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_1567928
_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 N2 Nd O, 1(C7 H8)'
_chemical_formula_sum            'C45 H63 N2 Nd O'
_chemical_formula_weight         792.21
_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             2021-11-01
_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                 112.9380(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.1816(2)
_cell_length_b                   22.1050(2)
_cell_length_c                   15.5529(2)
_cell_measurement_reflns_used    36361
_cell_measurement_temperature    100.00(13)
_cell_measurement_theta_max      76.0960
_cell_measurement_theta_min      3.6400
_cell_volume                     4173.45(10)
_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      100.00(13)
_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 0.990
_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 -32.00   0.50    1.26    --  -47.70 -60.00 -16.00  174
  2  \w    -24.00  64.00   0.50    1.26    --   47.70 -60.00 -16.00  176
  3  \w     32.00 119.00   0.50    1.26    --   47.70  60.00 123.00  174
  4  \w    -70.00 -14.00   0.50    5.06    --  -86.25  60.00 123.00  112
  5  \w   -158.00 -70.00   0.50    5.06    --  -86.25 -60.00 -16.00  176
  6  \w     92.00 178.00   0.50    5.06    --  107.75  60.00 123.00  172
  7  \w     36.00  71.00   0.50    5.06    --  107.75 -60.00 -16.00   70
  8  \w   -119.00 -87.00   0.50    1.26    --  -47.70-125.00  90.00   64
  9  \w    -64.00  24.00   0.50    1.26    --  -47.70  60.00 123.00  176
 10  \w    -22.00  28.00   0.50    1.26    --  -47.70  19.00  60.00  100
 11  \w   -119.00 -87.00   0.50    1.26    --  -47.70-125.00 150.00   64
 12  \w    -27.00  24.00   0.50    1.26    --   47.70 -19.00-120.00  102
 13  \w     34.00  95.00   0.50    1.26    --   47.70-125.00-150.00  122
 14  \w    -27.00  24.00   0.50    1.26    --   47.70 -19.00   0.00  102
 15  \w     82.00 120.00   0.50    1.26    --   47.70  57.00 -60.00   76
 16  \w    -71.00 -13.00   0.50    5.06    --  -86.25  61.00 -60.00  116
 17  \w    -71.00 -13.00   0.50    5.06    --  -86.25  61.00-180.00  116
 18  \w     35.00 106.00   0.50    5.06    --  107.75 -94.00  90.00  142
 19  \w     35.00 106.00   0.50    5.06    --  107.75 -94.00-120.00  142
 20  \w     94.00 178.00   0.50    5.06    --  107.75  15.00 120.00  168
 21  \w     95.00 178.00   0.50    5.06    --  107.75 125.00 -60.00  166
 22  \w     35.00 106.00   0.50    5.06    --  107.75 -96.00  43.67  142
 23  \w     91.00 178.00   0.50    5.06    --  107.75  61.00  37.60  174
 24  \w     45.00  70.00   0.50    5.06    --  107.75 -61.00 120.00   50
 25  \w     36.00  73.00   0.50    5.06    --  107.75 -61.00-120.00   74
 26  \w     35.00 104.00   0.50    5.06    --  107.75 -94.00   0.00  138
 27  \w    101.00 152.00   0.50    5.06    --  107.75  44.00-174.91  102
 28  \w     62.00 103.00   0.50    5.06    --  107.75 -94.00  60.00   82
 29  \w     43.00  97.00   0.50    5.06    --  107.75 -94.00 150.00  108
 30  \w     80.00 106.00   0.50    5.06    --  107.75 -94.00-180.00   52
 31  \w     36.00  73.00   0.50    5.06    --  107.75-106.00 -94.87   74
 32  \w     79.00 107.00   0.50    5.06    --  107.75-106.00 -94.87   56
 33  \w     68.00 111.00   0.50    5.06    --  107.75-125.00 -30.00   86
 34  \w     45.00 106.00   0.50    5.06    --  107.75-102.00 -29.29  122
 35  \w     95.00 167.00   0.50    5.06    --  107.75  44.00   9.89  144
 36  \w     96.00 123.00   0.50    5.06    --  107.75  45.00 -60.00   54
 37  \w     56.00 104.00   0.50    5.06    --  107.75 -94.00 -30.00   96
 38  \w     35.00 106.00   0.50    5.06    --  107.75 -94.00 120.00  142
 39  \w    152.00 178.00   0.50    5.06    --  107.75  45.00  60.00   52
 40  \w     96.00 177.00   0.50    5.06    --  107.75  61.00-150.00  162
 41  \w     39.00  66.00   0.50    5.06    --  107.75-125.00 -30.00   54
 42  \w     95.00 135.00   0.50    5.06    --  107.75  45.00  60.00   80
 43  \w     35.00  60.00   0.50    5.06    --  107.75 -61.00 -30.00   50
 44  \w     35.00  73.00   0.50    5.06    --  107.75-104.00-168.07   76
 45  \w     81.00 107.00   0.50    5.06    --  107.75-104.00-168.07   52
 46  \w     61.00 108.00   0.50    5.06    --  107.75-125.00 -90.00   94
 47  \w    103.00 133.00   0.50    5.06    --  107.75  77.00 -60.00   60
 48  \w    142.00 168.00   0.50    5.06    --  107.75  77.00 -60.00   52
 49  \w     43.00  97.00   0.50    5.06    --  107.75 -94.00 -90.00  108
 50  \w     36.00  73.00   0.50    5.06    --  107.75 -61.00-180.00   74
 51  \w     69.00 112.00   0.50    5.06    --  107.75-125.00  60.00   86
 52  \w     96.00 126.00   0.50    5.06    --  107.75 125.00-150.00   60
 53  \w    137.00 163.00   0.50    5.06    --  107.75 125.00-150.00   52
 54  \w     97.00 147.00   0.50    5.06    --  107.75 125.00  60.00  100
 55  \w    104.00 156.00   0.50    5.06    --  107.75  77.00   0.00  104
 56  \w     35.00  87.00   0.50    5.06    --  107.75-125.00-120.00  104
;
_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      0.1121458000
_diffrn_orient_matrix_UB_12      0.0292223000
_diffrn_orient_matrix_UB_13      0.0576698000
_diffrn_orient_matrix_UB_21      -0.0552593000
_diffrn_orient_matrix_UB_22      0.0399402000
_diffrn_orient_matrix_UB_23      0.0505635000
_diffrn_orient_matrix_UB_31      0.0220553000
_diffrn_orient_matrix_UB_32      -0.0490920000
_diffrn_orient_matrix_UB_33      0.0753979000
_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  0.0540
_diffrn_reflns_av_unetI/netI     0.0253
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            85278
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.797
_diffrn_reflns_theta_min         3.641
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.732
_exptl_absorpt_correction_T_max  0.646
_exptl_absorpt_correction_T_min  0.288
_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 blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.261
_exptl_crystal_description       block
_exptl_crystal_F_000             1660
_exptl_crystal_size_max          0.096
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.027
_refine_diff_density_max         0.590
_refine_diff_density_min         -1.308
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     524
_refine_ls_number_reflns         8821
_refine_ls_number_restraints     105
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.0369
_refine_ls_R_factor_gt           0.0334
_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^)+(0.0318P)^2^+5.7947P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0779
_refine_ls_wR_factor_ref         0.0795
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8258
_reflns_number_total             8821
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04192h1.cif
_cod_data_source_block           pla21043_refinalized
_cod_database_code               1567928
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Nd C25 H25 O1 N2'
_shelx_estimated_absorpt_t_max   0.779
_shelx_estimated_absorpt_t_min   0.455
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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. Restrained distances
 C017-C018 \\sim C43-C0
 with sigma of 0.02
 C017-C01A \\sim C43-C39
 with sigma of 0.02
 C018-C01C \\sim C0-C01D
 with sigma of 0.02
 C019-C01C \\sim C40-C01D
 with sigma of 0.04
 C01A-C01B \\sim C39-C42
 with sigma of 0.04
 C019-C01A \\sim C40-C39
 with sigma of 0.02
 C019-C01B \\sim C40-C42
 with sigma of 0.02
 C019-C41 \\sim C40-C1A
 with sigma of 0.02
 C01B-C01C \\sim C42-C01D
 with sigma of 0.02
 C01A-C41 \\sim C39-C1A
 with sigma of 0.04
 C017-C019 \\sim C43-C40
 with sigma of 0.04
 C017-C01C \\sim C43-C01D
 with sigma of 0.04
 C01B-C41 \\sim C42-C1A
 with sigma of 0.04
 C018-C01A \\sim C0-C39
 with sigma of 0.04
 C018-C01B \\sim C0-C42
 with sigma of 0.04
3. Rigid body (RIGU) restrains
 C017, C0, C018, C43, C01A, C39, C40, C1A, C41, C019, C01B, C42, C01D, C01C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C42)=Sof(H42)=Sof(C01D)=Sof(H01D)=Sof(C0)=Sof(H0)=Sof(C43)=Sof(H43)=
 Sof(C39)=Sof(H39)=Sof(C40)=Sof(C1A)=Sof(H1Aa)=Sof(H1Ab)=Sof(H1Ac)=1-FVAR(1)
 Sof(C017)=Sof(H017)=Sof(C018)=Sof(H018)=Sof(C019)=Sof(C01A)=Sof(H01A)=
 Sof(C01B)=Sof(H01B)=Sof(C01C)=Sof(H01C)=Sof(C41)=Sof(H41a)=Sof(H41b)=Sof(H41c)=
 FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C18(H18)
5.b Aromatic/amide H refined with riding coordinates:
 C15(H15), C5(H5), C3(H3), C21(H21), C16(H16), C30(H30), C017(H017),
 C018(H018), C01A(H01A), C01B(H01B), C01C(H01C), C42(H42), C01D(H01D), C0(H0),
 C43(H43), C39(H39)
5.c Idealised Me refined as rotating group:
 C26(H26a,H26b,H26c), C10(H10a,H10b,H10c), C29(H29a,H29b,H29c), C27(H27a,H27b,
 H27c), C8(H8a,H8b,H8c), C9(H9a,H9b,H9c), C12(H12a,H12b,H12c), C13(H13a,H13b,
 H13c), C20(H20a,H20b,H20c), C19(H19a,H19b,H19c), C28(H28a,H28b,H28c), C37(H37a,
 H37b,H37c), C36(H36a,H36b,H36c), C14(H14a,H14b,H14c), C35(H35a,H35b,H35c),
 C38(H38a,H38b,H38c), C41(H41a,H41b,H41c), C1A(H1Aa,H1Ab,H1Ac)
;
_shelx_res_checksum              37065
_shelx_hkl_checksum              98284
_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 1.414
_oxdiff_exptl_absorpt_empirical_full_min 0.586