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_1567923
_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         'C80 H116 Mg2 N8 O4, C6 H14, C6 H12'
_chemical_formula_sum            'C92 H142 Mg2 N8 O4'
_chemical_formula_weight         1472.75
_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     dual
_audit_creation_date             2021-11-04
_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                99.0740(10)
_cell_angle_beta                 98.3570(10)
_cell_angle_gamma                91.4750(10)
_cell_formula_units_Z            2
_cell_length_a                   13.91760(10)
_cell_length_b                   17.0140(3)
_cell_length_c                   19.2571(3)
_cell_measurement_reflns_used    38418
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      77.0280
_cell_measurement_theta_min      2.6450
_cell_volume                     4449.56(11)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (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(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_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    -81.00  14.00   0.50    1.16    --  -47.95 102.00 126.00  190
  2  \w      8.00  83.00   0.50    1.16    --   47.95-102.00  23.00  150
  3  \w    -81.00 -13.00   0.50    4.64    --  -86.25 102.00 126.00  136
  4  \w   -159.00 -85.00   0.50    4.64    --  -86.25-102.00  23.00  148
  5  \w     35.00 107.00   0.50    4.64    --  107.75-102.00  23.00  144
  6  \w    106.00 178.00   0.50    4.64    --  107.75 102.00 126.00  144
  7  \w   -119.00 -82.00   0.50    1.16    --  -47.95 -57.00 -60.00   74
  8  \w    -22.00  28.00   0.50    1.16    --  -47.95  19.00 -90.00  100
  9  \w   -119.00 -82.00   0.50    1.16    --  -47.95 -57.00 -90.00   74
 10  \w    -22.00  28.00   0.50    1.16    --  -47.95  19.00  60.00  100
 11  \w   -119.00 -82.00   0.50    1.16    --  -47.95 -57.00 -30.00   74
 12  \w    -22.00  28.00   0.50    1.16    --  -47.95  19.00 -30.00  100
 13  \w   -120.00 -87.00   0.50    1.16    --  -47.95-125.00-120.00   66
 14  \w   -120.00 -87.00   0.50    1.16    --  -47.95-125.00  90.00   66
 15  \w     82.00 119.00   0.50    1.16    --   47.95  57.00 120.00   74
 16  \w    -23.00  63.00   0.50    1.16    --   47.95 -57.00  90.00  172
 17  \w     82.00 119.00   0.50    1.16    --   47.95  57.00 150.00   74
 18  \w    -26.00  24.00   0.50    1.16    --   47.95 -19.00 120.00  100
 19  \w   -159.00 -91.00   0.50    4.64    --  -86.25 -61.00 120.00  136
 20  \w    -49.00 -14.00   0.50    4.64    --  -86.25  45.00  60.00   70
 21  \w    -49.00 -14.00   0.50    4.64    --  -86.25  45.00  90.00   70
 22  \w     95.00 178.00   0.50    4.64    --  107.75 125.00-150.00  166
 23  \w    110.00 136.00   0.50    4.64    --  107.75  15.00 120.00   52
 24  \w    102.00 174.00   0.50    4.64    --  107.75  77.00  90.00  144
 25  \w     36.00  64.00   0.50    4.64    --  107.75 -61.00  30.00   56
 26  \w     39.00 106.00   0.50    4.64    --  107.75 -98.00 -58.76  134
 27  \w     95.00 145.00   0.50    4.64    --  107.75 125.00   0.00  100
 28  \w     35.00  73.00   0.50    4.64    --  107.75 -61.00-180.00   76
 29  \w     62.00 106.00   0.50    4.64    --  107.75 -94.00 120.00   88
 30  \w     35.00  85.00   0.50    4.64    --  107.75-125.00 -90.00  100
 31  \w     36.00  63.00   0.50    4.64    --  107.75 -94.00  60.00   54
 32  \w     69.00 106.00   0.50    4.64    --  107.75 -94.00  60.00   74
 33  \w     57.00 102.00   0.50    4.64    --  107.75 -94.00 -90.00   90
 34  \w    151.00 178.00   0.50    4.64    --  107.75  15.00 120.00   54
 35  \w     36.00 105.00   0.50    4.64    --  107.75 -94.00-180.00  138
 36  \w     35.00  89.00   0.50    4.64    --  107.75-125.00 150.00  108
 37  \w     51.00  77.00   0.50    4.64    --  107.75 -94.00  90.00   52
 38  \w     38.00  69.00   0.50    4.64    --  107.75 -94.00 -30.00   62
 39  \w     39.00  65.00   0.50    4.64    --  107.75-125.00-180.00   52
 40  \w     98.00 176.00   0.50    4.64    --  107.75  62.00 163.19  156
 41  \w     95.00 123.00   0.50    4.64    --  107.75 125.00 -60.00   56
 42  \w     64.00 102.00   0.50    4.64    --  107.75 -94.00 150.00   76
 43  \w     41.00  73.00   0.50    4.64    --  107.75 -61.00  60.00   64
 44  \w     37.00  84.00   0.50    4.64    --  107.75-125.00 -60.00   94
 45  \w     48.00  89.00   0.50    4.64    --  107.75-125.00 -30.00   82
 46  \w     40.00 100.00   0.50    4.64    --  107.75 -94.00  30.00  120
 47  \w    133.00 162.00   0.50    4.64    --  107.75 125.00 -60.00   58
 48  \w    120.00 177.00   0.50    4.64    --  107.75  45.00  60.00  114
 49  \w     37.00 108.00   0.50    4.64    --  107.75-125.00  30.00  142
 50  \w     81.00 106.00   0.50    4.64    --  107.75 -94.00 -30.00   50
 51  \w     35.00  60.00   0.50    4.64    --  107.75 -94.00 150.00   50
 52  \w     80.00 106.00   0.50    4.64    --  107.75 -94.00  90.00   52
 53  \w     96.00 159.00   0.50    4.64    --  107.75 125.00  90.00  126
 54  \w    109.00 178.00   0.50    4.64    --  107.75  61.00-150.00  138
 55  \w    104.00 134.00   0.50    4.64    --  107.75 125.00  60.00   60
 56  \w     53.00 106.00   0.50    4.64    --  107.75 -94.00-150.00  106
 57  \w     62.00 106.00   0.50    4.64    --  107.75 -94.00-120.00   88
 58  \w     36.00  66.00   0.50    4.64    --  107.75 -77.00 -90.00   60
 59  \w     93.00 130.00   0.50    4.64    --  107.75 -77.00 -90.00   74
 60  \w     40.00  67.00   0.50    4.64    --  107.75 -61.00 120.00   54
 61  \w    126.00 152.00   0.50    4.64    --  107.75  77.00 150.00   52
 62  \w    125.00 178.00   0.50    4.64    --  107.75  61.00-180.00  106
;
_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      0.0316996000
_diffrn_orient_matrix_UB_12      0.0798836000
_diffrn_orient_matrix_UB_13      -0.0199787000
_diffrn_orient_matrix_UB_21      -0.0550008000
_diffrn_orient_matrix_UB_22      -0.0257298000
_diffrn_orient_matrix_UB_23      -0.0759754000
_diffrn_orient_matrix_UB_31      -0.0922943000
_diffrn_orient_matrix_UB_32      0.0372206000
_diffrn_orient_matrix_UB_33      0.0233595000
_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  0.0443
_diffrn_reflns_av_unetI/netI     0.0330
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            91809
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.498
_diffrn_reflns_theta_min         2.633
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.638
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.682
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.112a (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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.099
_exptl_crystal_description       needle
_exptl_crystal_F_000             1612
_exptl_crystal_size_max          0.164
_exptl_crystal_size_mid          0.149
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.502
_refine_diff_density_min         -0.345
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1077
_refine_ls_number_reflns         18131
_refine_ls_number_restraints     284
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0585
_refine_ls_R_factor_gt           0.0494
_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^)+(0.0510P)^2^+2.6857P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1188
_refine_ls_wR_factor_ref         0.1238
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15741
_reflns_number_total             18131
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04192h1.cif
_cod_data_source_block           pla21054_refinalized
_cod_database_code               1567923
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Mg2 O4 N8 C80 H120'
_shelx_estimated_absorpt_t_max   0.945
_shelx_estimated_absorpt_t_min   0.903
_reflns_odcompleteness_completeness 99.57
_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. Restrained distances
 C89-C90 = C90-C91 = C91-C92 = C92-C93 = C93-C94
 1.52 with sigma of 0.02
 C90-C92 = C91-C93
 2.54 with sigma of 0.04
 C89-C91 = C92-C94
 2.53 with sigma of 0.04
 C64-C72 \\sim C64-C71
 with sigma of 0.02
 C77-C79 \\sim C74-C78
 with sigma of 0.04
 C72-C77 \\sim C71-C74
 with sigma of 0.02
 C72-C76 \\sim C71-C75
 with sigma of 0.02
 C72-C79 \\sim C71-C78
 with sigma of 0.02
 C77-C76 \\sim C74-C75
 with sigma of 0.04
 C76-C79 \\sim C75-C78
 with sigma of 0.04
 C64-C77 \\sim C64-C74
 with sigma of 0.04
 C64-C76 \\sim C64-C75
 with sigma of 0.04
 C64-C79 \\sim C64-C78
 with sigma of 0.04
 C89-C90 \\sim C90-C91 \\sim C91-C92 \\sim C92-C93 \\sim C93-C94
 with sigma of 0.02
 C89-C91 \\sim C91-C93 \\sim C90-C92 \\sim C92-C94
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C89 \\sim C90 \\sim C91 \\sim C92 \\sim C93 \\sim C94: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C89 \\sim C90 \\sim C88 \\sim C91 \\sim C95 \\sim C92 \\sim C86 \\sim C93 \\sim
C87 \\sim C94 \\sim C73: within 1.7A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 1.7A
Uanis(C89) \\sim Ueq, Uanis(C90) \\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(C91)
\\sim Ueq, Uanis(C95) \\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C86) \\sim Ueq,
Uanis(C93) \\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(C94) \\sim Ueq, Uanis(C73)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
4. Rigid body (RIGU) restrains
 C74, C77, C75, C76, C72, C71, C78, C79
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C89, C90, C91, C92, C93, C94
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(H78C)=
 Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(H75C)=Sof(C71)=1-FVAR(1)
 Sof(C72)=Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(H77C)=Sof(C76)=Sof(H76A)=Sof(H76B)=
 Sof(H76C)=Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(H79C)=FVAR(1)
 Fixed Sof: H89A(0.5) H89B(0.5) H89C(0.5) C90(0.5) H90A(0.5) H90B(0.5)
 C91(0.5) H91A(0.5) H91B(0.5) C92(0.5) H92A(0.5) H92B(0.5) C93(0.5) H93A(0.5)
 H93B(0.5) C94(0.5) H94A(0.5) H94B(0.5) H94C(0.5) C87(0.5) H87A(0.5) H87B(0.5)
 C88(0.5) H88(0.5) C86(0.5) H86A(0.5) H86B(0.5) C95(0.5) H95A(0.5) H95B(0.5)
 C73(0.5) H73A(0.5) H73B(0.5) H73C(0.5)
6.a Ternary CH refined with riding coordinates:
 C58(H58), C83(H83), C38(H38), C18(H18)
6.b Secondary CH2 refined with riding coordinates:
 C02K(H02A,H02B), C02L(H02C,H02D), C02N(H02H,H02I), C02O(H02J,H02K), C90(H90A,
 H90B), C91(H91A,H91B), C92(H92A,H92B), C93(H93A,H93B), C87(H87A,H87B),
 C86(H86A,H86B), C95(H95A,H95B)
6.c Aromatic/amide H refined with riding coordinates:
 C55(H55), C3(H3), C5(H5), C45(H45), C56(H56), C25(H25), C43(H43), C80(H80),
 C23(H23), C81(H81), C35(H35), C65(H65), C36(H36), C15(H15), C16(H16), C63(H63),
  C88(H88)
6.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C8(H8A,H8B,H8C), C48(H48A,H48B,H48C),
 C59(H59A,H59B,H59C), C84(H84A,H84B,H84C), C12(H12A,H12B,H12C), C85(H85A,H85B,
 H85C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C60(H60A,H60B,H60C), C69(H69A,
 H69B,H69C), C50(H50A,H50B,H50C), C49(H49A,H49B,H49C), C29(H29A,H29B,H29C),
 C28(H28A,H28B,H28C), C40(H40A,H40B,H40C), C68(H68A,H68B,H68C), C39(H39A,H39B,
 H39C), C70(H70A,H70B,H70C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C19(H19A,
 H19B,H19C), C54(H54A,H54B,H54C), C53(H53A,H53B,H53C), C33(H33A,H33B,H33C),
 C20(H20A,H20B,H20C), C34(H34A,H34B,H34C), C52(H52A,H52B,H52C), C02M(H02E,H02F,
 H02G), C02Q(H02L,H02M,H02N), C77(H77A,H77B,H77C), C76(H76A,H76B,H76C),
 C79(H79A,H79B,H79C), C74(H74A,H74B,H74C), C78(H78A,H78B,H78C), C75(H75A,H75B,
 H75C), C89(H89A,H89B,H89C), C94(H94A,H94B,H94C), C73(H73A,H73B,H73C)
;
_shelx_res_checksum              29352
_shelx_hkl_checksum              67437
_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 2.516
_oxdiff_exptl_absorpt_empirical_full_min 0.401