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_1567930
_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         'C33 H49 Ce O'
_chemical_formula_sum            'C33 H49 Ce O'
_chemical_formula_weight         601.84
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2021-11-01
_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                93.2430(10)
_cell_angle_beta                 90.3960(10)
_cell_angle_gamma                107.6780(10)
_cell_formula_units_Z            2
_cell_length_a                   9.63360(10)
_cell_length_b                   10.07670(10)
_cell_length_c                   16.3047(2)
_cell_measurement_reflns_used    48178
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      31.0640
_cell_measurement_theta_min      2.1020
_cell_volume                     1505.14(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_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    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_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 0.858
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -67.00  28.00   0.50    5.00    --    4.95 -77.00 130.00  190
  2  \w    -28.00  67.00   0.50    5.00    --   -5.34  77.00-103.00  190
  3  \w    -78.00  17.00   0.50    5.00    --   -5.34 -77.00 130.00  190
  4  \w     11.00  51.00   0.50    5.00    --    4.95-122.00-128.47   80
  5  \w     -7.00  38.00   0.50    5.00    --    4.95 -99.00  90.00   90
  6  \w    -18.00  78.00   0.50    5.00    --    4.95  77.00-103.00  192
  7  \w    -68.00  17.00   0.50    5.00    --    4.95 -37.00 -30.00  170
  8  \w    -25.00  28.00   0.50    5.00    --    4.95 -77.00  30.00  106
  9  \w     -7.00  38.00   0.50    5.00    --    4.95 -99.00 -60.00   90
 10  \w    -18.00  68.00   0.50    5.00    --   -5.34  37.00 150.00  172
 11  \w    -18.00  70.00   0.50    5.00    --   -5.34  19.00  90.00  176
 12  \w    -18.00  70.00   0.50    5.00    --   -5.34  19.00-120.00  176
 13  \w    -17.00  43.00   0.50    5.00    --   -5.34  19.00   0.00  120
 14  \w    -70.00   3.00   0.50    5.00    --   -5.34 -19.00  30.00  146
 15  \w    -18.00  66.00   0.50    5.00    --   -5.34  30.00-173.31  168
 16  \w    -59.00  10.00   0.50    5.00    --   -5.34 -57.00-180.00  138
 17  \w    -80.00   3.00   0.50    5.00    --   -5.34 -19.00 -90.00  166
;
_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      0.0111474000
_diffrn_orient_matrix_UB_12      0.0464890000
_diffrn_orient_matrix_UB_13      0.0354544000
_diffrn_orient_matrix_UB_21      -0.0751412000
_diffrn_orient_matrix_UB_22      -0.0260814000
_diffrn_orient_matrix_UB_23      0.0086647000
_diffrn_orient_matrix_UB_31      0.0143197000
_diffrn_orient_matrix_UB_32      -0.0513553000
_diffrn_orient_matrix_UB_33      0.0238262000
_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  0.0451
_diffrn_reflns_av_unetI/netI     0.0277
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.858
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            67296
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.858
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.091
_diffrn_reflns_theta_min         2.125
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.534
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.703
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.104a (Rigaku Oxford Diffraction, 2021)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.328
_exptl_crystal_description       block
_exptl_crystal_F_000             626
_exptl_crystal_preparation       Luminescent
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.911
_refine_diff_density_min         -0.500
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     331
_refine_ls_number_reflns         8291
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0240
_refine_ls_R_factor_gt           0.0205
_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^)+(0.0183P)^2^+0.6402P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0438
_refine_ls_wR_factor_ref         0.0447
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7646
_reflns_number_total             8291
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04192h1.cif
_cod_data_source_block           pla21035_2_refinalized_equiv
_cod_database_code               1567930
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ce1 C25 H25 O1'
_shelx_estimated_absorpt_t_max   0.900
_shelx_estimated_absorpt_t_min   0.739
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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:
 C5(H5), C3(H3), C16(H16), C25(H25)
2.b Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C23(H23A,H23B,H23C), C22(H22A,H22B,H22C), C15(H15A,H15B,
 H15C), C14(H14A,H14B,H14C), C32(H32A,H32B,H32C), C11(H11A,H11B,H11C), C24(H24A,
 H24B,H24C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C), C13(H13A,H13B,H13C),
 C31(H31A,H31B,H31C), C21(H21A,H21B,H21C), C33(H33A,H33B,H33C), C30(H30A,H30B,
 H30C)
;
_shelx_res_checksum              98143
_shelx_hkl_checksum              5568
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.430
_oxdiff_exptl_absorpt_empirical_full_min 0.722