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_7129961
_publ_section_title
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 Metallation of sensitive fluoroarenes using a potassium TMP-zincate
 supported by a silyl(bis)amido ligand
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_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC00979J
_journal_year                    2022
_chemical_formula_moiety         'C42 H46 F3 N2 Si Zn, C24 H48 K O6, C4 H8 O'
_chemical_formula_sum            'C70 H102 F3 K N2 O7 Si Zn'
_chemical_formula_weight         1273.09
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-03-04
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
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2022-03-04 deposited with the CCDC.	2022-03-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.473(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   35.0797(7)
_cell_length_b                   15.7345(3)
_cell_length_c                   25.6152(4)
_cell_measurement_reflns_used    11400
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      72.5470
_cell_measurement_theta_min      4.3560
_cell_volume                     13984.3(4)
_computing_cell_refinement       CrysalisPro
_computing_data_collection       CrysalisPro
_computing_data_reduction        CrysalisPro
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXS 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      123(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'Oxford Diffraction Gemini S'
_diffrn_measurement_method       'omega scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0552
_diffrn_reflns_av_unetI/netI     0.0492
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       41
_diffrn_reflns_limit_h_min       -43
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            37197
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.126
_diffrn_reflns_theta_min         3.450
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    1.658
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.20491
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.209
_exptl_crystal_description       block
_exptl_crystal_F_000             5456
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.6
_exptl_crystal_size_min          0.6
_refine_diff_density_max         0.833
_refine_diff_density_min         -0.633
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     923
_refine_ls_number_reflns         13808
_refine_ls_number_restraints     397
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.1002
_refine_ls_R_factor_gt           0.0813
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1560P)^2^+18.6117P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2241
_refine_ls_wR_factor_ref         0.2547
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10485
_reflns_number_total             13808
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc00979j2.cif
_cod_data_source_block           pm355a
_cod_database_code               7129961
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Restrained distances
 O4-C55 = O4-C58 = O3-C51 = O3-C54 = O2-C47 = O2-C50 = O1-C43 = O1-C46
 1.43 with sigma of 0.01
 O4A-C55A = O4A-C58A = O3A-C51A = O3A-C54A
 1.43 with sigma of 0.01
 O2A-C47A = O2A-C50A = O1A-C43A = O1A-C46A
 1.43 with sigma of 0.01
 O5-C59 = O5-C62 = O6-C63 = O6-C66
 1.43 with sigma of 0.01
 O5A-C59A = O5A-C62A = O6A-C63A = O6A-C66A = O7-C67
 1.43 with sigma of 0.01
 O8-C71 = O8-C74 = O7-C70
 1.43 with sigma of 0.01
 C55-C56 = C56-C57 = C57-C58 = C51-C52 = C52-C53 = C53-C54
 1.53 with sigma of 0.01
 C47-C48 = C48-C49 = C49-C50 = C43-C44 = C44-C45 = C45-C46
 1.53 with sigma of 0.01
 C55A-C56A = C56A-C57A = C57A-C58A = C51A-C52A = C52A-C53A = C53A-C54A
 1.53 with sigma of 0.01
 C47A-C48A = C48A-C49A = C49A-C50A = C43A-C44A = C44A-C45A = C45A-C46A
 1.53 with sigma of 0.01
 C59-C60 = C60-C61 = C61-C62 = C63-C64 = C64-C65 = C65-C66
 1.53 with sigma of 0.01
 C67-C68 = C68-C69 = C69-C70
 1.53 with sigma of 0.01
 C59A-C60A = C60A-C61A = C61A-C62A = C63A-C64A = C64A-C65A = C65A-C66A
 1.53 with sigma of 0.01
 C71-C72 = C72-C73 = C73-C74
 1.53 with sigma of 0.01
 C63-C66 = C63A-C66A
 2.3 with sigma of 0.02
 C73-C71
 2.4 with sigma of 0.02
 C72-C74
 2.4 with sigma of 0.02
 C74-C71
 2.3 with sigma of 0.02
 O6A-C64A
 2.3 with sigma of 0.02
 C56-C57A
 2.3 with sigma of 0.02
 O2A-C49A
 2.3 with sigma of 0.02
2. Rigid bond restraints
 O4, C55, C56, C57, C58
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O1, C43, C44, C45, C46
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O3, C51, C52, C53, C54
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O2, C47, C48, C49, C50
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C69, C67, C68, O7, C70
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O8, C71, C72, C73, C74
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O6, C63, C64, C65, C66
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O5, C59, C60, C61, C62
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
O4 \\sim C55 \\sim C56 \\sim C57 \\sim C58: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.02 within 1.7A
O1 \\sim C43 \\sim C44 \\sim C45 \\sim C46: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.02 within 1.7A
O3 \\sim C51 \\sim C52 \\sim C53 \\sim C54: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.02 within 1.7A
O2 \\sim C47 \\sim C48 \\sim C49 \\sim C50: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.02 within 1.7A
C69 \\sim C67 \\sim C68 \\sim O7 \\sim C70: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.02 within 1.7A
O8 \\sim C71 \\sim C72 \\sim C73 \\sim C74: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.02 within 1.7A
O6 \\sim C63 \\sim C64 \\sim C65 \\sim C66: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.02 within 1.7A
O5 \\sim C59 \\sim C60 \\sim C61 \\sim C62: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.02 within 1.7A
Uanis(O3) = Uanis(O3A)
Uanis(O2) = Uanis(O2A)
Uanis(O1) = Uanis(O1A)
Uanis(O5) = Uanis(O5A)
Uanis(O6) = Uanis(O6A)
Uanis(C56) = Uanis(C55A)
Uanis(C57) = Uanis(C56A)
Uanis(C58) = Uanis(C57A)
Uanis(C46) = Uanis(C46A)
Uanis(C45) = Uanis(C45A)
Uanis(C44) = Uanis(C44A)
Uanis(C43) = Uanis(C43A)
Uanis(C50) = Uanis(C50A)
Uanis(C49) = Uanis(C49A)
Uanis(C48) = Uanis(C48A)
Uanis(C47) = Uanis(C47A)
Uanis(C54) = Uanis(C54A)
Uanis(C53) = Uanis(C53A)
Uanis(C52) = Uanis(C52A)
Uanis(C63) = Uanis(C63A)
Uanis(C64) = Uanis(C65A)
Uanis(C66) = Uanis(C66A)
Uanis(C62) = Uanis(C62A)
Uanis(C61) = Uanis(C61A)
Uanis(C60) = Uanis(C60A)
Uanis(C59) = Uanis(C59A)
Uanis(C51) = Uanis(C51A)
Uanis(O4) = Uanis(C58A)
4. Others
 Fixed Sof: O1(0.5) O2(0.5) O3(0.5) O4(0.5) O5(0.5) O6(0.5) C43(0.5) H43A(0.5)
 H43B(0.5) C44(0.5) H44A(0.5) H44B(0.5) C45(0.5) H45A(0.5) H45B(0.5) C46(0.5)
 H46A(0.5) H46B(0.5) C47(0.5) H47A(0.5) H47B(0.5) C48(0.5) H48A(0.5) H48B(0.5)
 C49(0.5) H49A(0.5) H49B(0.5) C50(0.5) H50A(0.5) H50B(0.5) C51(0.5) H51A(0.5)
 H51B(0.5) C52(0.5) H52A(0.5) H52B(0.5) C53(0.5) H53A(0.5) H53B(0.5) C54(0.5)
 H54A(0.5) H54B(0.5) C55(0.5) H55A(0.5) H55B(0.5) C56(0.5) H56A(0.5) H56B(0.5)
 C57(0.5) H57A(0.5) H57B(0.5) C58(0.5) H58A(0.5) H58B(0.5) C59(0.5) H59A(0.5)
 H59B(0.5) C60(0.5) H60A(0.5) H60B(0.5) C61(0.5) H61A(0.5) H61B(0.5) C62(0.5)
 H62A(0.5) H62B(0.5) C63(0.5) H63A(0.5) H63B(0.5) C64(0.5) H64A(0.5) H64B(0.5)
 C65(0.5) H65A(0.5) H65B(0.5) C66(0.5) H66A(0.5) H66B(0.5) O1A(0.5) C43A(0.5)
 H43C(0.5) H43D(0.5) C44A(0.5) H44C(0.5) H44D(0.5) C45A(0.5) H45C(0.5)
 H45D(0.5) C46A(0.5) H46C(0.5) H46D(0.5) O3A(0.5) C51A(0.5) H51C(0.5) H51D(0.5)
 C52A(0.5) H52C(0.5) H52D(0.5) C53A(0.5) H53C(0.5) H53D(0.5) C54A(0.5)
 H54C(0.5) H54D(0.5) O4A(0.5) C55A(0.5) H55C(0.5) H55D(0.5) C56A(0.5) H56C(0.5)
 H56D(0.5) C57A(0.5) H57C(0.5) H57D(0.5) C58A(0.5) H58C(0.5) H58D(0.5) O2A(0.5)
 C47A(0.5) H47C(0.5) H47D(0.5) C48A(0.5) H48C(0.5) H48D(0.5) C49A(0.5)
 H49C(0.5) H49D(0.5) C50A(0.5) H50C(0.5) H50D(0.5) O5A(0.5) C59A(0.5) H59C(0.5)
 H59D(0.5) C60A(0.5) H60C(0.5) H60D(0.5) C62A(0.5) H62C(0.5) H62D(0.5)
 C61A(0.5) H61C(0.5) H61D(0.5) O6A(0.5) C63A(0.5) H63C(0.5) H63D(0.5) C64A(0.5)
 H64C(0.5) H64D(0.5) C65A(0.5) H65C(0.5) H65D(0.5) C66A(0.5) H66C(0.5)
 H66D(0.5) O8(0.5) C71(0.5) H71A(0.5) H71B(0.5) C72(0.5) H72A(0.5) H72B(0.5)
 C73(0.5) H73A(0.5) H73B(0.5) C74(0.5) H74A(0.5) H74B(0.5) O7(0.5) C67(0.5)
 H67A(0.5) H67B(0.5) C68(0.5) H68A(0.5) H68B(0.5) C69(0.5) H69A(0.5) H69B(0.5)
 C70(0.5) H70A(0.5) H70B(0.5)
5.a Ternary CH refined with riding coordinates:
 C19(H19), C23(H23), C31(H31), C34(H34)
5.b Secondary CH2 refined with riding coordinates:
 C43(H43A,H43B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B), C47(H47A,
 H47B), C48(H48A,H48B), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B),
 C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B),
  C57(H57A,H57B), C58(H58A,H58B), C59(H59A,H59B), C60(H60A,H60B), C61(H61A,
 H61B), C62(H62A,H62B), C63(H63A,H63B), C64(H64A,H64B), C65(H65A,H65B),
 C66(H66A,H66B), C43A(H43C,H43D), C44A(H44C,H44D), C45A(H45C,H45D), C46A(H46C,
 H46D), C51A(H51C,H51D), C52A(H52C,H52D), C53A(H53C,H53D), C54A(H54C,H54D),
 C55A(H55C,H55D), C56A(H56C,H56D), C57A(H57C,H57D), C58A(H58C,H58D), C47A(H47C,
 H47D), C48A(H48C,H48D), C49A(H49C,H49D), C50A(H50C,H50D), C59A(H59C,H59D),
 C60A(H60C,H60D), C62A(H62C,H62D), C61A(H61C,H61D), C63A(H63C,H63D), C64A(H64C,
 H64D), C65A(H65C,H65D), C66A(H66C,H66D), C71(H71A,H71B), C72(H72A,H72B),
 C73(H73A,H73B), C74(H74A,H74B), C67(H67A,H67B), C68(H68A,H68B), C69(H69A,H69B),
  C70(H70A,H70B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C15(H15), C16(H16), C17(H17), C27(H27), C28(H28), C29(H29), C39(H39),
  C41(H41)
5.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C24(H24A,H24B,
 H24C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C36(H36A,
 H36B,H36C)
;
_shelx_res_checksum              72604
_shelx_hkl_checksum              17509
_olex2_submission_special_instructions 'No special instructions were received'