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_7712241
_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 Cl0.968 F N3 Ni0.968), 0.5(C4 H10 O), 0.032(Cl Ni)'
_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             2020-06-24
_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                 103.1380(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.2308(8)
_cell_length_b                   13.9982(5)
_cell_length_c                   22.5896(8)
_cell_measurement_reflns_used    9923
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      29.15
_cell_measurement_theta_min      2.35
_cell_volume                     6845.7(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 0.998
_diffrn_measurement_device       'Bruker D8 Kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_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  0.0606
_diffrn_reflns_av_unetI/netI     0.0506
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            101550
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.200
_diffrn_reflns_theta_min         1.462
_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    0.683
_exptl_absorpt_correction_T_max  0.915
_exptl_absorpt_correction_T_min  0.891
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker, 2016/2) was used for absorption correction.
wR2(int) was 0.0548 before and 0.0523 after correction.
The ratio of minimum to maximum transmission is 0.9736.
The \l/2 correction factor is not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.307
_exptl_crystal_description       prism
_exptl_crystal_F_000             2852
_exptl_crystal_recrystallization_method
'The material was recrystallised from Et2O by slow evaporation'
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.895
_refine_diff_density_min         -0.481
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1004
_refine_ls_number_reflns         18515
_refine_ls_number_restraints     683
_refine_ls_restrained_S_all      1.004
_refine_ls_R_factor_all          0.0672
_refine_ls_R_factor_gt           0.0402
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0361P)^2^+3.5497P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0848
_refine_ls_wR_factor_ref         0.0950
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13581
_reflns_number_total             18515
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03758k2.cif
_cod_data_source_block           jl334
_cod_original_formula_sum        'C78 H91 Cl2 F2 N6 Ni2 O0.50'
_cod_database_code               7712241
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.916
_shelx_estimated_absorpt_t_min   0.881
_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
 Ni2-N4 \\sim Ni2-N4A
 with sigma of 0.02
 Ni2-C41 \\sim Ni2-C41A
 with sigma of 0.02
 F2-C44 \\sim F2A-C44A
 with sigma of 0.02
 C49-C51 \\sim C49A-C51A
 with sigma of 0.04
 N4-C47 \\sim N4A-C47A
 with sigma of 0.02
 N4-C51 \\sim N4A-C51A
 with sigma of 0.02
 C41-C45 \\sim C41A-C45A
 with sigma of 0.04
 C42-C44 \\sim C42A-C44A
 with sigma of 0.04
 C41-C42 \\sim C41A-C42A
 with sigma of 0.02
 C41-C46 \\sim C41A-C46A
 with sigma of 0.02
 C45-C47 \\sim C45A-C47A
 with sigma of 0.04
 C42-C43 \\sim C42A-C43A
 with sigma of 0.02
 C43-C44 \\sim C43A-C44A
 with sigma of 0.02
 C44-C45 \\sim C44A-C45A
 with sigma of 0.02
 C45-C46 \\sim C45A-C46A
 with sigma of 0.02
 C46-C48 \\sim C46A-C48A
 with sigma of 0.04
 C47-C51 \\sim C47A-C51A
 with sigma of 0.04
 C46-C47 \\sim C46A-C47A
 with sigma of 0.02
 C47-C48 \\sim C47A-C48A
 with sigma of 0.02
 C41-C47 \\sim C41A-C47A
 with sigma of 0.04
 C48-C49 \\sim C48A-C49A
 with sigma of 0.02
 C42-C46 \\sim C42A-C46A
 with sigma of 0.04
 C43-C45 \\sim C43A-C45A
 with sigma of 0.04
 C49-C50 \\sim C49A-C50A
 with sigma of 0.02
 C44-C46 \\sim C44A-C46A
 with sigma of 0.04
 C50-C51 \\sim C50A-C51A
 with sigma of 0.02
 Ni2-C42 \\sim Ni2-C42A
 with sigma of 0.04
 Ni2-C46 \\sim Ni2-C46A
 with sigma of 0.04
 C47-C49 \\sim C47A-C49A
 with sigma of 0.04
 Ni2-C47 \\sim Ni2-C47A
 with sigma of 0.04
 Ni2-C51 \\sim Ni2-C51A
 with sigma of 0.04
 F2-C43 \\sim F2A-C43A
 with sigma of 0.04
 F2-C45 \\sim F2A-C45A
 with sigma of 0.04
 C48-C50 \\sim C48A-C50A
 with sigma of 0.04
 N4-C46 \\sim N4A-C46A
 with sigma of 0.04
 N4-C48 \\sim N4A-C48A
 with sigma of 0.04
 N4-C50 \\sim N4A-C50A
 with sigma of 0.04
 C41-C43 \\sim C41A-C43A
 with sigma of 0.04
 C53-C52 \\sim C13-C12
 with sigma of 0.01
 O1-C53 \\sim O1-C12
 with sigma of 0.01
 Ni2-Cl2 \\sim Ni3-Cl3
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
F2 \\sim N4 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim
C47 \\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim F2A \\sim N4A \\sim C41A
\\sim C42A \\sim C43A \\sim C44A \\sim C45A \\sim C46A \\sim C47A \\sim C48A
\\sim C49A \\sim C50A \\sim C51A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Uanis(C44) = Uanis(C44A)
Uanis(C41) = Uanis(C41A)
Uanis(Ni2) = Uanis(Ni3)
4. Rigid body (RIGU) restrains
 F2, N4, C41, C42, C43, C44, C45, C46, C47, C48, C49, C50, C51, F2A, N4A, C41A,
  C42A, C43A, C44A, C45A, C46A, C47A, C48A, C49A, C50A, C51A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F2A)=Sof(N4A)=Sof(C41A)=Sof(C42A)=Sof(H42A)=Sof(C43A)=Sof(H43A)=Sof(C44A)=
 Sof(C45A)=Sof(H45A)=Sof(C46A)=Sof(C47A)=Sof(C48A)=Sof(H48A)=Sof(C49A)=
 Sof(H49A)=Sof(C50A)=Sof(H50A)=Sof(C51A)=Sof(H51A)=Sof(Ni3)=Sof(Cl3)=1-FVAR(1)
 Sof(Ni2)=Sof(Cl2)=Sof(F2)=Sof(N4)=Sof(C41)=Sof(C42)=Sof(H42)=Sof(C43)=
 Sof(H43)=Sof(C44)=Sof(C45)=Sof(H45)=Sof(C46)=Sof(C47)=Sof(C48)=Sof(H48)=
 Sof(C49)=Sof(H49)=Sof(C50)=Sof(H50)=Sof(C51)=Sof(H51)=FVAR(1)
 Sof(C02G)=Sof(H02A)=Sof(H02B)=Sof(H02C)=Sof(C02H)=Sof(H02D)=Sof(H02E)=
 Sof(H02F)=Sof(H75A)=1-FVAR(2)
 Sof(H75)=Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=Sof(C77)=Sof(H77A)=Sof(H77B)=
 Sof(H77C)=FVAR(2)
 Sof(Ni4)=Sof(Cl4)=1-FVAR(3)
 Sof(Ni1)=Sof(Cl1)=FVAR(3)
 Fixed Sof: O1(0.5) C12(0.5) H12A(0.5) H12B(0.5) C13(0.5) H13A(0.5) H13B(0.5)
 H13C(0.5) C52(0.5) H52A(0.5) H52B(0.5) H52C(0.5) C53(0.5) H53A(0.5) H53B(0.5)
6.a Ternary CH refined with riding coordinates:
 C23(H23), C26(H26), C35(H35), C38(H38), C63(H63), C66(H66), C75(H75A),
 C75(H75), C78(H78)
6.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C53(H53A,H53B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11), C15(H15),
 C16(H16), C19(H19), C20(H20), C21(H21), C31(H31), C32(H32), C33(H33), C42(H42),
  C43(H43), C45(H45), C48(H48), C49(H49), C50(H50), C51(H51), C55(H55),
 C56(H56), C59(H59), C60(H60), C61(H61), C71(H71), C72(H72), C73(H73),
 C42A(H42A), C43A(H43A), C45A(H45A), C48A(H48A), C49A(H49A), C50A(H50A),
 C51A(H51A)
6.d Idealised Me refined as rotating group:
 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), C02G(H02A,H02B,H02C), C02H(H02D,H02E,H02F), 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), C13(H13A,
 H13B,H13C), C52(H52A,H52B,H52C)
;
_shelx_res_checksum              15667
_shelx_hkl_checksum              33227
_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 784'
_olex2_submission_special_instructions 'No special instructions were received'