Controlled monodefluorination and alkylation of C(sp3)-F Bonds by Lanthanide Photocatalysts: Importance of Metal – Ligand Cooperativity
Kynman, Amy E.; Elghanayan, Luca; Desnoyer, Addison; Yang, Yan; Severy, Laurent; Di Giuseppe, Andrea; Tilley, T. Don; Maron, Laurent; Arnold, Polly Louise; Chemical Science  (2022) –; doi:10.1039/D2SC04192H

data_1567925
_publ_section_title
;
 Controlled monodefluorination and alkylation of C(sp3)-F Bonds by
 Lanthanide Photocatalysts: Importance of Metal -- Ligand Cooperativity
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC04192H
_journal_year                    2022
_chemical_formula_moiety         'C23 H34 Ce F3 O4 S'
_chemical_formula_sum            'C23 H34 Ce F3 O4 S'
_chemical_formula_weight         603.68
_chemical_name_systematic        5-Ce
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'I -2ya'
_space_group_name_H-M_alt        'I 1 a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2021-12-08
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-01-04 deposited with the CCDC.	2022-11-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.821(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.5622(3)
_cell_length_b                   9.40990(10)
_cell_length_c                   16.2878(3)
_cell_measurement_reflns_used    21575
_cell_measurement_temperature    99.99(11)
_cell_measurement_theta_max      29.4540
_cell_measurement_theta_min      2.4800
_cell_volume                     2547.78(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.77a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.77a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.77a (Rigaku OD, 2020)'
_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_environment      N~2~
_diffrn_ambient_temperature      99.99(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.876
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0075481000
_diffrn_orient_matrix_UB_12      -0.0218671000
_diffrn_orient_matrix_UB_13      0.0435827000
_diffrn_orient_matrix_UB_21      -0.0080779000
_diffrn_orient_matrix_UB_22      0.0699134000
_diffrn_orient_matrix_UB_23      0.0112217000
_diffrn_orient_matrix_UB_31      -0.0412188000
_diffrn_orient_matrix_UB_32      -0.0176885000
_diffrn_orient_matrix_UB_33      -0.0095980000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0752
_diffrn_reflns_av_unetI/netI     0.0465
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.876
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            28412
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.790
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.870
_diffrn_reflns_theta_min         2.450
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.916
_exptl_absorpt_correction_T_max  0.839
_exptl_absorpt_correction_T_min  0.763
_exptl_absorpt_correction_type   analytical
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_density_diffrn    1.574
_exptl_crystal_description       block
_exptl_crystal_F_000             1220
_exptl_crystal_size_max          0.374
_exptl_crystal_size_mid          0.263
_exptl_crystal_size_min          0.203
_refine_diff_density_max         0.912
_refine_diff_density_min         -1.340
_refine_diff_density_rms         0.093
_refine_ls_abs_structure_details
;
 Flack x determined using 2516 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.033(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.928
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     297
_refine_ls_number_reflns         6338
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      0.928
_refine_ls_R_factor_all          0.0432
_refine_ls_R_factor_gt           0.0413
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1179
_refine_ls_wR_factor_ref         0.1200
_reflns_Friedel_coverage         0.802
_reflns_Friedel_fraction_full    0.957
_reflns_Friedel_fraction_max     0.704
_reflns_number_gt                5948
_reflns_number_total             6338
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04192h1.cif
_cod_data_source_block           pla21004_refinalized
_cod_database_code               1567925
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ce1 S1 O5 F3 C25 H35'
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.a Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C22(H22A,H22B), C19(H19A,H19B), C20(H20A,H20B)
2.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C3(H3)
2.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C16(H16A,H16B,H16C), C18(H18A,H18B,
 H18C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C)
;
_shelx_res_checksum              19777
_shelx_hkl_checksum              41900
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_full_max 1.419
_oxdiff_exptl_absorpt_empirical_full_min 0.691