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_7129966
_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 H46 Cl3 N2 Si Zn, C24 H48 K1 O6, C4 H8 O'
_chemical_formula_sum            'C70 H102 Cl3 K N2 O7 Si Zn'
_chemical_formula_weight         1322.44
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_Int_Tables_number      14
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-02-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-02-14 deposited with the CCDC.	2022-03-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.050(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.6110(6)
_cell_length_b                   15.6044(5)
_cell_length_c                   23.2737(8)
_cell_measurement_reflns_used    16207
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      71.4310
_cell_measurement_theta_min      3.4490
_cell_volume                     7075.4(4)
_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      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_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    -25.00  40.00   0.50    0.50    --   47.95 -38.00 -90.00  130
  2  \w    -28.00  56.00   0.50    0.50    --  -18.75  15.00-180.00  168
  3  \w     26.00 120.00   0.50    0.50    --   47.95  77.00-120.00  188
  4  \w     91.00 171.00   0.50    2.75    --  107.11  61.00-120.00  160
  5  \w     95.00 171.00   0.50    2.75    --  107.11  45.00  30.00  152
  6  \w    101.00 171.00   0.50    2.75    --  107.11  84.00 171.00  140
  7  \w     95.00 171.00   0.50    2.75    --  107.11  30.00  90.00  152
  8  \w     95.00 171.00   0.50    2.75    --  107.11  30.00 -60.00  152
  9  \w     95.00 171.00   0.50    2.75    --  107.11  45.00 -90.00  152
 10  \w     95.00 171.00   0.50    2.75    --  107.11 125.00 -90.00  152
 11  \w     91.00 171.00   0.50    2.75    --  107.11  61.00 -30.00  160
 12  \w     35.00 134.00   0.50    2.75    --  107.11 -84.00  51.00  198
 13  \w     35.00  96.00   0.50    0.50    --   47.95-125.00 -90.00  122
 14  \w     35.00  68.00   0.50    2.75    --  107.11 -61.00-180.00   66
 15  \w     35.00 106.00   0.50    2.75    --  107.11 -94.00-150.00  142
 16  \w     35.00 102.00   0.50    2.75    --  107.11 -77.00 -30.00  134
 17  \w     35.00  68.00   0.50    2.75    --  107.11 -61.00 -30.00   66
 18  \w     35.00  68.00   0.50    2.75    --  107.11 -61.00 -90.00   66
 19  \w     35.00  68.00   0.50    2.75    --  107.11 -61.00-150.00   66
 20  \w    -26.00  23.00   0.50    0.50    --   47.95 -19.00-180.00   98
 21  \w     33.00 120.00   0.50    0.50    --   47.95  57.00-150.00  174
 22  \w     26.00 120.00   0.50    0.50    --   47.95  77.00   0.00  188
 23  \w     26.00 120.00   0.50    0.50    --   47.95  77.00 120.00  188
 24  \w    -20.00  74.00   0.50    0.50    --   47.95 -84.00  51.00  188
 25  \w    -44.00  43.00   0.50    0.50    --  -18.75  84.00 171.00  174
 26  \w    -66.00 -12.00   0.50    0.50    --  -18.75 125.00-150.00  108
;
_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      -0.0739723000
_diffrn_orient_matrix_UB_12      0.0350413000
_diffrn_orient_matrix_UB_13      -0.0226378000
_diffrn_orient_matrix_UB_21      0.0157334000
_diffrn_orient_matrix_UB_22      0.0557779000
_diffrn_orient_matrix_UB_23      0.0573834000
_diffrn_orient_matrix_UB_31      0.0230247000
_diffrn_orient_matrix_UB_32      0.0735642000
_diffrn_orient_matrix_UB_33      -0.0332084000
_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  0.1091
_diffrn_reflns_av_unetI/netI     0.1368
_diffrn_reflns_Laue_measured_fraction_full 1
_diffrn_reflns_Laue_measured_fraction_max 1
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            75990
_diffrn_reflns_point_group_measured_fraction_full 1
_diffrn_reflns_point_group_measured_fraction_max 1
_diffrn_reflns_theta_full        64.653
_diffrn_reflns_theta_max         64.653
_diffrn_reflns_theta_min         3.473
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.613
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.408
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.241
_exptl_crystal_description       needle
_exptl_crystal_F_000             2824
_exptl_crystal_size_max          0.264
_exptl_crystal_size_mid          0.083
_exptl_crystal_size_min          0.067
_refine_diff_density_max         1.053
_refine_diff_density_min         -0.62
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.414
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     822
_refine_ls_number_reflns         11930
_refine_ls_number_restraints     556
_refine_ls_restrained_S_all      1.527
_refine_ls_R_factor_all          0.1547
_refine_ls_R_factor_gt           0.1244
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3502
_refine_ls_wR_factor_ref         0.3854
_reflns_Friedel_coverage         0
_reflns_number_gt                7789
_reflns_number_total             11930
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc00979j2.cif
_cod_data_source_block           19EH060_PM438
_cod_database_code               7129966
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C280  H408  Cl12  K4  N8  O28  Si4  Zn4  '
_shelx_estimated_absorpt_t_max   0.844
_shelx_estimated_absorpt_t_min   0.545
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 C65-C64 \\sim C65A-C64A \\sim C57-C56 \\sim C61-C60 \\sim C69-C68 \\sim
C53-C52 \\sim C49-C48 \\sim C45-C44
 with sigma of 0.002
 C44-C43 \\sim C46-C45 \\sim C48-C47 \\sim C50-C49 \\sim C54-C53 \\sim C52-C51
\\sim C58-C57 \\sim C56-C55
 \\sim C62-C61 \\sim C60-C59 \\sim C66-C65 \\sim C64-C63 \\sim C70-C69 \\sim
C68-C67 \\sim C66A-C65A \\sim C64A-
 C63A
 with sigma of 0.002
 O5-C59 \\sim O5-C62 \\sim O4-C55 \\sim O4-C58 \\sim O7-C67 \\sim O7-C70 \\sim
O6-C63 \\sim O6-C66 \\sim O3-
 C54 \\sim O3-C51 \\sim O2-C47 \\sim O2-C50 \\sim O1-C43 \\sim O1-C46 \\sim
O6A-C63A \\sim O6A-C66A
 with sigma of 0.002
3. Rigid bond restraints
 O6, C63, C64, C65, C66
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C63A, C64A, C65A, O6A, C66A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C53, C54, O3, C51, C52
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C67, C68, C69, C70, O7
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C43, O1, C46, C45, C44
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C49, C48, C47, O2, C50
 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(Cl3) \\sim Ueq, Uanis(Cl1) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.003
Uanis(C66) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C65A) \\sim Ueq, Uanis(C64A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C41) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C30)
\\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C38) \\sim Ueq,
Uanis(C36) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C33)
\\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C40) \\sim Ueq,
Uanis(C17) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C18)
\\sim Ueq, Uanis(C23) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(O1) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C44) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C53) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O4) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C58)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O5) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C59) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C63) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C24) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(C63A)=Sof(H63C)=Sof(H63D)=Sof(O6A)=Sof(C66A)=Sof(H66C)=Sof(H66D)=
 Sof(C65A)=Sof(H65C)=Sof(H65D)=Sof(C64A)=Sof(H64C)=Sof(H64D)=1-FVAR(1)
 Sof(O6)=Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(C63)=
 Sof(H63A)=Sof(H63B)=Sof(C66)=Sof(H66A)=Sof(H66B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C28(H28), C40(H40), C37(H37), C25(H25)
6.b Secondary CH2 refined with riding coordinates:
 C47(H47A,H47B), C55(H55A,H55B), C48(H48A,H48B), C46(H46A,H46B), C61(H61A,
 H61B), C56(H56A,H56B), C62(H62A,H62B), C43(H43B,H43A), C70(H70A,H70B),
 C59(H59A,H59B), C69(H69A,H69B), C65(H65A,H65B), C57(H57A,H57B), C60(H60A,H60B),
  C58(H58A,H58B), C49(H49A,H49B), C45(H45A,H45B), C52(H52A,H52B), C54(H54A,
 H54B), C53(H53A,H53B), C68(H68A,H68B), C64(H64A,H64B), C50(H50A,H50B),
 C51(H51A,H51B), C67(H67A,H67B), C44(H44A,H44B), C63(H63A,H63B), C66(H66A,H66B),
  C63A(H63C,H63D), C66A(H66C,H66D), C65A(H65C,H65D), C64A(H64C,H64D)
6.c Me refined with riding coordinates:
 C41(H41A,H41B,H41C)
6.d Aromatic/amide H refined with riding coordinates:
 C14(H14), C8(H8), C5(H5), C12(H12), C23(H23), C21(H21), C11(H11), C10(H10),
 C34(H34), C9(H9), C15(H15), C3(H3), C18(H18), C22(H22), C33(H33), C17(H17),
 C16(H16), C35(H35)
6.e Idealised Me refined as rotating group:
 C42(H42A,H42B,H42C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,
 H29C), C38(H38A,H38B,H38C), C30(H30A,H30B,H30C), C39(H39A,H39B,H39C)
;
_shelx_res_checksum              73233
_shelx_hkl_checksum              41488
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 9.655
_oxdiff_exptl_absorpt_empirical_full_min 0.479