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_1567920
_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         'C37 H57 Ce O2'
_chemical_formula_sum            'C37 H57 Ce O2'
_chemical_formula_weight         673.94
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_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                90
_cell_angle_beta                 107.666(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.4698(2)
_cell_length_b                   12.0899(3)
_cell_length_c                   13.9747(3)
_cell_measurement_reflns_used    24821
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      31.1270
_cell_measurement_theta_min      2.0230
_cell_volume                     1685.48(7)
_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 0.9997
_diffrn_measured_fraction_theta_max 0.8226
_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    -25.00  28.00   0.50   10.00    --    4.95 -77.00 -90.00  106
  2  \w      7.00  32.00   0.50   10.00    --    4.95-117.00-140.52   50
  3  \w     -7.00  28.00   0.50   10.00    --   -5.34 -99.00 -30.00   70
  4  \w     -7.00  38.00   0.50   10.00    --    4.95 -99.00  60.00   90
  5  \w    -25.00  28.00   0.50   10.00    --    4.95 -77.00 120.00  106
  6  \w    -18.00  67.00   0.50   10.00    --   -5.34  48.00 117.00  170
  7  \w    -10.00  59.00   0.50   10.00    --    4.95  57.00 150.00  138
  8  \w    -59.00  20.00   0.50   10.00    --    4.95 -57.00  30.00  158
  9  \w    -10.00  59.00   0.50   10.00    --    4.95  57.00 -90.00  138
 10  \w    -10.00  59.00   0.50   10.00    --    4.95  57.00-150.00  138
 11  \w    -78.00   9.00   0.50   10.00    --   -5.34 -48.00 -30.00  174
;
_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      -0.0501958000
_diffrn_orient_matrix_UB_12      -0.0125904000
_diffrn_orient_matrix_UB_13      0.0228685000
_diffrn_orient_matrix_UB_21      0.0073111000
_diffrn_orient_matrix_UB_22      0.0534921000
_diffrn_orient_matrix_UB_23      0.0217202000
_diffrn_orient_matrix_UB_31      -0.0497981000
_diffrn_orient_matrix_UB_32      0.0205874000
_diffrn_orient_matrix_UB_33      -0.0429222000
_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  0.0419
_diffrn_reflns_av_unetI/netI     0.0359
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.873
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            39085
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.823
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.969
_diffrn_reflns_theta_min         2.041
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.380
_exptl_absorpt_correction_T_max  0.834
_exptl_absorpt_correction_T_min  0.769
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.77a (Rigaku Oxford Diffraction, 2020)
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 light yellow'
_exptl_crystal_density_diffrn    1.328
_exptl_crystal_description       plate
_exptl_crystal_F_000             706
_exptl_crystal_preparation       Luminescent
_exptl_crystal_size_max          0.272
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.206
_refine_diff_density_max         0.686
_refine_diff_density_min         -0.388
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 3517 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.017(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     376
_refine_ls_number_reflns         8812
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0270
_refine_ls_R_factor_gt           0.0226
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0210P)^2^+0.2392P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0464
_refine_ls_wR_factor_ref         0.0474
_reflns_Friedel_coverage         0.808
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.768
_reflns_number_gt                8160
_reflns_number_total             8812
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04192h1.cif
_cod_data_source_block           pla21006_refinalized
_cod_database_code               1567920
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ce1 C50 H30 O2'
_shelx_estimated_absorpt_t_max   0.764
_shelx_estimated_absorpt_t_min   0.705
_diffrn_oxdiff_digest_frames
;
017af61608cbba08553cc3d281aca3f71d013388a9e
;
_diffrn_oxdiff_digest_hkl
;
016f0f9400618600167d8444f0d4d217154076
;
_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, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B), C34(H34A,H34B)
2.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C3(H3), C16(H16), C25(H25)
2.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C14(H14A,H14B,H14C), C13(H13A,H13B,H13C), C11(H11A,H11B,
 H11C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C), C9(H9A,H9B,H9C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C30(H30A,
 H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C)
;
_shelx_res_checksum              66715
_shelx_hkl_checksum              48939
_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 1.653
_oxdiff_exptl_absorpt_empirical_full_min 0.817