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_7712236
_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, 0.222(C4 H10 O), 0.5(C1.302 H3.204 O0.351)'
_chemical_formula_sum            'C40.54 H46.83 Cl F3 N3 Ni O0.4'
_chemical_formula_weight         733.66
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-04-29
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   18.9031(13)
_cell_length_b                   26.3085(17)
_cell_length_c                   30.518(2)
_cell_measurement_reflns_used    9993
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      30.51
_cell_measurement_theta_min      2.31
_cell_volume                     15177.0(17)
_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 2014/5 (Sheldrick, 2014)'
_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 0.999
_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  0.0452
_diffrn_reflns_av_unetI/netI     0.0444
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            87895
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.523
_diffrn_reflns_theta_min         1.485
_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    0.629
_exptl_absorpt_correction_T_max  0.876
_exptl_absorpt_correction_T_min  0.829
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker, 2016/2) was used for absorption correction.
wR2(int) was 0.0556 before and 0.0470 after correction.
The ratio of minimum to maximum transmission is 0.9461.
The \l/2 correction factor is not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.284
_exptl_crystal_description       prism
_exptl_crystal_F_000             6180
_exptl_crystal_recrystallization_method
'The material was recrystallised from Et2O by slow evaporation'
_exptl_crystal_size_max          0.41
_exptl_crystal_size_mid          0.38
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.550
_refine_diff_density_min         -0.376
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1055
_refine_ls_number_reflns         23172
_refine_ls_number_restraints     2076
_refine_ls_restrained_S_all      0.989
_refine_ls_R_factor_all          0.0687
_refine_ls_R_factor_gt           0.0413
_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^)+(0.0484P)^2^+7.9846P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0987
_refine_ls_wR_factor_ref         0.1127
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16696
_reflns_number_total             23172
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03758k2.cif
_cod_data_source_block           jl329
_cod_original_cell_volume        15177.2(18)
_cod_original_formula_sum        'C40.54 H46.83 Cl F3 N3 Ni O0.40'
_cod_database_code               7712236
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.879
_shelx_estimated_absorpt_t_min   0.782
_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
 O1-C80
 1.43 with sigma of 0.01
 C80-C79
 1.54 with sigma of 0.01
 F4A-C51 \\sim F4-C51 \\sim F6A-C51 \\sim F6-C51 \\sim F5A-C51 \\sim F5-C51
 with sigma of 0.01
 O1-C80 \\sim O1-C81
 with sigma of 0.01
 C79-C80 \\sim C82-C81
 with sigma of 0.01
 C81A-C82A \\sim C80-C79
 with sigma of 0.01
 C80-C81 \\sim C80A-C81A
 with sigma of 0.01
 C80A-C79A \\sim C81A-C82A
 with sigma of 0.01
 O1A-C80A \\sim O1A-C81A
 with sigma of 0.01
 C79A-O1A \\sim C82A-O1A
 with sigma of 0.01
 C79-O1 \\sim C79A-O1A
 with sigma of 0.01
 O1-C82 \\sim O1A-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(C82A) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C80) \\sim Ueq, Uanis(C79A) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C79A) = Uanis(C80)
Uanis(C81A) = Uanis(C82)
Uanis(C28) = Uanis(C28A)
Uanis(C35A) = Uanis(C35)
Uanis(C34) = Uanis(C34A)
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(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(1)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(1)
 Sof(O1)=Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(H79C)=Sof(C80)=Sof(H80A)=Sof(H80B)=
 Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(H82C)=FVAR(2)
 Sof(O1A)=Sof(C79A)=Sof(H79D)=Sof(H79E)=Sof(H79F)=Sof(C80A)=Sof(H80C)=
 Sof(H80D)=Sof(C81A)=Sof(H81C)=Sof(H81D)=FVAR(3)
 Sof(C38A)=Sof(H38D)=Sof(H38E)=Sof(H38F)=Sof(C39A)=Sof(H39D)=Sof(H39E)=
 Sof(H39F)=Sof(C83)=Sof(H83)=Sof(C28A)=Sof(C33A)=Sof(C32A)=Sof(H32A)=Sof(C31A)=
 Sof(H31A)=Sof(C30A)=Sof(H30A)=Sof(C29A)=Sof(C35A)=Sof(H35D)=Sof(H35E)=
 Sof(H35F)=Sof(C34A)=Sof(H34A)=Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=1-FVAR(4)
 Sof(C28)=Sof(C29)=Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31)=Sof(C32)=Sof(H32)=
 Sof(C33)=Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C36)=
 Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C37)=Sof(H37)=Sof(C39)=Sof(H39A)=Sof(H39B)=
 Sof(H39C)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=FVAR(4)
 Fixed Sof: C82A(0.25) H82D(0.25) H82E(0.25) H82F(0.25)
6.a Ternary CH refined with riding coordinates:
 C22(H22), C25(H25), C34(H34), C37(H37), C61(H61), C64(H64), C73(H73),
 C76(H76), C83(H83), C34A(H34A)
6.b Secondary CH2 refined with riding coordinates:
 C80(H80A,H80B), C81(H81A,H81B), C80A(H80C,H80D), C81A(H81C,H81D)
6.c Me refined with riding coordinates:
 C35(H35A,H35B,H35C), C82A(H82D,H82E,H82F), C35A(H35D,H35E,H35F)
6.d 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), C41(H41),
  C42(H42), C44(H44), C47(H47), C48(H48), C49(H49), C50(H50), C53(H53),
 C54(H54), C57(H57), C58(H58), C59(H59), C69(H69), C70(H70), C71(H71),
 C32A(H32A), C31A(H31A), C30A(H30A)
6.e Fitted hexagon refined as free rotating group:
 C28A(C33A,C32A,C31A,C30A,C29A)
6.f Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C), C36(H36A,H36B,H36C), 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), C79(H79A,H79B,H79C), C82(H82A,H82B,
 H82C), C79A(H79D,H79E,H79F), C39(H39A,H39B,H39C), C38(H38A,H38B,H38C),
 C38A(H38D,H38E,H38F), C39A(H39D,H39E,H39F), C36A(H36D,H36E,H36F)
;
_shelx_res_checksum              15784
_shelx_hkl_checksum              62104
_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 WC801
_olex2_submission_special_instructions 'No special instructions were received'