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_7129960
_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         'C54 H70 F2 K N3 O5 Si Zn'
_chemical_formula_sum            'C54 H70 F2 K N3 O5 Si Zn'
_chemical_formula_weight         1011.69
_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     dual
_audit_creation_date             2022-03-04T10:52:41-00:00
_audit_update_record
;
2022-03-04 deposited with the CCDC.	2022-03-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.4303(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.68683(6)
_cell_length_b                   14.09772(9)
_cell_length_c                   31.61154(15)
_cell_measurement_reflns_used    36358
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.779
_cell_measurement_theta_min      2.78
_cell_volume                     5206.62(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.54a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.54a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.54a (Rigaku OD, 2020)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_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 0.98
_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    -50.00  29.00   0.50    0.10    --  -18.75  96.00 116.00  158
  2  \w     -7.00  80.00   0.50    0.10    --   47.95 -96.00   6.00  174
  3  \w    106.00 171.00   0.50    0.25    --  107.11  96.00 116.00  130
  4  \w     35.00 106.00   0.50    0.25    --  107.11 -96.00   6.00  142
  5  \w    -66.00 -12.00   0.50    0.10    --  -18.75 125.00 -30.00  108
  6  \w    -66.00 -12.00   0.50    0.10    --  -18.75 125.00   0.00  108
  7  \w     36.00 121.00   0.50    0.10    --   47.95  38.00-150.00  170
  8  \w    -25.00  40.00   0.50    0.10    --   47.95 -38.00  60.00  130
  9  \w    -26.00  23.00   0.50    0.10    --   47.95 -19.00 -30.00   98
 10  \w    -25.00  40.00   0.50    0.10    --   47.95 -38.00 -90.00  130
 11  \w     35.00  68.00   0.50    0.25    --  107.11 -61.00 -90.00   66
 12  \w     35.00  68.00   0.50    0.25    --  107.11 -61.00  90.00   66
 13  \w     35.00  68.00   0.50    0.25    --  107.11 -61.00-120.00   66
 14  \w     35.00  68.00   0.50    0.25    --  107.11 -61.00   0.00   66
 15  \w     95.00 171.00   0.50    0.25    --  107.11  30.00   0.00  152
 16  \w     35.00  68.00   0.50    0.25    --  107.11 -61.00  60.00   66
 17  \w     35.00 102.00   0.50    0.25    --  107.11 -77.00  60.00  134
 18  \w     95.00 171.00   0.50    0.25    --  107.11  45.00  30.00  152
 19  \w     35.00  68.00   0.50    0.25    --  107.11 -61.00-150.00   66
 20  \w     35.00 112.00   0.50    0.25    --  107.11-125.00 120.00  154
 21  \w     95.00 171.00   0.50    0.25    --  107.11  30.00 120.00  152
 22  \w     35.00  68.00   0.50    0.25    --  107.11 -61.00  30.00   66
 23  \w     35.00  68.00   0.50    0.25    --  107.11 -61.00 150.00   66
 24  \w     35.00  68.00   0.50    0.25    --  107.11 -61.00 120.00   66
 25  \w     35.00 102.00   0.50    0.25    --  107.11 -77.00 -60.00  134
 26  \w     35.00  68.00   0.50    0.25    --  107.11 -61.00-180.00   66
 27  \w     26.00 120.00   0.50    0.10    --   47.95  77.00  60.00  188
 28  \w     33.00  68.00   0.50    0.10    --   47.95  57.00-120.00   70
 29  \w     26.00 120.00   0.50    0.10    --   47.95  77.00 -60.00  188
;
_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      0.0407281
_diffrn_orient_matrix_UB_12      -0.0488595
_diffrn_orient_matrix_UB_13      -0.040549
_diffrn_orient_matrix_UB_21      -0.0677954
_diffrn_orient_matrix_UB_22      -0.089694
_diffrn_orient_matrix_UB_23      0.0114622
_diffrn_orient_matrix_UB_31      -0.1054938
_diffrn_orient_matrix_UB_32      0.038797
_diffrn_orient_matrix_UB_33      -0.0245394
_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  0.0366
_diffrn_reflns_av_unetI/netI     0.0529
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.98
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            55788
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.98
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.117
_diffrn_reflns_theta_min         2.797
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.043
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.47425
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.41.54a (Rigaku Oxford Diffraction, 2020)
        Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.291
_exptl_crystal_description       block
_exptl_crystal_F_000             2144
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.618
_refine_diff_density_min         -0.501
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     622
_refine_ls_number_reflns         10802
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0412
_refine_ls_R_factor_gt           0.0358
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0371P)^2^+4.3848P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0873
_refine_ls_wR_factor_ref         0.0908
_reflns_Friedel_coverage         0
_reflns_number_gt                9700
_reflns_number_total             10802
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc00979j2.cif
_cod_data_source_block           20EH047_PM537
_cod_database_code               7129960
_shelx_estimated_absorpt_t_min   0.723
_shelx_estimated_absorpt_t_max   0.837
_oxdiff_exptl_absorpt_empirical_details
;
        Empirical correction (ABSPACK) includes:
        - Absorption correction using spherical harmonics
        - Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.873
_oxdiff_exptl_absorpt_empirical_full_min 0.783
_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. Others
 Sof(C55B)=Sof(H55C)=Sof(H55D)=1-FVAR(1)
 Sof(C55A)=Sof(H55A)=Sof(H55B)=FVAR(1)
 Fixed Sof: H54A(0.5) H54B(0.5) H54C(0.5) H54D(0.5)
        3.a Ternary CH refined with riding coordinates:
 C38(H38), C20(H20), C17(H17), C35(H35)
        3.b Secondary CH2 refined with riding coordinates:
 C47(H47A,H47B), C42(H42A,H42B), C49(H49A,H49B), C48(H48A,H48B), C50(H50A,
 H50B), C43(H43A,H43B), C53(H53A,H53B), C54(H54A,H54B), C54(H54C,H54D),
 C55A(H55A,H55B), C52(H52A,H52B), C45(H45A,H45B), C44(H44A,H44B), C55B(H55C,
 H55D)
        3.c Aromatic/amide H refined with riding coordinates:
 C33(H33), C24(H24), C32(H32), C31(H31), C28(H28), C5(H5), C27(H27), C57(H57),
 C6(H6), C61(H61), C13(H13), C25(H25), C26(H26), C15(H15), C14(H14), C60(H60),
 C58(H58), C59(H59)
        3.d Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C22(H22A,H22B,H22C), C37(H37A,H37B,
 H37C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C36(H36A,
 H36B,H36C)
;
_shelx_res_checksum              50297
_shelx_hkl_checksum              60712