Investigating the Mechanism of Ni-Mediated Trifluoromethylthiolation of Aryl Halides using AgSCF3
Chiu, Weiling; Nadeau, Ben E.; Patrick, Brian O.; Love, Jennifer; Dalton Transactions  (2023) –; doi:10.1039/D2DT03758K

data_7712239
_publ_section_title
;
 Investigating the Mechanism of Ni-Mediated Trifluoromethylthiolation of
 Aryl Halides using AgSCF3
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT03758K
_journal_year                    2023
_chemical_formula_moiety         '2(C39 H46 Cl N3 Ni), 0.295(C4 H10 O)'
_chemical_formula_sum            'C79.18 H94.94 Cl2 N6 Ni2 O0.3'
_chemical_formula_weight         1323.72
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-06-23
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2023-01-09 deposited with the CCDC.	2023-01-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.175(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.1680(12)
_cell_length_b                   13.8817(7)
_cell_length_c                   23.0618(13)
_cell_measurement_reflns_used    9938
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      25.305
_cell_measurement_theta_min      2.322
_cell_volume                     6962.2(6)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_collection       APEX3
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'XT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      90(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'Bruker D8 Kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'TRIUMPH curved-crystal'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0677
_diffrn_reflns_av_unetI/netI     0.0578
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            79098
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.422
_diffrn_reflns_theta_min         1.721
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.35
_diffrn_source_voltage           45.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.666
_exptl_absorpt_correction_T_max  0.954
_exptl_absorpt_correction_T_min  0.878
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker, 2016/2) was used for absorption correction.
wR2(int) was 0.0573 before and 0.0515 after correction.
The ratio of minimum to maximum transmission is 0.9204.
The \l/2 correction factor is not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.263
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2817
_exptl_crystal_recrystallization_method
'The material was recrystallised from Et2O by slow evaporation'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.508
_refine_diff_density_min         -0.471
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.173
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1010
_refine_ls_number_reflns         12828
_refine_ls_number_restraints     889
_refine_ls_restrained_S_all      1.143
_refine_ls_R_factor_all          0.0953
_refine_ls_R_factor_gt           0.0613
_refine_ls_shift/su_max          0.008
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+19.2103P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1082
_refine_ls_wR_factor_ref         0.1172
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9326
_reflns_number_total             12828
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03758k2.cif
_cod_data_source_block           jl333
_cod_original_formula_sum        'C79.18 H94.94 Cl2 N6 Ni2 O0.30'
_cod_database_code               7712239
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.955
_shelx_estimated_absorpt_t_min   0.907
_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
 Ni2-Cl2 \\sim Ni2A-Cl2A
 with sigma of 0.02
 C58-C63 \\sim C58A-C63A
 with sigma of 0.02
 C57-C63 \\sim C57A-C63A
 with sigma of 0.04
 C58-C65 \\sim C58A-C65A
 with sigma of 0.04
 C59-C63 \\sim C59A-C63A
 with sigma of 0.04
 C63-C64 \\sim C63A-C64A
 with sigma of 0.02
 C63-C65 \\sim C63A-C65A
 with sigma of 0.02
 C58-C59 \\sim C58A-C59A
 with sigma of 0.02
 N5-C58 \\sim N5-C58A
 with sigma of 0.04
 C58-C62 \\sim C58A-C62A
 with sigma of 0.04
 Ni2-N4 \\sim Ni2A-N4A
 with sigma of 0.02
 C57-C58 \\sim C57A-C58A
 with sigma of 0.02
 C58-C60 \\sim C58A-C60A
 with sigma of 0.04
 C58-C64 \\sim C58A-C64A
 with sigma of 0.04
 Ni2-C41 \\sim Ni2A-C41A
 with sigma of 0.02
 Ni2-C54 \\sim Ni2A-C54
 with sigma of 0.02
 C46-C48 \\sim C46A-C48A
 with sigma of 0.04
 C41-C45 \\sim C41A-C45A
 with sigma of 0.04
 C45-C47 \\sim C45A-C47A
 with sigma of 0.04
 N4-C47 \\sim N4A-C47A
 with sigma of 0.02
 N4-C51 \\sim N4A-C51A
 with sigma of 0.02
 C42-C44 \\sim C42A-C44A
 with sigma of 0.04
 C43-C52 \\sim C43A-C52A
 with sigma of 0.04
 C41-C42 \\sim C41A-C42A
 with sigma of 0.02
 C41-C46 \\sim C41A-C46A
 with sigma of 0.02
 C42-C43 \\sim C42A-C43A
 with sigma of 0.02
 C41-C54 \\sim C41A-C54
 with sigma of 0.04
 C43-C44 \\sim C43A-C44A
 with sigma of 0.02
 C44-C45 \\sim C44A-C45A
 with sigma of 0.02
 C44-C52 \\sim C44A-C52A
 with sigma of 0.02
 C45-C46 \\sim C45A-C46A
 with sigma of 0.02
 C47-C49 \\sim C47A-C49A
 with sigma of 0.04
 C46-C47 \\sim C46A-C47A
 with sigma of 0.02
 C47-C48 \\sim C47A-C48A
 with sigma of 0.02
 C41-C43 \\sim C41A-C43A
 with sigma of 0.04
 C48-C49 \\sim C48A-C49A
 with sigma of 0.02
 C41-C47 \\sim C41A-C47A
 with sigma of 0.04
 C49-C50 \\sim C49A-C50A
 with sigma of 0.02
 C50-C51 \\sim C50A-C51A
 with sigma of 0.02
 C42-C46 \\sim C42A-C46A
 with sigma of 0.04
 C43-C45 \\sim C43A-C45A
 with sigma of 0.04
 C44-C46 \\sim C44A-C46A
 with sigma of 0.04
 Ni2-C42 \\sim Ni2A-C42A
 with sigma of 0.04
 C45-C52 \\sim C45A-C52A
 with sigma of 0.04
 Ni2-C46 \\sim Ni2A-C46A
 with sigma of 0.04
 Ni2-C47 \\sim Ni2A-C47A
 with sigma of 0.04
 Ni2-C51 \\sim Ni2A-C51A
 with sigma of 0.04
 C47-C51 \\sim C47A-C51A
 with sigma of 0.04
 Cl2-N4 \\sim Cl2A-N4A
 with sigma of 0.04
 C48-C50 \\sim C48A-C50A
 with sigma of 0.04
 Cl2-C41 \\sim Cl2A-C41A
 with sigma of 0.04
 Cl2-C54 \\sim Cl2A-C54
 with sigma of 0.04
 C49-C51 \\sim C49A-C51A
 with sigma of 0.04
 N4-C41 \\sim N4A-C41A
 with sigma of 0.04
 N4-C46 \\sim N4A-C46A
 with sigma of 0.04
 N4-C48 \\sim N4A-C48A
 with sigma of 0.04
 N4-C50 \\sim N4A-C50A
 with sigma of 0.04
 N4-C54 \\sim N4A-C54
 with sigma of 0.04
 C57-C59 \\sim C57A-C59A
 with sigma of 0.04
 C57-C62 \\sim C57A-C62A
 with sigma of 0.02
 C59-C61 \\sim C59A-C61A
 with sigma of 0.04
 C59-C60 \\sim C59A-C60A
 with sigma of 0.02
 C67-C68 \\sim C67A-C68A
 with sigma of 0.04
 C60-C61 \\sim C60A-C61A
 with sigma of 0.02
 N5-C62 \\sim N5-C62A
 with sigma of 0.04
 C57-C61 \\sim C57A-C61A
 with sigma of 0.04
 C57-C66 \\sim C57A-C66A
 with sigma of 0.04
 C61-C66 \\sim C61A-C66A
 with sigma of 0.04
 C62-C67 \\sim C62A-C67A
 with sigma of 0.04
 C60-C62 \\sim C60A-C62A
 with sigma of 0.04
 C61-C62 \\sim C61A-C62A
 with sigma of 0.02
 C62-C66 \\sim C62A-C66A
 with sigma of 0.02
 C62-C68 \\sim C62A-C68A
 with sigma of 0.04
 C64-C65 \\sim C64A-C65A
 with sigma of 0.04
 C66-C67 \\sim C66A-C67A
 with sigma of 0.02
 C66-C68 \\sim C66A-C68A
 with sigma of 0.02
 N5-C57 \\sim N5-C57A
 with sigma of 0.02
 C83-C84 \\sim C82-C81
 with sigma of 0.01
 O1-C82 \\sim O1-C83
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim
C65 \\sim C66 \\sim C67 \\sim C68 \\sim C57A \\sim C58A \\sim C59A \\sim C60A
\\sim C61A \\sim C62A \\sim C63A \\sim C64A \\sim C65A \\sim C66A \\sim C67A
\\sim C68A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
N4 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim
C48 \\sim C49 \\sim C50 \\sim C51 \\sim C52: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
C41A \\sim C42A \\sim C43A \\sim C44A \\sim C52A \\sim C45A \\sim C46A \\sim
C47A \\sim C48A \\sim C49A \\sim C50A \\sim C51A \\sim N4A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C63A) \\sim Ueq, Uanis(C63) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.02
Uanis(C58) \\sim Ueq, Uanis(C58A) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.02
Uanis(C58) = Uanis(C58A)
Uanis(N4) = Uanis(N4A)
Uanis(C64) = Uanis(C64A)
Uanis(C65A) = Uanis(C65)
Uanis(C60) = Uanis(C60A)
Uanis(C61A) = Uanis(C61)
Uanis(C62A) = Uanis(C62)
Uanis(C59A) = Uanis(C59)
Uanis(C57A) = Uanis(C57)
Uanis(C41A) = Uanis(C41)
Uanis(C42) = Uanis(C42A)
Uanis(C81) = Uanis(C84)
Uanis(Cl2) = Uanis(Cl2A)
Uanis(C67A) = Uanis(C67)
Uanis(C47A) = Uanis(C47)
Uanis(C46A) = Uanis(C46)
4. Rigid body (RIGU) restrains
 C57, C58, C59, C60, C61, C62, C63, C64, C65, C66, C67, C68, C57A, C58A, C59A,
 C60A, C61A, C62A, C63A, C64A, C65A, C66A, C67A, C68A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C41A, C42A, C43A, C44A, C52A, C45A, C46A, C47A, C48A, C49A, C50A, C51A, N4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Ni2A)=Sof(Cl2A)=Sof(C41A)=Sof(C42A)=Sof(H42A)=Sof(C43A)=Sof(H43A)=
 Sof(C44A)=Sof(C52A)=Sof(H52D)=Sof(H52E)=Sof(H52F)=Sof(C45A)=Sof(H45A)=
 Sof(C46A)=Sof(C47A)=Sof(C48A)=Sof(H48A)=Sof(C49A)=Sof(H49A)=Sof(C50A)=
 Sof(H50A)=Sof(C51A)=Sof(H51A)=Sof(N4A)=1-FVAR(1)
 Sof(Ni2)=Sof(Cl2)=Sof(N4)=Sof(C41)=Sof(C42)=Sof(H42)=Sof(C43)=Sof(H43)=
 Sof(C44)=Sof(C45)=Sof(H45)=Sof(C46)=Sof(C47)=Sof(C48)=Sof(H48)=Sof(C49)=
 Sof(H49)=Sof(C50)=Sof(H50)=Sof(C51)=Sof(H51)=Sof(C52)=Sof(H52A)=Sof(H52B)=
 Sof(H52C)=FVAR(1)
 Sof(C57A)=Sof(C58A)=Sof(C59A)=Sof(H59A)=Sof(C60A)=Sof(H60A)=Sof(C61A)=
 Sof(H61A)=Sof(C62A)=Sof(C63A)=Sof(H63A)=Sof(C64A)=Sof(H64D)=Sof(H64E)=
 Sof(H64F)=Sof(C65A)=Sof(H65D)=Sof(H65E)=Sof(H65F)=Sof(C66A)=Sof(H66A)=
 Sof(C67A)=Sof(H67D)=Sof(H67E)=Sof(H67F)=Sof(C68A)=Sof(H68D)=Sof(H68E)=
 Sof(H68F)=1-FVAR(2)
 Sof(C57)=Sof(C58)=Sof(C59)=Sof(H59)=Sof(C60)=Sof(H60)=Sof(C61)=Sof(H61)=
 Sof(C62)=Sof(C63)=Sof(H63)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=Sof(C65)=
 Sof(H65A)=Sof(H65B)=Sof(H65C)=Sof(C66)=Sof(H66)=Sof(C67)=Sof(H67A)=Sof(H67B)=
 Sof(H67C)=Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=FVAR(2)
 Sof(O1)=Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(C83)=Sof(H83A)=Sof(H83B)=Sof(C84)=
 Sof(H84A)=Sof(H84B)=Sof(H84C)=Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(H81C)=0.5*
 FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C23(H23), C26(H26), C35(H35), C38(H38), C63(H63), C66(H66), C75(H75),
 C78(H78), C63A(H63A), C66A(H66A)
6.b Secondary CH2 refined with riding coordinates:
 C82(H82A,H82B), C83(H83A,H83B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11), C15(H15),
 C16(H16), C19(H19), C20(H20), C21(H21), C31(H31), C32(H32), C33(H33), C42(H42),
  C43(H43), C45(H45), C48(H48), C49(H49), C50(H50), C51(H51), C55(H55),
 C56(H56), C59(H59), C60(H60), C61(H61), C71(H71), C72(H72), C73(H73),
 C42A(H42A), C43A(H43A), C45A(H45A), C48A(H48A), C49A(H49A), C50A(H50A),
 C51A(H51A), C59A(H59A), C60A(H60A), C61A(H61A)
6.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,
 H27C), C28(H28A,H28B,H28C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C39(H39A,
 H39B,H39C), C40(H40A,H40B,H40C), C52(H52A,H52B,H52C), C64(H64A,H64B,H64C),
 C65(H65A,H65B,H65C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C76(H76A,H76B,
 H76C), C77(H77A,H77B,H77C), C79(H79A,H79B,H79C), C80(H80A,H80B,H80C),
 C52A(H52D,H52E,H52F), C64A(H64D,H64E,H64F), C65A(H65D,H65E,H65F), C67A(H67D,
 H67E,H67F), C68A(H68D,H68E,H68F), C84(H84A,H84B,H84C), C81(H81A,H81B,H81C)
;
_shelx_res_checksum              37969
_shelx_hkl_checksum              20435
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mylar loop in oil'
_olex2_submission_original_sample_id 'WC 783'
_olex2_submission_special_instructions 'No special instructions were received'