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_7712244
_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 H46 Cl N3 Ni O'
_chemical_formula_sum            'C39 H46 Cl N3 Ni O'
_chemical_formula_weight         666.95
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_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                 99.6570(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.7071(4)
_cell_length_b                   15.4345(4)
_cell_length_c                   15.4090(4)
_cell_measurement_reflns_used    9863
_cell_measurement_temperature    133(2)
_cell_measurement_theta_max      30.51
_cell_measurement_theta_min      2.48
_cell_volume                     3448.23(16)
_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      133(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-Nonius Kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II area detector'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0369
_diffrn_reflns_av_unetI/netI     0.0327
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            45912
_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         30.508
_diffrn_reflns_theta_min         1.881
_diffrn_source                   'microsource sealed X-ray tube'
_diffrn_source_current           0.99
_diffrn_source_power             0.0495
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.675
_exptl_absorpt_correction_T_max  0.922
_exptl_absorpt_correction_T_min  0.862
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker, 2016/2) was used for absorption correction.
wR2(int) was 0.0918 before and 0.0439 after correction.
The ratio of minimum to maximum transmission is 0.9342.
The \l/2 correction factor is not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.285
_exptl_crystal_description       prism
_exptl_crystal_F_000             1416
_exptl_crystal_recrystallization_method
'The material was recrystallised from THF by slow evaporation'
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.387
_refine_diff_density_min         -0.291
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     439
_refine_ls_number_reflns         10490
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0484
_refine_ls_R_factor_gt           0.0337
_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^)+(0.0336P)^2^+1.2683P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0763
_refine_ls_wR_factor_ref         0.0834
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8323
_reflns_number_total             10490
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03758k2.cif
_cod_data_source_block           jl338
_cod_database_code               7712244
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.923
_shelx_estimated_absorpt_t_min   0.774
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C34A) = Uanis(C34)
3. Others
 Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=Sof(C35A)=Sof(H35D)=Sof(H35E)=
 Sof(H35F)=Sof(C34A)=Sof(H34A)=1-FVAR(1)
 Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C36)=Sof(H36A)=
 Sof(H36B)=Sof(H36C)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C22(H22), C25(H25), C34(H34), C37(H37), C34A(H34A)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11), C14(H14),
 C15(H15), C18(H18), C19(H19), C20(H20), C30(H30), C31(H31), C32(H32)
4.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), 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), C36A(H36D,H36E,H36F), C35A(H35D,H35E,H35F)
;
_shelx_res_checksum              38403
_shelx_hkl_checksum              45594
_olex2_diffrn_ambient_temperature_device Kryoflex
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mylar loop in oil'
_olex2_submission_original_sample_id 'WC 786'
_olex2_submission_special_instructions 'No special instructions were received'