.25-113.00  51.37  134
 46  \w     42.00  68.00   0.50    4.00    --  113.25 -61.00 -90.00   52
 47  \w     42.00 108.00   0.50    4.00    --  113.25-112.00-122.73  132
 48  \w    101.00 177.00   0.50    4.00    --  113.25  45.00  60.00  152
 49  \w     98.00 177.00   0.50    4.00    --  113.25  59.00  29.34  158
 50  \w     25.00 101.00   0.50    0.70    --   47.70  77.00 -60.00  152
 51  \w     25.00 120.00   0.50    0.70    --   47.70  77.00  60.00  190
;
_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      0.0008588
_diffrn_orient_matrix_UB_12      -0.0979049
_diffrn_orient_matrix_UB_13      0.007954
_diffrn_orient_matrix_UB_21      0.0319294
_diffrn_orient_matrix_UB_22      0.0101833
_diffrn_orient_matrix_UB_23      0.0483565
_diffrn_orient_matrix_UB_31      -0.0307698
_diffrn_orient_matrix_UB_32      0.0079148
_diffrn_orient_matrix_UB_33      0.0364776
_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  0.0487
_diffrn_reflns_av_unetI/netI     0.0524
_diffrn_reflns_Laue_measured_fraction_full 1
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -44
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            140186
_diffrn_reflns_point_group_measured_fraction_full 1
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.02
_diffrn_reflns_theta_min         3.105
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.733
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.78838
_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            colourless
_exptl_crystal_density_diffrn    1.256
_exptl_crystal_description       block
_exptl_crystal_F_000             5584
_exptl_crystal_size_max          0.263
_exptl_crystal_size_mid          0.215
_exptl_crystal_size_min          0.161
_refine_diff_density_max         0.713
_refine_diff_density_min         -0.661
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     976
_refine_ls_number_reflns         14236
_refine_ls_number_restraints     233
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0793
_refine_ls_R_factor_gt           0.0727
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1064P)^2^+31.2698P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1995
_refine_ls_wR_factor_ref         0.2065
_reflns_Friedel_coverage         0
_reflns_number_gt                12538
_reflns_number_total             14236
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc00979j2.cif
_cod_data_source_block           21EH199_PM542
_cod_original_cell_volume        13841.39(17)
_cod_database_code               7129967
_shelx_estimated_absorpt_t_min   0.659
_shelx_estimated_absorpt_t_max   0.768
_oxdiff_exptl_absorpt_empirical_details
;
        Empirical correction (ABSPACK) includes:
        - Absorption correction using spherical harmonics
        - Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.665
_oxdiff_exptl_absorpt_empirical_full_min 0.589
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
        2. Restrained distances
 C65-C64
 1.54 with sigma of 0.02
 C66-C65 = C64-C63
 1.53 with sigma of 0.02
 O6-C66 = O6-C63
 1.44 with sigma of 0.02
 O6-C65 = O6-C64 = C66-C64 = C65-C63
 2.38 with sigma of 0.04
 O6-C65 \\sim O6-C64
 with sigma of 0.04
 C66-C65 \\sim C65-C64 \\sim C64-C63
 with sigma of 0.02
 C65-C63 \\sim C66-C64
 with sigma of 0.04
 O6-C66 \\sim O6-C63
 with sigma of 0.02
        3. Rigid bond restraints
 C53, O3, C51, C52, C54
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 O2, C50, C49, C48, C47
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
        4. Uiso/Uaniso restraints and constraints
O6 \\sim C66 \\sim C65 \\sim C64 \\sim C63: within 2A with sigma of 0.04 and
        sigma for terminal atoms of 0.08 within 2A
Uanis(C70A) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C67) \\sim Ueq: with sigma
        of 0.015 and sigma for terminal atoms of 0.02
Uanis(O3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C57A) \\sim Ueq, Uanis(C58A) \\sim Ueq: with sigma of 0.02 and sigma for
        terminal atoms of 0.02
Uanis(C52) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C70) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C77) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C48) \\sim Ueq: with sigma of
        0.02 and sigma for terminal atoms of 0.02
Uanis(C74A) \\sim Ueq, Uanis(C71A) \\sim Ueq, Uanis(O8A) \\sim Ueq: with sigma
        of 0.02 and sigma for terminal atoms of 0.02
Uanis(F5A) \\sim Ueq, Uanis(F4A) \\sim Ueq, Uanis(C63) \\sim Ueq: with sigma of
        0.01 and sigma for terminal atoms of 0.02
Uanis(C51) \\sim Ueq, Uanis(C54) \\sim Ueq: with sigma of 0.01 and sigma for
        terminal atoms of 0.02
Uanis(O9) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C74A) \\sim Ueq, Uanis(C15)
\\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C75) \\sim Ueq:
        with sigma of 0.01 and sigma for terminal atoms of 0.02
        5. Rigid body (RIGU) restrains
 O6, C66, C65, C64, C63
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
        6. Others
 Sof(H69C)=Sof(H69D)=Sof(C70A)=Sof(H70C)=Sof(H70D)=1-FVAR(1)
 Sof(H69A)=Sof(H69B)=Sof(C70)=Sof(H70A)=Sof(H70B)=FVAR(1)
 Sof(H56C)=Sof(H56D)=Sof(C55A)=Sof(H55C)=Sof(H55D)=Sof(C58A)=Sof(H58C)=
 Sof(H58D)=Sof(C57A)=Sof(H57C)=Sof(H57D)=1-FVAR(2)
 Sof(H56A)=Sof(H56B)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(C58)=Sof(H58A)=Sof(H58B)=
 Sof(C55)=Sof(H55A)=Sof(H55B)=FVAR(2)
 Sof(H73C)=Sof(H73D)=Sof(O8A)=Sof(C72A)=Sof(H72C)=Sof(H72D)=Sof(C71A)=
 Sof(H71C)=Sof(H71D)=Sof(C74A)=Sof(H74C)=Sof(H74D)=1-FVAR(3)
 Sof(O8)=Sof(H73A)=Sof(H73B)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(C72)=Sof(H72A)=
 Sof(H72B)=Sof(C71)=Sof(H71A)=Sof(H71B)=FVAR(3)
 Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(O3)=Sof(C51)=Sof(H51B)=Sof(H51A)=Sof(C53)=
 Sof(H53A)=Sof(H53B)=Sof(C54)=Sof(H54A)=Sof(H54B)=1-FVAR(4)
 Sof(O2)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(C49)=
 Sof(H49A)=Sof(H49B)=Sof(C48)=Sof(H48A)=Sof(H48B)=FVAR(4)
 Sof(Zn1A)=Sof(F5A)=Sof(F4A)=1-FVAR(5)
 Sof(Zn1)=Sof(F5)=Sof(F4)=FVAR(5)
 Fixed Sof: O5(0.5) C59(0.5) H59A(0.5) H59B(0.5) C60(0.5) H60A(0.5) H60B(0.5)
 C62(0.5) H62A(0.5) H62B(0.5) C61(0.5) H61A(0.5) H61B(0.5) O6(0.5) C66(0.5)
 H66A(0.5) H66B(0.5) C65(0.5) H65A(0.5) H65B(0.5) C64(0.5) H64A(0.5) H64B(0.5)
 C63(0.5) H63A(0.5) H63B(0.5)
 Fixed U11: C70(0.264801) C70A(0.072908)
 Fixed U12: C70(0.05623) C70A(0.022047)
 Fixed U13: C70(-0.082696) C70A(-0.003495)
 Fixed U22: C70(0.08134) C70A(0.09477)
 Fixed U23: C70(-0.00418) C70A(-0.01238)
 Fixed U33: C70(0.13671) C70A(0.05789)
        7.a Ternary CH refined with riding coordinates:
 C37(H37), C40(H40), C25(H25), C28(H28)
        7.b Secondary CH2 refined with riding coordinates:
 C46(H46A,H46B), C45(H45A,H45B), C56(H56A,H56B), C56(H56C,H56D), C57(H57A,
 H57B), C68(H68A,H68B), C43(H43A,H43B), C58(H58A,H58B), C75(H75A,H75B),
 C50(H50A,H50B), C47(H47A,H47B), C73(H73A,H73B), C73(H73C,H73D), C69(H69A,H69B),
  C69(H69C,H69D), C74(H74A,H74B), C44(H44A,H44B), C67(H67A,H67B), C78(H78A,
 H78B), C72(H72A,H72B), C55(H55A,H55B), C49(H49A,H49B), C71(H71A,H71B),
 C76(H76A,H76B), C59(H59A,H59B), C60(H60A,H60B), C70(H70A,H70B), C77(H77A,H77B),
  C70A(H70C,H70D), C48(H48A,H48B), C55A(H55C,H55D), C72A(H72C,H72D), C71A(H71C,
 H71D), C74A(H74C,H74D), C52(H52A,H52B), C51(H51B,H51A), C53(H53A,H53B),
 C54(H54A,H54B), C62(H62A,H62B), C61(H61A,H61B), C66(H66A,H66B), C65(H65A,H65B),
  C64(H64A,H64B), C63(H63A,H63B), C58A(H58C,H58D), C57A(H57C,H57D)
        7.c Aromatic/amide H refined with riding coordinates:
 C35(H35), C33(H33), C34(H34), C8(H8), C18(H18), C9(H9), C21(H21), C12(H12),
 C17(H17), C22(H22), C23(H23), C10(H10), C11(H11), C14(H14), C16(H16), C15(H15)
        7.d Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C38(H38A,H38B,H38C), C41(H41A,H41B,H41C), C42(H42A,H42B,
 H42C), C27(H27A,H27B,H27C), C30(H30A,H30B,H30C), C29(H29A,H29B,H29C), C26(H26A,
 H26B,H26C)
;
_shelx_res_checksum              92166
_shelx_hkl_checksum              42875