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_1567927
_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         'C54 H72 Mg2 N4 O2, 0.5(C7 H8)'
_chemical_formula_sum            'C57.5 H76 Mg2 N4 O2'
_chemical_formula_weight         903.84
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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             2021-11-01
_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                 104.996(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.1713(2)
_cell_length_b                   18.0503(2)
_cell_length_c                   23.2076(4)
_cell_measurement_reflns_used    40071
_cell_measurement_temperature    99.99(13)
_cell_measurement_theta_max      75.9820
_cell_measurement_theta_min      3.1250
_cell_volume                     5329.61(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(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 0.987
_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   -120.00 -73.00   0.50    2.69    --  -47.45-125.00 178.00   94
  2  \w    -86.00 -13.00   0.50    2.69    --  -47.45 125.00-103.00  146
  3  \w   -120.00 -60.00   0.50    2.69    --  -47.45-145.00  12.00  120
  4  \w   -101.00 -23.00   0.50    2.69    --  -47.45 145.00  63.00  156
  5  \w     45.00 107.00   0.50    2.69    --   47.45-145.00  12.00  124
  6  \w     34.00  95.00   0.50    2.69    --   47.45-125.00 178.00  122
  7  \w    -86.00 -13.00   0.50   10.74    --  -86.25 125.00-103.00  146
  8  \w   -153.00 -60.00   0.50   10.74    --  -86.25-145.00  12.00  186
  9  \w   -101.00 -23.00   0.50   10.74    --  -86.25 145.00  63.00  156
 10  \w   -159.00 -73.00   0.50   10.74    --  -86.25-125.00 178.00  172
 11  \w     95.00 155.00   0.50   10.74    --  107.75 125.00-103.00  120
 12  \w    100.00 126.00   0.50   10.74    --  107.75-145.00  12.00   52
 13  \w     49.00  74.00   0.50   10.74    --  107.75-125.00 178.00   50
 14  \w    100.00 127.00   0.50   10.74    --  107.75 145.00  63.00   54
 15  \w   -119.00 -86.00   0.50    2.69    --  -47.45 -57.00-120.00   66
 16  \w    -16.00  23.00   0.50    2.69    --  -47.45  19.00 -30.00   78
 17  \w   -118.00 -83.00   0.50    2.69    --  -47.45 -57.00 120.00   70
 18  \w    -13.00  14.00   0.50    2.69    --  -47.45  19.00   0.00   54
 19  \w   -119.00 -90.00   0.50    2.69    --  -47.45-125.00  30.00   58
 20  \w   -116.00 -84.00   0.50    2.69    --  -47.45 -57.00 -30.00   64
 21  \w    -21.00  25.00   0.50    2.69    --  -47.45  19.00  30.00   92
 22  \w   -120.00 -87.00   0.50    2.69    --  -47.45 -57.00  90.00   66
 23  \w   -116.00 -82.00   0.50    2.69    --  -47.45 -57.00  30.00   68
 24  \w     83.00 114.00   0.50    2.69    --   47.45  57.00 -90.00   62
 25  \w     82.00 107.00   0.50    2.69    --   47.45  57.00-150.00   50
 26  \w   -146.00-119.00   0.50   10.74    --  -86.25 -54.00  55.00   54
 27  \w   -109.00 -72.00   0.50   10.74    --  -86.25 -54.00  55.00   74
 28  \w     35.00  92.00   0.50   10.74    --  107.75-125.00 -90.00  114
 29  \w     99.00 128.00   0.50   10.74    --  107.75 -77.00  90.00   58
 30  \w     36.00  90.00   0.50   10.74    --  107.75 -77.00 -30.00  108
 31  \w     47.00  73.00   0.50   10.74    --  107.75 -61.00-120.00   52
 32  \w    124.00 177.00   0.50   10.74    --  107.75  77.00-150.00  106
 33  \w    103.00 133.00   0.50   10.74    --  107.75  77.00-120.00   60
 34  \w     45.00  73.00   0.50   10.74    --  107.75 -61.00-150.00   56
 35  \w     61.00 101.00   0.50   10.74    --  107.75 -94.00 150.00   80
 36  \w     37.00  70.00   0.50   10.74    --  107.75 -61.00 -90.00   66
 37  \w     44.00  82.00   0.50   10.74    --  107.75-125.00 -60.00   76
 38  \w     41.00 112.00   0.50   10.74    --  107.75-125.00  60.00  142
 39  \w     97.00 178.00   0.50   10.74    --  107.75  51.00  59.97  162
 40  \w     40.00  67.00   0.50   10.74    --  107.75 -77.00  90.00   54
 41  \w     95.00 177.00   0.50   10.74    --  107.75  15.00 -30.00  164
 42  \w     52.00 106.00   0.50   10.74    --  107.75 -94.00 -60.00  108
 43  \w     92.00 166.00   0.50   10.74    --  107.75  61.00 150.00  148
 44  \w     35.00  68.00   0.50   10.74    --  107.75 -94.00 -90.00   66
 45  \w     78.00 106.00   0.50   10.74    --  107.75-100.00-173.99   56
 46  \w     96.00 175.00   0.50   10.74    --  107.75  45.00-180.00  158
 47  \w     36.00  71.00   0.50   10.74    --  107.75 -61.00 150.00   70
 48  \w     45.00 106.00   0.50   10.74    --  107.75 -94.00  90.00  122
 49  \w     36.00  87.00   0.50   10.74    --  107.75-125.00 150.00  102
 50  \w     48.00  74.00   0.50   10.74    --  107.75-100.00-173.99   52
 51  \w     69.00 106.00   0.50   10.74    --  107.75 -94.00 -30.00   74
 52  \w     96.00 161.00   0.50   10.74    --  107.75  15.00  90.00  130
 53  \w     38.00  67.00   0.50   10.74    --  107.75 -94.00 -30.00   58
 54  \w     74.00 104.00   0.50   10.74    --  107.75 -94.00 -90.00   60
 55  \w     36.00  67.00   0.50   10.74    --  107.75 -97.00-139.23   62
 56  \w     81.00 106.00   0.50   10.74    --  107.75 -97.00-139.23   50
 57  \w     35.00 107.00   0.50   10.74    --  107.75-108.00-123.36  144
 58  \w     38.00  73.00   0.50   10.74    --  107.75 -61.00  90.00   70
 59  \w     65.00 106.00   0.50   10.74    --  107.75 -99.00  72.29   82
 60  \w     95.00 123.00   0.50   10.74    --  107.75  15.00   0.00   56
 61  \w    130.00 175.00   0.50   10.74    --  107.75  15.00   0.00   90
 62  \w     78.00 106.00   0.50   10.74    --  107.75 -94.00-120.00   56
 63  \w     35.00 107.00   0.50   10.74    --  107.75-102.00  48.76  144
 64  \w     66.00 106.00   0.50   10.74    --  107.75 -97.00 126.16   80
 65  \w    105.00 145.00   0.50   10.74    --  107.75  77.00  90.00   80
 66  \w     46.00  89.00   0.50   10.74    --  107.75-125.00  30.00   86
 67  \w     37.00  68.00   0.50   10.74    --  107.75 -61.00  30.00   62
;
_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      0.0967585000
_diffrn_orient_matrix_UB_12      0.0001044000
_diffrn_orient_matrix_UB_13      0.0540905000
_diffrn_orient_matrix_UB_21      -0.0722507000
_diffrn_orient_matrix_UB_22      0.0097866000
_diffrn_orient_matrix_UB_23      0.0421678000
_diffrn_orient_matrix_UB_31      -0.0081990000
_diffrn_orient_matrix_UB_32      -0.0847574000
_diffrn_orient_matrix_UB_33      0.0048932000
_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  0.0709
_diffrn_reflns_av_unetI/netI     0.0316
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            104258
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.414
_diffrn_reflns_theta_min         3.143
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.731
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.594
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.104a (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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.126
_exptl_crystal_description       block
_exptl_crystal_F_000             1956
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.842
_refine_diff_density_min         -0.414
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     699
_refine_ls_number_reflns         11176
_refine_ls_number_restraints     524
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0708
_refine_ls_R_factor_gt           0.0598
_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^)+(0.0844P)^2^+4.5565P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1611
_refine_ls_wR_factor_ref         0.1696
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9334
_reflns_number_total             11176
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04192h1.cif
_cod_data_source_block           pla21042_refinalized
_cod_original_formula_sum        'C57.50 H76 Mg2 N4 O2'
_cod_database_code               1567927
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Mg2 O2 N4 C57 H72'
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.868
_reflns_odcompleteness_completeness 99.81
_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
 C56-C57 = C56-C61 = C58-C59
 1.39 with sigma of 0.02
 C57-C58 = C59-C60 = C60-C61
 1.38 with sigma of 0.02
 C55-C56
 1.51 with sigma of 0.02
 C23A-C24A = C25A-C26A = C26A-C27A
 1.38 with sigma of 0.02
 C22A-C23A = C22A-C27A = C24A-C25A
 1.39 with sigma of 0.02
 C58-C60 = C59-C61
 2.4 with sigma of 0.04
 C57-C59
 2.39 with sigma of 0.04
 C55-C57 = C55-C61
 2.52 with sigma of 0.04
 C56-C58
 2.42 with sigma of 0.04
 C56-C60
 2.41 with sigma of 0.04
 C24A-C26A = C25A-C27A
 2.4 with sigma of 0.04
 C22A-C26A
 2.41 with sigma of 0.04
 C22A-C24A
 2.42 with sigma of 0.04
 C23A-C25A
 2.39 with sigma of 0.04
 C11-C12A \\sim C11-C13B
 with sigma of 0.02
 C11-C13A \\sim C11-C14B
 with sigma of 0.02
 C11-C14A \\sim C11-C12B
 with sigma of 0.02
 C56-C60 \\sim C56-C58 \\sim C61-C59 \\sim C57-C61 \\sim C58-C60 \\sim C57-C59
 with sigma of 0.04
 C55-C61 \\sim C55-C57
 with sigma of 0.04
 C56-C57 \\sim C57-C58 \\sim C58-C59 \\sim C59-C60 \\sim C60-C61 \\sim C61-C56
 with sigma of 0.02
 C22A-C23A \\sim C23A-C24A \\sim C24A-C25A \\sim C25A-C26A \\sim C26A-C27A
\\sim C27A-C22A
 with sigma of 0.02
 C22A-C26A \\sim C22A-C24A \\sim C27A-C25A \\sim C23A-C27A \\sim C24A-C26A
\\sim C23A-C25A
 with sigma of 0.04
 C22A-C23A \\sim C22B-C23B
 with sigma of 0.02
 C24A-C26A \\sim C24B-C26B
 with sigma of 0.04
 C24A-C25A \\sim C24B-C25B
 with sigma of 0.02
 C21A-C22A \\sim C21B-C22B
 with sigma of 0.02
 C23A-C25A \\sim C23B-C25B
 with sigma of 0.04
 C22A-C27A \\sim C22B-C27B
 with sigma of 0.02
 C25A-C26A \\sim C25B-C26B
 with sigma of 0.02
 C23A-C27A \\sim C23B-C27B
 with sigma of 0.04
 C26A-C27A \\sim C26B-C27B
 with sigma of 0.02
 C23A-C24A \\sim C23B-C24B
 with sigma of 0.02
 C25A-C27A \\sim C25B-C27B
 with sigma of 0.04
 Mg1-C21A \\sim Mg1-C21B
 with sigma of 0.04
 Mg1-C22A \\sim Mg1-C22B
 with sigma of 0.04
 Mg1-C23A \\sim Mg1-C23B
 with sigma of 0.04
 Mg1-C27A \\sim Mg1-C27B
 with sigma of 0.04
 C21A-C23A \\sim C21B-C23B
 with sigma of 0.04
 C21A-C27A \\sim C21B-C27B
 with sigma of 0.04
 C22A-C24A \\sim C22B-C24B
 with sigma of 0.04
 C22A-C26A \\sim C22B-C26B
 with sigma of 0.04
3. Restrained planarity
 C55, C56, C57, C58, C59, C60, C61
 with sigma of 0.1
 C22A, C23A, C24A, C25A, C26A, C27A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C22A \\sim C23A \\sim C24A \\sim C25A \\sim C26A \\sim C27A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C21B \\sim C21A \\sim C22A \\sim C22B \\sim C23A \\sim C23B \\sim C24A \\sim
C24B \\sim C25A \\sim C25B \\sim C26A \\sim C26B \\sim C27B \\sim C27A: within
1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
Uanis(C22A) \\sim Ueq, Uanis(C22B) \\sim Ueq, Uanis(C21B) \\sim Ueq,
Uanis(C21A) \\sim Ueq, Uanis(C27B) \\sim Ueq, Uanis(C27A) \\sim Ueq,
Uanis(C23B) \\sim Ueq, Uanis(C23A) \\sim Ueq, Uanis(C24A) \\sim Ueq,
Uanis(C24B) \\sim Ueq, Uanis(C25A) \\sim Ueq, Uanis(C25B) \\sim Ueq,
Uanis(C26A) \\sim Ueq, Uanis(C26B) \\sim Ueq: with sigma of 0.05 and sigma for
terminal atoms of 0.1
5. Rigid body (RIGU) restrains
 C55, C56, C57, C58, C59, C60, C61
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C22A, C23A, C24A, C25A, C26A, C27A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C14B)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C12B)=Sof(H12D)=Sof(H12E)=
 Sof(H12F)=Sof(C13B)=Sof(H13D)=Sof(H13E)=Sof(H13F)=1-FVAR(1)
 Sof(C12A)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C13A)=Sof(H13A)=Sof(H13B)=
 Sof(H13C)=Sof(C14A)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(1)
 Sof(C27B)=Sof(H27B)=Sof(C22B)=Sof(C21B)=Sof(H21C)=Sof(H21D)=Sof(C23B)=
 Sof(H23B)=Sof(C24B)=Sof(H24B)=Sof(C25B)=Sof(H25B)=Sof(C26B)=Sof(H26B)=1-FVAR(2)
 Sof(C21A)=Sof(H21A)=Sof(H21B)=Sof(C22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=
 Sof(H24A)=Sof(C25A)=Sof(H25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(H27A)=FVAR(2)
 Fixed Sof: C55(0.5) H55A(0.5) H55B(0.5) H55C(0.5) C56(0.5) C57(0.5) H57(0.5)
 C58(0.5) H58(0.5) C59(0.5) H59(0.5) C60(0.5) H60(0.5) C61(0.5) H61(0.5)
7.a Ternary CH refined with riding coordinates:
 C45(H45), C18(H18)
7.b Secondary CH2 refined with riding coordinates:
 C48(H48A,H48B), C21A(H21A,H21B), C21B(H21C,H21D)
7.c Aromatic/amide H refined with riding coordinates:
 C32(H32), C30(H30), C5(H5), C42(H42), C3(H3), C15(H15), C43(H43), C54(H54),
 C16(H16), C53(H53), C50(H50), C52(H52), C51(H51), C57(H57), C58(H58), C59(H59),
  C60(H60), C61(H61), C23A(H23A), C24A(H24A), C25A(H25A), C26A(H26A),
 C27A(H27A), C27B(H27B), C23B(H23B), C24B(H24B), C25B(H25B), C26B(H26B)
7.d Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C46(H46A,H46B,H46C), C36(H36A,H36B,H36C), C9(H9A,H9B,
 H9C), C37(H37A,H37B,H37C), C20(H20A,H20B,H20C), C41(H41A,H41B,H41C), C39(H39A,
 H39B,H39C), C8(H8A,H8B,H8C), C40(H40A,H40B,H40C), C47(H47A,H47B,H47C),
 C10(H10A,H10B,H10C), C19(H19A,H19B,H19C), C12A(H12A,H12B,H12C), C13A(H13A,H13B,
 H13C), C14A(H14A,H14B,H14C), C14B(H14D,H14E,H14F), C12B(H12D,H12E,H12F),
 C13B(H13D,H13E,H13F), C55(H55A,H55B,H55C)
;
_shelx_res_checksum              73401
_shelx_hkl_checksum              94293
_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 3.172
_oxdiff_exptl_absorpt_empirical_full_min 0.517