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_1567926
_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         'C38 H55 Ce N2 O'
_chemical_formula_sum            'C38 H55 Ce N2 O'
_chemical_formula_weight         695.96
_chemical_name_systematic        1-Ce
_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     iterative
_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                 89.9070(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.66730(10)
_cell_length_b                   17.46410(10)
_cell_length_c                   19.30400(10)
_cell_measurement_reflns_used    32656
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      28.7940
_cell_measurement_theta_min      3.6410
_cell_volume                     3596.23(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.54a (Rigaku OD, 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    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1042
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -50.00  51.00   1.00    5.00    --  -20.34  71.00 -28.00  101
  2  \w    -53.00  53.00   1.00    5.00    --  -20.34  37.00-120.00  106
  3  \w   -102.00 -35.00   1.00    5.00    --  -20.34 178.00-120.00   67
  4  \w    -95.00  55.00   1.00    5.00    --  -20.34   0.00-180.00  150
  5  \w    -39.00  13.00   1.00    5.00    --  -20.34 -77.00-150.00   52
  6  \w    -11.00  39.00   1.00    5.00    --   21.90  77.00-180.00   50
  7  \w    -11.00  39.00   1.00    5.00    --   21.90  77.00  90.00   50
  8  \w     -2.00  92.00   1.00    5.00    --   21.90  57.00 120.00   94
  9  \w    -39.00  13.00   1.00    5.00    --  -20.34 -77.00 -60.00   52
 10  \w    -53.00  39.00   1.00    5.00    --  -20.34  77.00   0.00   92
 11  \w   -102.00 -35.00   1.00    5.00    --  -20.34 178.00   0.00   67
 12  \w    -11.00  39.00   1.00    5.00    --   21.90  77.00-120.00   50
 13  \w    -11.00  39.00   1.00    5.00    --   21.90  77.00  30.00   50
 14  \w    -20.00  67.00   1.00    5.00    --   21.90 -99.00 -90.00   87
 15  \w     -2.00  90.00   1.00    5.00    --   21.90  57.00   0.00   92
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0663851000
_diffrn_orient_matrix_UB_12      0.0011700000
_diffrn_orient_matrix_UB_13      0.0018019000
_diffrn_orient_matrix_UB_21      -0.0038584000
_diffrn_orient_matrix_UB_22      0.0243134000
_diffrn_orient_matrix_UB_23      0.0293511000
_diffrn_orient_matrix_UB_31      -0.0005325000
_diffrn_orient_matrix_UB_32      -0.0325120000
_diffrn_orient_matrix_UB_33      0.0220256000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0362
_diffrn_reflns_av_unetI/netI     0.0180
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            72839
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         3.374
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.295
_exptl_absorpt_correction_T_max  0.926
_exptl_absorpt_correction_T_min  0.861
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.54a (Rigaku Oxford Diffraction, 2019)
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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.285
_exptl_crystal_description       block
_exptl_crystal_F_000             1452
_exptl_crystal_size_max          0.351
_exptl_crystal_size_mid          0.251
_exptl_crystal_size_min          0.164
_refine_diff_density_max         0.338
_refine_diff_density_min         -0.343
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     395
_refine_ls_number_reflns         7352
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0232
_refine_ls_R_factor_gt           0.0190
_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^)+(0.0164P)^2^+2.1295P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0434
_refine_ls_wR_factor_ref         0.0453
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6666
_reflns_number_total             7352
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04192h1.cif
_cod_data_source_block           p19070_refinalised
_cod_database_code               1567926
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C100 H100 Ce1 N2 O1'
_reflns_odcompleteness_completeness 99.71
_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 Ternary CH refined with riding coordinates:
 C18(H18)
2.b Aromatic/amide H refined with riding coordinates:
 C30(H30), C21(H21), C3(H3), C5(H5), C15(H15), C16(H16)
2.c Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C35(H35A,H35B,H35C), C26(H26A,H26B,
 H26C), C13(H13A,H13B,H13C), C36(H36A,H36B,H36C), C27(H27A,H27B,H27C), C14(H14A,
 H14B,H14C), C19(H19A,H19B,H19C), C12(H12A,H12B,H12C), C10(H10A,H10B,H10C),
 C20(H20A,H20B,H20C), C29(H29A,H29B,H29C), C28(H28A,H28B,H28C), C9(H9A,H9B,H9C),
  C8(H8A,H8B,H8C)
;
_shelx_res_checksum              59055
_shelx_hkl_checksum              50963
_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 1.126
_oxdiff_exptl_absorpt_empirical_full_min 0.917