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_4519379
_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         'C15 H14 Bi F3'
_chemical_formula_sum            'C15 H14 Bi F3'
_chemical_formula_weight         460.24
_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             2021-05-24
_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                   17.435(3)
_cell_length_b                   9.004(2)
_cell_length_c                   18.230(4)
_cell_measurement_reflns_used    7532
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.14
_cell_measurement_theta_min      3.23
_cell_volume                     2861.8(10)
_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  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.994
_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  0.0522
_diffrn_reflns_av_unetI/netI     0.0347
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            21282
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.149
_diffrn_reflns_theta_min         2.336
_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    12.338
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.2661
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1497 before and 0.0616 after correction.
The Ratio of minimum to maximum transmission is 0.3569.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.136
_exptl_crystal_description       plate
_exptl_crystal_F_000             1712
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.692
_refine_diff_density_min         -1.986
_refine_diff_density_rms         0.138
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     174
_refine_ls_number_reflns         3159
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0353
_refine_ls_R_factor_gt           0.0248
_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^)+(0.0223P)^2^+3.8898P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0568
_refine_ls_wR_factor_ref         0.0612
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2534
_reflns_number_total             3159
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c05959_si_005.cif
_cod_data_source_block           hyvl100_0m_a
_cod_original_cell_volume        2861.8(11)
_cod_database_code               4519379
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.372
_shelx_estimated_absorpt_t_min   0.124
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C10(H10), C11(H11), C13(H13), C14(H14)
2.b Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C15(H15A,H15B,H15C)
;
_shelx_res_checksum              16526
_shelx_hkl_checksum              85388
_olex2_submission_special_instructions 'No special instructions were received'