Stabilizing Effect of Pre-equilibria: A Trifluoromethyl Complex as a CF2 Reservoir in Catalytic Olefin Difluorocarbenation
Louis-Goff, Thomas; Trinh, Huu Vinh; Chen, Eileen; Rheingold, Arnold L.; Ehm, Christian; Hyvl, Jakub; ACS Catalysis 12 (2022) 3719–3730; doi:10.1021/acscatal.1c05959

data_4519380
_publ_section_title
;
 Stabilizing Effect of Pre-equilibria: A Trifluoromethyl Complex as a CF2
 Reservoir in Catalytic Olefin Difluorocarbenation
;
_journal_issue                   6
_journal_name_full               'ACS Catalysis'
_journal_page_first              3719
_journal_page_last               3730
_journal_paper_doi               10.1021/acscatal.1c05959
_journal_volume                  12
_journal_year                    2022
_chemical_formula_moiety         'C16 H14 Bi F3'
_chemical_formula_sum            'C16 H14 Bi F3'
_chemical_formula_weight         472.25
_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     direct
_audit_creation_date             2021-05-21
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.7284(4)
_cell_length_b                   9.7063(4)
_cell_length_c                   30.3122(14)
_cell_measurement_reflns_used    9924
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.11
_cell_measurement_theta_min      2.69
_cell_volume                     2862.3(2)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 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  0.0391
_diffrn_reflns_av_unetI/netI     0.0207
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            30084
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.142
_diffrn_reflns_theta_min         2.488
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           50.0
_diffrn_source_power             2.5
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    12.339
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.4120
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1330 before and 0.0482 after correction.
The Ratio of minimum to maximum transmission is 0.5526.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.192
_exptl_crystal_description       plate
_exptl_crystal_F_000             1760
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.859
_refine_diff_density_min         -1.304
_refine_diff_density_rms         0.108
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.151
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     181
_refine_ls_number_reflns         3151
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.151
_refine_ls_R_factor_all          0.0254
_refine_ls_R_factor_gt           0.0211
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+7.3414P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0380
_refine_ls_wR_factor_ref         0.0391
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2814
_reflns_number_total             3151
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c05959_si_006.cif
_cod_data_source_block           hyvl104_a
_cod_database_code               4519380
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.525
_shelx_estimated_absorpt_t_min   0.192
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C9(H9A,H9B), C8(H8A,H8B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6), C5(H5), C4(H4), C15(H15), C14(H14), C13(H13), C12(H12)
;
_shelx_res_checksum              5991
_shelx_hkl_checksum              77773
_olex2_submission_special_instructions 'No special instructions were received'