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_7120726
_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         'C41 H54 Mg N2 O2'
_chemical_formula_sum            'C41 H54 Mg N2 O2'
_chemical_formula_weight         631.17
_chemical_name_systematic
;
 ?
;
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-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'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2016-07-13
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2017-08-06 deposited with the CCDC.
2017-09-29 downloaded from the CCDC.
;
_cell_angle_alpha                72.767(7)
_cell_angle_beta                 86.724(7)
_cell_angle_gamma                84.098(7)
_cell_formula_units_Z            2
_cell_length_a                   9.1082(8)
_cell_length_b                   11.6359(9)
_cell_length_c                   18.2169(17)
_cell_measurement_reflns_used    5926
_cell_measurement_temperature    122.8
_cell_measurement_theta_max      30.2241
_cell_measurement_theta_min      3.0258
_cell_volume                     1833.5(3)
_computing_cell_refinement
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET)
(compiled Aug 27 2010,11:50:40)
;
_computing_data_collection
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CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET)
(compiled Aug 27 2010,11:50:40)
;
_computing_data_reduction
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CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET)
(compiled Aug 27 2010,11:50:40)
;
_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      122.8
_diffrn_detector_area_resol_mean 16.0727
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.965
_diffrn_measurement_details
;
  1 omega   -5.00   94.00   1.0000    9.1000
omega____ theta____ kappa____ phi______ frames
    -       21.2765   37.0000 -150.0000 99

  2 omega   53.00   80.00   1.0000    9.1000
omega____ theta____ kappa____ phi______ frames
    -       21.2765 -131.0000  175.0000 27

  3 omega  -45.00   47.00   1.0000    9.1000
omega____ theta____ kappa____ phi______ frames
    -       21.2765  -37.0000   30.0000 92

  4 omega  -78.00    6.00   1.0000    9.1000
omega____ theta____ kappa____ phi______ frames
    -      -22.0578  122.0000  -57.0000 84

  5 omega  -89.00   -9.00   1.0000    9.1000
omega____ theta____ kappa____ phi______ frames
    -      -22.0578  144.0000 -161.0000 80

  6 omega  -92.00   -6.00   1.0000    9.1000
omega____ theta____ kappa____ phi______ frames
    -      -22.0578  -77.0000   30.0000 86
;
_diffrn_measurement_device_type  'Oxford Diffraction Xcalibur, E'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0408172000
_diffrn_orient_matrix_UB_12      0.0332064000
_diffrn_orient_matrix_UB_13      0.0225389000
_diffrn_orient_matrix_UB_21      0.0209274000
_diffrn_orient_matrix_UB_22      0.0546774000
_diffrn_orient_matrix_UB_23      -0.0261581000
_diffrn_orient_matrix_UB_31      -0.0634834000
_diffrn_orient_matrix_UB_32      0.0037957000
_diffrn_orient_matrix_UB_33      -0.0217016000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0309
_diffrn_reflns_av_unetI/netI     0.0617
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            18520
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.000
_diffrn_reflns_theta_min         3.032
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.084
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83485
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET)
(compiled Aug 27 2010,11:50:40)
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    1.143
_exptl_crystal_description       block
_exptl_crystal_F_000             684
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.310
_refine_diff_density_min         -0.274
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     433
_refine_ls_number_reflns         9403
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0892
_refine_ls_R_factor_gt           0.0526
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0418P)^2^+0.7222P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1085
_refine_ls_wR_factor_ref         0.1296
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6415
_reflns_number_total             9403
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cc07193k2.cif
_cod_data_source_block           ld321xb
_cod_database_code               7120726
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 99.63
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.82
_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, All C(H,H,H,H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C25) = Uanis(C25A)
Uanis(C26) = Uanis(C26A)
3. Others
 Sof(H24A)=Sof(C25A)=Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C26A)=Sof(H26D)=
 Sof(H26E)=Sof(H26F)=1-FVAR(1)
 Sof(H24)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C26)=Sof(H26A)=Sof(H26B)=
 Sof(H26C)=FVAR(1)
 Fixed Sof: H4A(0.5) H4B(0.5) H4C(0.5) H4D(0.5) H4E(0.5) H4F(0.5)
4.a Riding coordinates:
 C24(H24,H24A)
4.b Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C27(H27)
4.c Secondary CH2 refined with riding coordinates:
 C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B)
4.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C9(H9), C10(H10), C20(H20), C21(H21), C22(H22), C36(H36),
 C38(H38), C39(H39), C40(H40), C41(H41)
4.e Disordered Me refined with riding coordinates:
 C4(H4A,H4B,H4C,H4D,H4E,H4F)
4.f Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C16(H16A,H16B,
 H16C), C17(H17A,H17B,H17C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,
 H28B,H28C), C29(H29A,H29B,H29C), C25A(H25D,H25E,H25F), C26A(H26D,H26E,H26F)
;
_shelx_res_checksum              93908
_olex2_submission_original_sample_id ld321xb
_olex2_submission_special_instructions 'No special instructions were received'