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_7712238
_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         'C40 H45 Cl F3 N3 Ni O, 0.5(C4 H10 O)'
_chemical_formula_sum            'C42 H50 Cl F3 N3 Ni O1.5'
_chemical_formula_weight         772.01
_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             2020-05-01
_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                 109.669(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.283(3)
_cell_length_b                   31.858(6)
_cell_length_c                   18.444(4)
_cell_measurement_reflns_used    9960
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      25.31
_cell_measurement_theta_min      2.25
_cell_volume                     7903(3)
_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, 2015)'
_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 0.963
_diffrn_measured_fraction_theta_max 0.956
_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  0.0601
_diffrn_reflns_av_unetI/netI     0.0959
_diffrn_reflns_Laue_measured_fraction_full 0.963
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_number            13908
_diffrn_reflns_point_group_measured_fraction_full 0.963
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.390
_diffrn_reflns_theta_min         1.278
_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    0.610
_exptl_absorpt_correction_T_max  0.913
_exptl_absorpt_correction_T_min  0.585
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.

Final HKLF 4 output contains 86273 reflections, Rint = 0.0980
 (29583 with I > 3sig(I), Rint = 0.0697)
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.298
_exptl_crystal_description       prism
_exptl_crystal_F_000             3256
_exptl_crystal_recrystallization_method
'The material was recrystallised from Et2O by slow evaporation'
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.702
_refine_diff_density_min         -0.458
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     984
_refine_ls_number_reflns         13908
_refine_ls_number_restraints     1618
_refine_ls_restrained_S_all      0.993
_refine_ls_R_factor_all          0.1014
_refine_ls_R_factor_gt           0.0603
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0650P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1308
_refine_ls_wR_factor_ref         0.1430
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9312
_reflns_number_total             13908
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03758k2.cif
_cod_data_source_block           jl331
_cod_original_formula_sum        'C42 H50 Cl F3 N3 Ni O1.50'
_cod_database_code               7712238
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.914
_shelx_estimated_absorpt_t_min   0.848
_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
 O3A-C83A \\sim O3A-C82A \\sim O3-C83
 with sigma of 0.01
 C81-C82 \\sim C81A-C82A
 with sigma of 0.01
 C84A-C83A \\sim C81-C82 \\sim C81A-C82A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(C84) = Uanis(C84A)
Uanis(O3) = Uanis(O3A)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O3A)=Sof(C81A)=Sof(H81D)=Sof(H81E)=Sof(H81F)=Sof(C82A)=Sof(H82C)=
 Sof(H82D)=Sof(C83A)=Sof(H83C)=Sof(H83D)=Sof(C84A)=Sof(H84D)=Sof(H84E)=
 Sof(H84F)=1-FVAR(1)
 Sof(O3)=Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(H81C)=Sof(C82)=Sof(H82A)=Sof(H82B)=
 Sof(C83)=Sof(H83A)=Sof(H83B)=Sof(C84)=Sof(H84A)=Sof(H84B)=Sof(H84C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C23(H23), C26(H26), C35(H35), C38(H38), C63(H63), C66(H66), C75(H75), C78(H78)
6.b Secondary CH2 refined with riding coordinates:
 C82(H82A,H82B), C83(H83A,H83B), C82A(H82C,H82D), C83A(H83C,H83D)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C8(H8), 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), C50(H50), C51(H51), C55(H55), C56(H56), C59(H59),
 C60(H60), C61(H61), C71(H71), C72(H72), C73(H73)
6.d Idealised Me refined as rotating group:
 C81(H81A,H81B,H81C), C84(H84A,H84B,H84C), C81A(H81D,H81E,H81F), C84A(H84D,
 H84E,H84F), 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)
;
_shelx_res_checksum              48803
_shelx_hkl_checksum              74668
_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 WC803
_olex2_submission_special_instructions 'No special instructions were received'