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_7712247
_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         'C39 H43 Cl F3 N3 Ni'
_chemical_formula_sum            'C39 H43 Cl F3 N3 Ni'
_chemical_formula_weight         704.92
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-10-26
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2023-01-09 deposited with the CCDC.	2023-01-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   26.2539(19)
_cell_length_b                   9.9978(7)
_cell_length_c                   27.6095(19)
_cell_measurement_reflns_used    9783
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      28.58
_cell_measurement_theta_min      2.30
_cell_volume                     7247.0(9)
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      120(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 0.996
_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  0.0603
_diffrn_reflns_av_unetI/netI     0.0574
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            73697
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.690
_diffrn_reflns_theta_min         1.475
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.35
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           45.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.655
_exptl_absorpt_correction_T_max  0.949
_exptl_absorpt_correction_T_min  0.907
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker, 2016/2) was used for absorption correction.
wR2(int) was 0.0532 before and 0.0502 after correction.
The ratio of minimum to maximum transmission is 0.9563.
The \l/2 correction factor is not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.292
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2960
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of THF and Et2O  by slow evaporation'
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.358
_refine_diff_density_min         -0.414
_refine_diff_density_rms         0.060
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.377(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     864
_refine_ls_number_reflns         18272
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0583
_refine_ls_R_factor_gt           0.0395
_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^)+(0.0294P)^2^+1.2521P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0699
_refine_ls_wR_factor_ref         0.0756
_reflns_Friedel_coverage         0.921
_reflns_Friedel_fraction_full    0.984
_reflns_Friedel_fraction_max     0.955
_reflns_number_gt                14943
_reflns_number_total             18272
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03758k2.cif
_cod_data_source_block           jl339
_cod_database_code               7712247
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.949
_shelx_estimated_absorpt_t_min   0.864
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.623(10)
 0.377(10)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Ternary CH refined with riding coordinates:
 C22(H22), C25(H25), C34(H34), C37(H37), C61(H61), C64(H64), C73(H73), C76(H76)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C10(H10), C11(H11), C14(H14),
 C15(H15), C18(H18), C19(H19), C20(H20), C30(H30), C31(H31), C32(H32), C41(H41),
  C42(H42), C43(H43), C44(H44), C47(H47), C49(H49), C50(H50), C53(H53),
 C54(H54), C57(H57), C58(H58), C59(H59), C69(H69), C70(H70), C71(H71)
3.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C38(H38A,H38B,H38C), C39(H39A,
 H39B,H39C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C65(H65A,H65B,H65C),
 C66(H66A,H66B,H66C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C77(H77A,H77B,
 H77C), C78(H78A,H78B,H78C)
;
_shelx_res_checksum              67785
_shelx_hkl_checksum              34796
_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 805'
_olex2_submission_special_instructions 'No special instructions were received'