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_7129959
_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         'C52 H52 F10 K N2 O Si Zn'
_chemical_formula_sum            'C52 H52 F10 K N2 O Si Zn'
_chemical_formula_weight         1043.51
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_cell_setting           triclinic
_symmetry_Int_Tables_number      2
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-03-03T14:22:55-00:00
_audit_update_record
;
2022-03-04 deposited with the CCDC.	2022-03-08 downloaded from the CCDC.
;
_cell_angle_alpha                86.8366(16)
_cell_angle_beta                 86.8944(13)
_cell_angle_gamma                72.2944(17)
_cell_formula_units_Z            2
_cell_length_a                   10.92365(17)
_cell_length_b                   15.3180(4)
_cell_length_c                   15.4312(2)
_cell_measurement_reflns_used    20668
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      76.442
_cell_measurement_theta_min      2.86
_cell_volume                     2454.12(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_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      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1
_diffrn_measured_fraction_theta_max 0.978
_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    -31.00  55.00   0.50    0.80    --  -18.75  38.00  90.00  172
  2  \w     26.00 121.00   0.50    0.80    --   48.03  77.00 120.00  190
  3  \w     85.00 174.00   0.50    3.10    --  107.16  77.00 120.00  178
  4  \w     95.00 174.00   0.50    3.10    --  107.16  19.00  30.00  158
  5  \w     95.00 174.00   0.50    3.10    --  107.16  19.00 -60.00  158
  6  \w     98.00 174.00   0.50    3.10    --  107.16  87.00-148.00  152
  7  \w     95.00 174.00   0.50    3.10    --  107.16  19.00 -90.00  158
  8  \w     95.00 174.00   0.50    3.10    --  107.16  19.00-180.00  158
  9  \w     94.00 174.00   0.50    3.10    --  107.16  38.00-180.00  160
 10  \w     85.00 174.00   0.50    3.10    --  107.16  77.00   0.00  178
 11  \w     85.00 174.00   0.50    3.10    --  107.16  77.00  60.00  178
 12  \w     85.00 174.00   0.50    3.10    --  107.16  77.00  90.00  178
 13  \w     35.00 135.00   0.50    3.10    --  107.16 -87.00  94.00  200
 14  \w     32.00  96.00   0.50    0.80    --   48.03-125.00   0.00  128
 15  \w     35.00 102.00   0.50    3.10    --  107.16 -77.00 -30.00  134
 16  \w     35.00 110.00   0.50    3.10    --  107.16 -99.00  60.00  150
 17  \w     35.00 102.00   0.50    3.10    --  107.16 -77.00 -60.00  134
 18  \w     35.00 117.00   0.50    3.10    --  107.16-125.00-180.00  164
 19  \w     35.00  62.00   0.50    3.10    --  107.16 -57.00-180.00   54
 20  \w     35.00 117.00   0.50    3.10    --  107.16-125.00 -90.00  164
 21  \w     35.00 110.00   0.50    3.10    --  107.16 -99.00   0.00  150
 22  \w     35.00  62.00   0.50    3.10    --  107.16 -57.00 150.00   54
 23  \w     35.00  62.00   0.50    3.10    --  107.16 -57.00  30.00   54
 24  \w     35.00  62.00   0.50    3.10    --  107.16 -57.00   0.00   54
 25  \w     35.00 110.00   0.50    3.10    --  107.16 -99.00 -60.00  150
 26  \w     35.00 110.00   0.50    3.10    --  107.16 -99.00 -90.00  150
 27  \w     35.00 117.00   0.50    3.10    --  107.16-125.00-120.00  164
 28  \w    -23.00  76.00   0.50    0.80    --   48.03 -87.00  94.00  198
 29  \w     26.00 121.00   0.50    0.80    --   48.03  77.00 -30.00  190
 30  \w     26.00 121.00   0.50    0.80    --   48.03  77.00 -60.00  190
 31  \w     26.00 121.00   0.50    0.80    --   48.03  77.00-150.00  190
 32  \w     26.00 102.00   0.50    0.80    --   48.03  77.00-120.00  152
 33  \w     26.00 121.00   0.50    0.80    --   48.03  77.00  30.00  190
 34  \w    -26.00  23.00   0.50    0.80    --   48.03 -19.00-180.00   98
 35  \w    -26.00  23.00   0.50    0.80    --   48.03 -19.00 -60.00   98
 36  \w    -26.00  23.00   0.50    0.80    --   48.03 -19.00  30.00   98
 37  \w    -26.00  23.00   0.50    0.80    --   48.03 -19.00  90.00   98
 38  \w    -66.00  -9.00   0.50    0.80    --  -18.75 125.00 -90.00  114
 39  \w    -46.00  46.00   0.50    0.80    --  -18.75  87.00-148.00  184
 40  \w    -91.00  -5.00   0.50    0.80    --  -18.75 -38.00 120.00  172
;
_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      0.0409253
_diffrn_orient_matrix_UB_12      0.0387452
_diffrn_orient_matrix_UB_13      0.0798798
_diffrn_orient_matrix_UB_21      -0.0505792
_diffrn_orient_matrix_UB_22      0.0977604
_diffrn_orient_matrix_UB_23      -0.0407331
_diffrn_orient_matrix_UB_31      -0.1331066
_diffrn_orient_matrix_UB_32      0.0102868
_diffrn_orient_matrix_UB_33      0.0444169
_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  0.0666
_diffrn_reflns_av_unetI/netI     0.0554
_diffrn_reflns_Laue_measured_fraction_full 1
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            47554
_diffrn_reflns_point_group_measured_fraction_full 1
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.371
_diffrn_reflns_theta_min         2.87
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.363
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.58024
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.40.45a (Rigaku Oxford Diffraction, 2019)
        Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_density_diffrn    1.412
_exptl_crystal_description       plate
_exptl_crystal_F_000             1078
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.138
_refine_diff_density_min         -1.018
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     597
_refine_ls_number_reflns         10199
_refine_ls_number_restraints     77
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0716
_refine_ls_R_factor_gt           0.0659
_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^)+(0.1274P)^2^+1.6530P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.195
_refine_ls_wR_factor_ref         0.2012
_reflns_Friedel_coverage         0
_reflns_number_gt                8910
_reflns_number_total             10199
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc00979j2.cif
_cod_data_source_block           19EH020_PM473
_cod_database_code               7129959
_shelx_estimated_absorpt_t_min   0.718
_shelx_estimated_absorpt_t_max   0.891
_oxdiff_exptl_absorpt_empirical_details
;
        Empirical correction (ABSPACK) includes:
        - Absorption correction using spherical harmonics
        - Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.253
_oxdiff_exptl_absorpt_empirical_full_min 0.531
_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
 C50-C45 \\sim C46-C45 \\sim C47-C46 \\sim C48-C47 \\sim C49-C48 \\sim C50-C49
        \\sim C40-C39 \\sim C44-C39
 \\sim C44-C43 \\sim C43-C42 \\sim C42-C41 \\sim C41-C40
 with sigma of 0.002
        3. Rigid bond restraints
 C46, C47, C48, C49
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
        4. Uiso/Uaniso restraints and constraints
Uanis(F7) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.005
        Uanis(C54) = Uanis(C55) = Uanis(C53) = Uanis(C52) = Uanis(O51)
        5.a Ternary CH refined with riding coordinates:
 C24(H24), C8(H8), C11(H11), C21(H21)
        5.b Secondary CH2 refined with riding coordinates:
 C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B)
        5.c Aromatic/amide H refined with riding coordinates:
 C34(H34), C32(H32), C28(H28), C38(H38), C4(H4), C6(H6), C35(H35), C19(H19),
 C5(H5), C31(H31), C36(H36), C29(H29), C30(H30), C17(H17), C18(H18), C37(H37)
        5.d Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C25(H25A,H25B,H25C), C9(H9A,H9B,H9C), C13(H13A,H13B,
 H13C), C12(H12A,H12B,H12C), C10(H10A,H10B,H10C), C23(H23A,H23B,H23C), C22(H22A,
 H22B,H22C)
;
_shelx_res_checksum              26153
_shelx_hkl_checksum              22742