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_1567922
_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         'C29 H41 Ce O'
_chemical_formula_sum            'C29 H41 Ce O'
_chemical_formula_weight         545.74
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-11-03
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2021-11-09 deposited with the CCDC.	2022-11-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.1410(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.2557(2)
_cell_length_b                   8.82900(10)
_cell_length_c                   18.3743(2)
_cell_measurement_reflns_used    38581
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      31.1240
_cell_measurement_theta_min      2.2810
_cell_volume                     2545.56(5)
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(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 0.886
_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      0.0206015000
_diffrn_orient_matrix_UB_12      0.0158877000
_diffrn_orient_matrix_UB_13      -0.0287358000
_diffrn_orient_matrix_UB_21      -0.0376014000
_diffrn_orient_matrix_UB_22      -0.0203561000
_diffrn_orient_matrix_UB_23      -0.0277605000
_diffrn_orient_matrix_UB_31      -0.0143329000
_diffrn_orient_matrix_UB_32      0.0760904000
_diffrn_orient_matrix_UB_33      -0.0014200000
_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  0.0350
_diffrn_reflns_av_unetI/netI     0.0217
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.886
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            57712
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.886
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.952
_diffrn_reflns_theta_min         2.297
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.806
_exptl_absorpt_correction_T_max  0.935
_exptl_absorpt_correction_T_min  0.791
_exptl_absorpt_correction_type   analytical
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.424
_exptl_crystal_description       plate
_exptl_crystal_F_000             1124
_exptl_crystal_size_max          0.306
_exptl_crystal_size_mid          0.217
_exptl_crystal_size_min          0.096
_refine_diff_density_max         0.489
_refine_diff_density_min         -0.358
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     288
_refine_ls_number_reflns         7165
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0216
_refine_ls_R_factor_gt           0.0183
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0166P)^2^+1.1165P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0399
_refine_ls_wR_factor_ref         0.0407
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6522
_reflns_number_total             7165
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04192h1.cif
_cod_data_source_block           pla21005_refinalized
_cod_database_code               1567922
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C25 H33 Ce1'
_reflns_odcompleteness_completeness 99.95
_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:
 C19(H19A,H19B), C26(H26A,H26B), C29(H29A,H29B), C28(H28A,H28B), C27(H27A,H27B)
2.b Aromatic/amide H refined with riding coordinates:
 C21(H21), C22(H22), C10(H10), C1(H1), C25(H25), C23(H23), C24(H24)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C6(H6A,H6B,H6C), C15(H15A,H15B,H15C), C8(H8A,H8B,H8C),
 C18(H18A,H18B,H18C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C9(H9A,H9B,H9C)
;
_shelx_res_checksum              55274
_shelx_hkl_checksum              30224
_olex2_submission_original_sample_id PLA21005
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_full_max 1.261
_oxdiff_exptl_absorpt_empirical_full_min 0.795