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_1567929
_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         '2(C22 H34 Cl La O)'
_chemical_formula_sum            'C44 H68 Cl2 La2 O2'
_chemical_formula_weight         977.70
_chemical_name_systematic        3-La
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_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                 91.155(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.3760(4)
_cell_length_b                   15.3980(7)
_cell_length_c                   12.4103(4)
_cell_measurement_reflns_used    12724
_cell_measurement_temperature    99.99(14)
_cell_measurement_theta_max      74.0010
_cell_measurement_theta_min      4.5510
_cell_volume                     2173.44(14)
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(14)
_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 1.000
_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   -119.00 -28.00   0.50    3.05    --  -47.70 -70.00 -99.00  182
  2  \w    -68.00  25.00   0.50    3.05    --  -47.70  70.00  31.00  186
  3  \w    -24.00  68.00   0.50    3.05    --   47.70 -70.00 -99.00  184
  4  \w     28.00 120.00   0.50    3.05    --   47.70  70.00  31.00  184
  5  \w    -88.00 -13.00   0.50   10.00    --  -86.25  70.00  31.00  150
  6  \w   -159.00 -66.00   0.50   10.00    --  -86.25 -70.00 -99.00  186
  7  \w     88.00 178.00   0.50   10.00    --  107.75  70.00  31.00  180
  8  \w     35.00  90.00   0.50   10.00    --  107.75 -70.00 -99.00  110
  9  \w   -119.00 -82.00   0.50    3.05    --  -47.70 -57.00 -30.00   74
 10  \w    -63.00  25.00   0.50    3.05    --  -47.70  57.00-180.00  176
 11  \w   -119.00 -82.00   0.50    3.05    --  -47.70 -57.00 -60.00   74
 12  \w    -27.00  24.00   0.50    3.05    --   47.70 -19.00 -30.00  102
 13  \w     34.00  95.00   0.50    3.05    --   47.70-125.00 -90.00  122
 14  \w    -27.00  24.00   0.50    3.05    --   47.70 -19.00-180.00  102
 15  \w   -159.00-101.00   0.50   10.00    --  -86.25 -77.00 -30.00  116
 16  \w     35.00 106.00   0.50   10.00    --  107.75 -94.00   0.00  142
 17  \w     35.00  73.00   0.50   10.00    --  107.75 -61.00-180.00   76
 18  \w    101.00 178.00   0.50   10.00    --  107.75  77.00 -60.00  154
 19  \w     35.00 108.00   0.50   10.00    --  107.75-110.00  89.86  146
 20  \w     35.00 106.00   0.50   10.00    --  107.75 -94.00 -30.00  142
 21  \w     35.00 106.00   0.50   10.00    --  107.75 -97.00 -66.63  142
 22  \w     95.00 178.00   0.50   10.00    --  107.75  30.00-120.00  166
 23  \w     95.00 178.00   0.50   10.00    --  107.75 125.00  60.00  166
 24  \w     95.00 178.00   0.50   10.00    --  107.75  45.00   0.00  166
 25  \w     95.00 178.00   0.50   10.00    --  107.75 125.00  90.00  166
 26  \w     35.00 106.00   0.50   10.00    --  107.75 -94.00  30.00  142
 27  \w    101.00 178.00   0.50   10.00    --  107.75  77.00 -90.00  154
 28  \w     94.00 115.50   0.50   10.00    --  107.75  15.00-180.00   43
 29  \w     35.00  71.00   0.50   10.00    --  107.75-100.00 120.18   72
 30  \w     81.00 106.00   0.50   10.00    --  107.75-100.00 120.18   50
 31  \w     36.00  63.00   0.50   10.00    --  107.75 -94.00-150.00   54
 32  \w     65.00  91.00   0.50   10.00    --  107.75 -94.00-150.00   52
 33  \w     69.00 101.00   0.50   10.00    --  107.75-125.00 -30.00   64
 34  \w     43.00  72.00   0.50   10.00    --  107.75 -61.00-150.00   58
 35  \w     36.00  95.00   0.50   10.00    --  107.75-125.00  90.00  118
 36  \w     42.00  68.00   0.50   10.00    --  107.75 -61.00  90.00   52
 37  \w     56.00 106.00   0.50   10.00    --  107.75 -94.00-180.00  100
 38  \w     97.00 178.00   0.50   10.00    --  107.75  15.00 -90.00  162
 39  \w     99.00 145.00   0.50   10.00    --  107.75 125.00 120.00   92
 40  \w     38.00  64.00   0.50   10.00    --  107.75 -94.00-120.00   52
 41  \w     79.00 105.00   0.50   10.00    --  107.75 -94.00-120.00   52
 42  \w     96.00 167.00   0.50   10.00    --  107.75  15.00 -30.00  142
 43  \w     45.00 105.00   0.50   10.00    --  107.75 -94.00 150.00  120
 44  \w     40.00  72.00   0.50   10.00    --  107.75 -61.00-120.00   64
 45  \w     36.00  73.00   0.50   10.00    --  107.75 -61.00 150.00   74
 46  \w     75.00 107.00   0.50   10.00    --  107.75-105.00-106.36   64
 47  \w    123.00 149.00   0.50   10.00    --  107.75  77.00-180.00   52
 48  \w     61.00  87.00   0.50   10.00    --  107.75-125.00  30.00   52
 49  \w     36.00  72.00   0.50   10.00    --  107.75 -61.00  60.00   72
;
_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      -0.0988245000
_diffrn_orient_matrix_UB_12      0.0660080000
_diffrn_orient_matrix_UB_13      0.0212235000
_diffrn_orient_matrix_UB_21      -0.0779717000
_diffrn_orient_matrix_UB_22      -0.0445631000
_diffrn_orient_matrix_UB_23      -0.0865879000
_diffrn_orient_matrix_UB_31      -0.0499449000
_diffrn_orient_matrix_UB_32      -0.0606889000
_diffrn_orient_matrix_UB_33      0.0863043000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1585
_diffrn_reflns_av_unetI/netI     0.0559
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            40521
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.498
_diffrn_reflns_theta_min         4.577
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    16.351
_exptl_absorpt_correction_T_max  0.892
_exptl_absorpt_correction_T_min  0.745
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.104a (Rigaku Oxford Diffraction, 2021)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.494
_exptl_crystal_description       block
_exptl_crystal_F_000             992
_exptl_crystal_size_max          0.104
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.031
_refine_diff_density_max         1.057
_refine_diff_density_min         -1.551
_refine_diff_density_rms         0.138
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.136
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     234
_refine_ls_number_reflns         4453
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.136
_refine_ls_R_factor_all          0.0712
_refine_ls_R_factor_gt           0.0558
_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^)+(0.0706P)^2^+2.8834P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1345
_refine_ls_wR_factor_ref         0.1422
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3661
_reflns_number_total             4453
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04192h1.cif
_cod_data_source_block           pla21044_refinalized
_cod_database_code               1567929
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'La C25 H25 Cl'
_shelx_estimated_absorpt_t_max   0.631
_shelx_estimated_absorpt_t_min   0.281
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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), C20(H20A,H20B), C22(H22A,H22B), C21(H21A,H21B)
2.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C1(H1)
2.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C17(H17A,H17B,H17C), C9(H9A,H9B,H9C), C16(H16A,H16B,H16C),
 C6(H6A,H6B,H6C), C18(H18A,H18B,H18C), C15(H15A,H15B,H15C), C7(H7A,H7B,H7C)
;
_shelx_res_checksum              8836
_shelx_hkl_checksum              6488
_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 2.894
_oxdiff_exptl_absorpt_empirical_full_min 0.184