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_7712245
_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(C40 H48 Cl N3 Ni O2), C6.5 H6.5 N0.5 O, C4 H10 O'
_chemical_formula_sum            'C90.5 H112.5 Cl2 N6.5 Ni2 O6'
_chemical_formula_weight         1575.68
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-06-29
_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                87.202(2)
_cell_angle_beta                 76.107(2)
_cell_angle_gamma                75.606(2)
_cell_formula_units_Z            2
_cell_length_a                   12.2319(7)
_cell_length_b                   17.7599(11)
_cell_length_c                   20.0345(12)
_cell_measurement_reflns_used    9304
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      30.55
_cell_measurement_theta_min      2.26
_cell_volume                     4092.0(4)
_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      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 0.982
_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  0.0580
_diffrn_reflns_av_unetI/netI     0.0344
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            233094
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.819
_diffrn_reflns_theta_min         1.571
_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    0.583
_exptl_absorpt_correction_T_max  0.960
_exptl_absorpt_correction_T_min  0.893
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker, 2016/2) was used for absorption correction.
wR2(int) was 0.0622 before and 0.0571 after correction.
The ratio of minimum to maximum transmission is 0.9304.
The \l/2 correction factor is not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.279
_exptl_crystal_description       prism
_exptl_crystal_F_000             1678
_exptl_crystal_recrystallization_method
'The material was recrystallised from Et2O by slow evaporation'
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.542
_refine_diff_density_min         -0.349
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1005
_refine_ls_number_reflns         25243
_refine_ls_number_restraints     29
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0474
_refine_ls_R_factor_gt           0.0328
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0300P)^2^+2.1955P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0728
_refine_ls_wR_factor_ref         0.0790
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20392
_reflns_number_total             25243
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03758k2.cif
_cod_data_source_block           jl336
_cod_original_formula_sum        'C90.50 H112.50 Cl2 N6.50 Ni2 O6'
_cod_database_code               7712245
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.960
_shelx_estimated_absorpt_t_min   0.826
_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, All C(H,H,H,H,H,H) groups
2. Shared sites
{C84, N84}
3. Restrained distances
 C91A-C90 \\sim C91-C90A
 with sigma of 0.01
 C89-C88 \\sim C89A-C88
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C89 \\sim C89A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
Uanis(C84) = Uanis(N84)
Uanis(C91) = Uanis(C91A)
Uanis(C89) = Uanis(C89A)
5. Rigid body (RIGU) restrains
 C90, C91, C90A, C91A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O6, C88, H88A, H88B, H88C, H88D, H88E, H88F, C89, H89A, H89B, C89A, H89C, H89D
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C91)=Sof(H91A)=Sof(H91B)=Sof(H91C)=Sof(C90A)=Sof(H90C)=Sof(H90D)=1-FVAR(1)
 Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(C91A)=Sof(H91D)=Sof(H91E)=Sof(H91F)=FVAR(1)
 Sof(H88D)=Sof(H88E)=Sof(H88F)=Sof(C89A)=Sof(H89C)=Sof(H89D)=1-FVAR(2)
 Sof(H88A)=Sof(H88B)=Sof(H88C)=Sof(C89)=Sof(H89A)=Sof(H89B)=FVAR(2)
 Fixed Sof: N84(0.5) C84(0.5) H84(0.5)
7.a Ternary CH refined with riding coordinates:
 C23(H23), C26(H26), C35(H35), C38(H38), C63(H63), C66(H66), C75(H75), C78(H78)
7.b Secondary CH2 refined with riding coordinates:
 C89(H89A,H89B), C90(H90A,H90B), C90A(H90C,H90D), C89A(H89C,H89D)
7.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C7(H7), C9(H9), C10(H10), C15(H15), C16(H16),
 C19(H19), C20(H20), C21(H21), C31(H31), C32(H32), C33(H33), C41(H41), C42(H42),
  C44(H44), C47(H47), C49(H49), C50(H50), C55(H55), C56(H56), C59(H59),
 C60(H60), C61(H61), C71(H71), C72(H72), C73(H73), C82(H82), C83(H83), C84(H84),
  C86(H86)
7.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), 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),
 C53(H53A,H53B,H53C), 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), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C),
 C88(H88D,H88E,H88F), C91(H91A,H91B,H91C), C91A(H91D,H91E,H91F)
;
_shelx_res_checksum              11943
_shelx_hkl_checksum              33702
_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 789'
_olex2_submission_special_instructions 'No special instructions were received'