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_7712243
_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(C38 H43 Cl F N3 Ni), 0.5(C4 H10 O)'
_chemical_formula_sum            'C78 H91 Cl2 F2 N6 Ni2 O0.5'
_chemical_formula_weight         1346.88
_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             2020-12-16
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2023-01-09 deposited with the CCDC.	2023-01-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.877(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.2136(8)
_cell_length_b                   14.0529(5)
_cell_length_c                   23.0928(11)
_cell_measurement_reflns_used    9797
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      30.39
_cell_measurement_theta_min      2.30
_cell_volume                     7027.5(5)
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2016)'
_computing_data_collection       APEX3
_computing_data_reduction        'SAINT V8.40B (Bruker, 2016)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'Bruker-Nonius Kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II area detector'
_diffrn_measurement_method       '\w and \f 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  0.0503
_diffrn_reflns_av_unetI/netI     0.0509
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            92174
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.479
_diffrn_reflns_theta_min         1.443
_diffrn_source                   'microfocus 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    0.665
_exptl_absorpt_correction_T_max  0.875
_exptl_absorpt_correction_T_min  0.833
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker, 2016/2) was used for absorption correction.
wR2(int) was 0.0896 before and 0.0498 after correction.
The ratio of minimum to maximum transmission is 0.9519.
The \l/2 correction factor is not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.273
_exptl_crystal_description       prism
_exptl_crystal_F_000             2852
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of THF and Et2O  by slow evaporation'
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.902
_refine_diff_density_min         -0.571
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     865
_refine_ls_number_reflns         21298
_refine_ls_number_restraints     76
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0639
_refine_ls_R_factor_gt           0.0409
_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^)+(0.0382P)^2^+2.6417P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0888
_refine_ls_wR_factor_ref         0.0983
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15870
_reflns_number_total             21298
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03758k2.cif
_cod_data_source_block           jl340
_cod_original_formula_sum        'C78 H91 Cl2 F2 N6 Ni2 O0.50'
_cod_database_code               7712243
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.878
_shelx_estimated_absorpt_t_min   0.857
_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
 O6-C80 = O6-C81
 1.45 with sigma of 0.01
 O6-C79 = C82-O6
 2.5 with sigma of 0.005
 C80-C79 = C82-C81
 1.54 with sigma of 0.005
 C78-C76 \\sim C78A-C76 \\sim C77-C76 \\sim C77A-C76
 with sigma of 0.01
 O6-C80 \\sim O6-C81
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C81 \\sim C82: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
O6 \\sim C80 \\sim C81 \\sim C82 \\sim C79: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
Uanis(C81) = Uanis(C80)
Uanis(C82) = Uanis(C79)
4. Rigid body (RIGU) restrains
 C76, C77, C77A, C78, C78A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O6, C80, C81, C82
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C77, C77A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O6, C80, C81, C82, C79
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H76A)=Sof(C77A)=Sof(H77D)=Sof(H77E)=Sof(H77F)=Sof(C78A)=Sof(H78D)=
 Sof(H78E)=Sof(H78F)=1-FVAR(1)
 Sof(H76)=Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(H77C)=Sof(C78)=Sof(H78A)=Sof(H78B)=
 Sof(H78C)=FVAR(1)
 Fixed Sof: O6(0.5) C80(0.5) H80A(0.5) H80B(0.5) C81(0.5) H81A(0.5) H81B(0.5)
 C82(0.5) H82A(0.5) H82B(0.5) H82C(0.5) C79(0.5) H79A(0.5) H79B(0.5) H79C(0.5)
6.a Ternary CH refined with riding coordinates:
 C22(H22), C25(H25), C34(H34), C37(H37), C61(H61), C64(H64), C73(H73),
 C76(H76), C76(H76A)
6.b Secondary CH2 refined with riding coordinates:
 C80(H80A,H80B), C81(H81A,H81B)
6.c 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)
6.d 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), C77A(H77D,H77E,H77F), C78(H78A,H78B,H78C), C78A(H78D,H78E,H78F),
 C82(H82A,H82B,H82C), C79(H79A,H79B,H79C)
;
_shelx_res_checksum              34595
_shelx_hkl_checksum              80841
_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 792'
_olex2_submission_special_instructions 'No special instructions were received'