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_7129968
_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         'C102 H136 F4 K2 N4 O6 Si2 Zn2, 2(C4 H8 O)'
_chemical_formula_sum            'C110 H152 F4 K2 N4 O8 Si2 Zn2'
_chemical_formula_weight         1999.47
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-12-06T20:57:19-00:00
_audit_update_record
;
2022-02-14 deposited with the CCDC.	2022-03-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.0495(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.14746(7)
_cell_length_b                   29.80377(15)
_cell_length_c                   15.17589(8)
_cell_measurement_reflns_used    67574
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      79.598
_cell_measurement_theta_min      2.965
_cell_volume                     5305.84(5)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_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 1
_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    -63.00  -2.00   0.50    0.80    --  -23.00 111.00  -5.00  122
  2  \w     24.00  88.00   0.50    0.80    --   47.95-111.00 -99.00  128
  3  \w     42.00 108.00   0.50    3.00    --  113.25-111.00 -99.00  132
  4  \w    -95.00   0.00   0.50    0.80    --  -23.00 -77.00  60.00  190
  5  \w    -36.00  50.00   0.50    0.80    --  -23.00  38.00 120.00  172
  6  \w    -39.00  50.00   0.50    0.80    --  -23.00  61.00-180.00  178
  7  \w    -26.00  23.00   0.50    0.80    --   47.95 -19.00-180.00   98
  8  \w     -1.00  81.00   0.50    0.80    --   47.95 -99.00 -30.00  164
  9  \w     -1.00  81.00   0.50    0.80    --   47.95 -99.00-150.00  164
 10  \w    -25.00  40.00   0.50    0.80    --   47.95 -38.00-120.00  130
 11  \w    -24.00  71.00   0.50    0.80    --   47.95 -77.00 -60.00  190
 12  \w     42.00  68.00   0.50    3.00    --  113.25 -61.00-120.00   52
 13  \w     42.00  68.00   0.50    3.00    --  113.25 -61.00 -90.00   52
 14  \w     97.00 177.00   0.50    3.00    --  113.25  61.00-180.00  160
 15  \w     42.00  68.00   0.50    3.00    --  113.25 -61.00-180.00   52
 16  \w     42.00 106.00   0.50    3.00    --  113.25 -94.00  30.00  128
 17  \w    101.00 177.00   0.50    3.00    --  113.25  45.00-150.00  152
 18  \w     42.00 106.00   0.50    3.00    --  113.25 -94.00  90.00  128
 19  \w    101.00 177.00   0.50    3.00    --  113.25  45.00 -60.00  152
 20  \w     42.00 106.00   0.50    3.00    --  113.25 -94.00 -90.00  128
 21  \w    101.00 177.00   0.50    3.00    --  113.25  45.00  30.00  152
 22  \w     42.00 106.00   0.50    3.00    --  113.25 -94.00   0.00  128
 23  \w    101.00 177.00   0.50    3.00    --  113.25  30.00 -90.00  152
 24  \w     42.00 106.00   0.50    3.00    --  113.25 -94.00-180.00  128
 25  \w     42.00 108.00   0.50    3.00    --  113.25-108.00  88.69  132
 26  \w     95.00 177.00   0.50    3.00    --  113.25  67.00 100.80  164
 27  \w     42.00  68.00   0.50    3.00    --  113.25 -61.00 -60.00   52
 28  \w     42.00  68.00   0.50    3.00    --  113.25 -61.00 -30.00   52
 29  \w     42.00 106.00   0.50    3.00    --  113.25 -94.00 150.00  128
 30  \w     42.00 109.00   0.50    3.00    --  113.25-115.00  23.26  134
 31  \w     42.00  68.00   0.50    3.00    --  113.25 -61.00 150.00   52
 32  \w     91.00 177.00   0.50    3.00    --  113.25  77.00 122.08  172
 33  \w     42.00 106.00   0.50    3.00    --  113.25 -94.00-120.00  128
 34  \w     95.00 177.00   0.50    3.00    --  113.25  67.00 -30.97  164
 35  \w     97.00 177.00   0.50    3.00    --  113.25  61.00  90.00  160
 36  \w    101.00 177.00   0.50    3.00    --  113.25  45.00  60.00  152
 37  \w     42.00 106.00   0.50    3.00    --  113.25 -94.00 -60.00  128
 38  \w     42.00 106.00   0.50    3.00    --  113.25 -94.00-150.00  128
 39  \w     42.00  68.00   0.50    3.00    --  113.25 -61.00-150.00   52
 40  \w     42.00 102.00   0.50    3.00    --  113.25 -77.00 120.00  120
 41  \w     42.00 106.00   0.50    3.00    --  113.25 -94.00 -30.00  128
 42  \w     42.00 106.00   0.50    3.00    --  113.25 -94.00 120.00  128
 43  \w     93.00 177.00   0.50    3.00    --  113.25  72.00  45.74  168
 44  \w     42.00  68.00   0.50    3.00    --  113.25 -61.00   0.00   52
 45  \w     42.00 106.00   0.50    3.00    --  113.25 -94.00  60.00  128
 46  \w     91.00 177.00   0.50    3.00    --  113.25  77.00-120.00  172
 47  \w     25.00 120.00   0.50    0.80    --   47.95  77.00 -90.00  190
 48  \w     25.00 120.00   0.50    0.80    --   47.95  77.00-180.00  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      -0.0965501
_diffrn_orient_matrix_UB_12      0.0309491
_diffrn_orient_matrix_UB_13      -0.0523845
_diffrn_orient_matrix_UB_21      -0.0560965
_diffrn_orient_matrix_UB_22      -0.0399722
_diffrn_orient_matrix_UB_23      -0.0592092
_diffrn_orient_matrix_UB_31      -0.0691708
_diffrn_orient_matrix_UB_32      -0.0107294
_diffrn_orient_matrix_UB_33      0.069289
_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  0.0412
_diffrn_reflns_av_unetI/netI     0.0452
_diffrn_reflns_Laue_measured_fraction_full 1
_diffrn_reflns_Laue_measured_fraction_max 1
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            100664
_diffrn_reflns_point_group_measured_fraction_full 1
_diffrn_reflns_point_group_measured_fraction_max 1
_diffrn_reflns_theta_full        67.573
_diffrn_reflns_theta_max         67.573
_diffrn_reflns_theta_min         2.965
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.976
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.59934
_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    1.252
_exptl_crystal_description       block
_exptl_crystal_F_000             2132
_exptl_crystal_size_max          0.254
_exptl_crystal_size_mid          0.088
_exptl_crystal_size_min          0.068
_refine_diff_density_max         0.516
_refine_diff_density_min         -0.488
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.03
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     818
_refine_ls_number_reflns         9576
_refine_ls_number_restraints     99
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0372
_refine_ls_R_factor_gt           0.0359
_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^)+(0.0505P)^2^+3.7426P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0965
_refine_ls_wR_factor_ref         0.0975
_reflns_Friedel_coverage         0
_reflns_number_gt                9124
_reflns_number_total             9576
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc00979j2.cif
_cod_data_source_block           21EH216_PM955
_cod_database_code               7129968
_shelx_estimated_absorpt_t_min   0.634
_shelx_estimated_absorpt_t_max   0.877
_oxdiff_exptl_absorpt_empirical_details
;
        Empirical correction (ABSPACK) includes:
        - Absorption correction using spherical harmonics
        - Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.583
_oxdiff_exptl_absorpt_empirical_full_min 0.702
_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
 C55-C54 \\sim C52-C53 \\sim C53A-C52A \\sim C55A-C54A
 with sigma of 0.002
 O4-C55 \\sim O4-C52 \\sim O4A-C55A \\sim O4A-C52A
 with sigma of 0.002
 C54-C53 \\sim C53A-C54A
 with sigma of 0.002
        3. Rigid bond restraints
 C55A, C52A, H52C, H52D, C53A, O4A, H53C, H53D, C54A, H54C, H54D, H55C, H55D
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C53, O4, C52, C55, H52A, H52B, C54, H55A, H55B, H53A, H53B, H54A, H54B
 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(C55A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C44A) \\sim Ueq, Uanis(C46A) \\sim Ueq: with sigma of 0.02 and sigma for
        terminal atoms of 0.02
Uanis(C43A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C49) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C53A) \\sim Ueq, Uanis(C52A) \\sim Ueq: with sigma of 0.01 and sigma for
        terminal atoms of 0.02
Uanis(C10A) \\sim Ueq, Uanis(C15A) \\sim Ueq, Uanis(C11A) \\sim Ueq,
Uanis(C13A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
        5. Others
 Sof(H25A)=Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C27A)=Sof(H27D)=
 Sof(H27E)=Sof(H27F)=1-FVAR(1)
 Sof(H25)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C26)=Sof(H26A)=Sof(H26B)=
 Sof(H26C)=FVAR(1)
 Sof(O1A)=Sof(C43A)=Sof(H43C)=Sof(H43D)=Sof(C42A)=Sof(H42C)=Sof(H42D)=
 Sof(C41A)=Sof(H41C)=Sof(H41D)=Sof(C40A)=Sof(H40C)=Sof(H40D)=1-FVAR(2)
 Sof(O1)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(C40)=
 Sof(H40B)=Sof(H40A)=Sof(C43)=Sof(H43A)=Sof(H43B)=FVAR(2)
 Sof(H47C)=Sof(H47D)=Sof(C44A)=Sof(H44C)=Sof(H44D)=Sof(O2A)=Sof(C46A)=
 Sof(H46C)=Sof(H46D)=Sof(C45A)=Sof(H45C)=Sof(H45D)=1-FVAR(3)
 Sof(O2)=Sof(H47A)=Sof(H47B)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C45)=Sof(H45A)=
 Sof(H45B)=Sof(C46)=Sof(H46A)=Sof(H46B)=FVAR(3)
 Sof(H49C)=Sof(H49D)=Sof(C48A)=Sof(H48C)=Sof(H48D)=1-FVAR(4)
 Sof(H49A)=Sof(H49B)=Sof(C48)=Sof(H48A)=Sof(H48B)=FVAR(4)
 Sof(C52A)=Sof(H52C)=Sof(H52D)=Sof(C53A)=Sof(H53C)=Sof(H53D)=Sof(C54A)=
 Sof(H54C)=Sof(H54D)=Sof(C55A)=Sof(H55C)=Sof(H55D)=Sof(O4A)=1-FVAR(5)
 Sof(O4)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(C52)=
 Sof(H52A)=Sof(H52B)=Sof(C55)=Sof(H55A)=Sof(H55B)=FVAR(5)
 Sof(C12A)=Sof(H12A)=Sof(C11A)=Sof(H11A)=Sof(C13A)=Sof(H13A)=Sof(C14A)=
 Sof(H14A)=Sof(C15A)=Sof(H15A)=Sof(C10A)=1-FVAR(6)
 Sof(C10)=Sof(C15)=Sof(H15)=Sof(C11)=Sof(H11)=Sof(C14)=Sof(H14)=Sof(C13)=
 Sof(H13)=Sof(C12)=Sof(H12)=FVAR(6)
        6.a Ternary CH refined with riding coordinates:
 C25(H25), C25(H25A), C22(H22), C34(H34), C37(H37)
        6.b Secondary CH2 refined with riding coordinates:
 C47(H47A,H47B), C47(H47C,H47D), C51(H51A,H51B), C42(H42A,H42B), C44(H44A,
 H44B), C41(H41A,H41B), C40(H40B,H40A), C43(H43A,H43B), C50(H50A,H50B),
 C45(H45A,H45B), C46(H46A,H46B), C49(H49A,H49B), C49(H49C,H49D), C53(H53A,H53B),
  C54(H54A,H54B), C48(H48A,H48B), C52(H52A,H52B), C55(H55A,H55B), C43A(H43C,
 H43D), C42A(H42C,H42D), C41A(H41C,H41D), C40A(H40C,H40D), C44A(H44C,H44D),
 C46A(H46C,H46D), C45A(H45C,H45D), C48A(H48C,H48D), C52A(H52C,H52D), C53A(H53C,
 H53D), C54A(H54C,H54D), C55A(H55C,H55D)
        6.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C20(H20), C9(H9), C18(H18), C19(H19), C32(H32), C8(H8), C15(H15),
 C7(H7), C6(H6), C11(H11), C14(H14), C30(H30), C31(H31), C13(H13), C12(H12),
 C12A(H12A), C11A(H11A), C13A(H13A), C14A(H14A), C15A(H15A)
        6.d Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C27(H27A,H27B,H27C), C26(H26A,
 H26B,H26C), C26A(H26D,H26E,H26F), C27A(H27D,H27E,H27F)
;
_shelx_res_checksum              78757
_shelx_hkl_checksum              49932