Ligand-induced reactivity of β-diketiminate magnesium complexes for regioselective functionalization of fluoroarenes via C-H or C-F bond activations
Hevia, Eva; Davin, Laia; McLellan, Ross; Kennedy, Alan; Chem. Commun.  (2017) –; doi:10.1039/C7CC07193K

data_7120725
_publ_section_title
;
 Ligand-induced reactivity of \b-diketiminate magnesium complexes for
 regioselective functionalization of fluoroarenes via C-H or C-F bond
 activations
;
_journal_name_full               'Chem. Commun.'
_journal_paper_doi               10.1039/C7CC07193K
_journal_year                    2017
_chemical_formula_moiety         'C39 H50 F4 Mg N2 O'
_chemical_formula_sum            'C39 H50 F4 Mg N2 O'
_chemical_formula_weight         663.14
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_primary     iterative
_audit_creation_date             2016-04-18
_audit_creation_method
;
Olex2 1.2
(compiled Jan 19 2015 12:28:14 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2017-08-06 deposited with the CCDC.
2017-09-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.499(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.4430(4)
_cell_length_b                   16.6363(6)
_cell_length_c                   18.2241(6)
_cell_measurement_reflns_used    6350
_cell_measurement_temperature    123(1)
_cell_measurement_theta_max      72.5880
_cell_measurement_theta_min      3.6170
_cell_volume                     3740.2(2)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      123.15
_diffrn_measured_fraction_theta_full 0.9959
_diffrn_measured_fraction_theta_max 0.9783
_diffrn_measurement_device_type  'Oxford Diffraction Gemini S'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0246
_diffrn_reflns_av_unetI/netI     0.0302
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            15184
_diffrn_reflns_theta_full        70.0000
_diffrn_reflns_theta_max         73.17
_diffrn_reflns_theta_min         3.61
_exptl_absorpt_coefficient_mu    0.833
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77231
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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    1.1776
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             1421.1513
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.4161
_refine_diff_density_min         -0.2267
_refine_diff_density_rms         0.0599
_refine_ls_d_res_high            0.8054
_refine_ls_d_res_low             12.2386
_refine_ls_goodness_of_fit_ref   1.0423
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    90
_refine_ls_number_parameters     445
_refine_ls_number_reflns         7339
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.0420
_refine_ls_R_factor_all          0.0642
_refine_ls_R_factor_gt           0.0539
_refine_ls_shift/su_max          0.0008
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0941P)^2^+1.0795P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1511
_refine_ls_wR_factor_ref         0.1603
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              11
_reflns_limit_h_min              -15
_reflns_limit_k_max              20
_reflns_limit_k_min              0
_reflns_limit_l_max              22
_reflns_limit_l_min              -11
_reflns_number_gt                6085
_reflns_number_total             7339
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            c7cc07193k2.cif
_cod_data_source_block           ld404
_cod_database_code               7120725
_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
 C25-C24 = C25A-C24A = C24-C26 = C24A-C26A
 1.53 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C24) = Uanis(C24A)
Uanis(C25) = Uanis(C25A)
Uanis(C26) = Uanis(C26A)
4. Others
 Sof(C25A)=Sof(H25d)=Sof(H25e)=Sof(H25f)=Sof(C24A)=Sof(H24A)=Sof(C26A)=
 Sof(H26d)=Sof(H26e)=Sof(H26f)=1-FVAR(1)
 Sof(C24)=Sof(H24)=Sof(C25)=Sof(H25a)=Sof(H25b)=Sof(H25c)=Sof(C26)=Sof(H26a)=
 Sof(H26b)=Sof(H26c)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C27(H27), C10(H10), C7(H7), C24(H24), C24A(H24A)
5.b Secondary CH2 refined with riding coordinates:
 C39(H39a,H39b), C37(H37a,H37b), C38(H38a,H38b), C36(H36a,H36b)
5.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C33(H33), C3(H3), C5(H5), C4(H4), C22(H22), C20(H20), C21(H21)
5.d Idealised Me refined as rotating group:
 C17(H17a,H17b,H17c), C13(H13a,H13b,H13c), C29(H29a,H29b,H29c), C12(H12a,H12b,
 H12c), C9(H9a,H9b,H9c), C28(H28a,H28b,H28c), C8(H8a,H8b,H8c), C11(H11a,H11b,
 H11c), C25(H25a,H25b,H25c), C26(H26a,H26b,H26c), C25A(H25d,H25e,H25f),
 C26A(H26d,H26e,H26f)
;
_olex2_submission_original_sample_id LD404
_olex2_submission_special_instructions 'No special instructions were received'