Direct Comparison of C-H Bond Amination Efficacy through Manipulation of Nitrogen-Valence Centered Redox: Imido versus Iminyl.
Wilding, Matthew J. T.; Iovan, Diana A.; Wrobel, Alexandra T.; Lukens, James T.; MacMillan, Samantha N.; Lancaster, Kyle M.; Betley, Theodore A.; Journal of the American Chemical Society 139 (2017) 14757–14766; doi:10.1021/jacs.7b08714

data_4131684
_publ_section_title
;
 Direct Comparison of C-H Bond Amination Efficacy through Manipulation of
 Nitrogen-Valence Centered Redox: Imido versus Iminyl.
;
_journal_issue                   41
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14757
_journal_page_last               14766
_journal_paper_doi               10.1021/jacs.7b08714
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety         'C76 H62 Fe N3'
_chemical_formula_sum            'C76 H62 Fe N3'
_chemical_formula_weight         1073.14
_space_group_crystal_system      tetragonal
_space_group_IT_number           88
_space_group_name_Hall           '-I 4ad'
_space_group_name_H-M_alt        'I 41/a :2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-05-20
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            16
_cell_length_a                   42.4313(18)
_cell_length_b                   42.4313(18)
_cell_length_c                   15.8882(8)
_cell_measurement_reflns_used    9417
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.78
_cell_measurement_theta_min      2.15
_cell_volume                     28605(2)
_computing_cell_refinement       'SAINT 8.34A (Bruker-AXS,2014)'
_computing_data_collection       'APEX2 v2014.3.0 (Bruker-AXS,2014)'
_computing_data_reduction        'SAINT 8.34A (Bruker-AXS,2014)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XLMP (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.01
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type
;
Bruker D8 goniometer with CCD area detector
;
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0000
_diffrn_reflns_av_unetI/netI     0.0724
_diffrn_reflns_limit_h_max       51
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_k_max       51
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            13709
_diffrn_reflns_theta_full        25.82
_diffrn_reflns_theta_max         25.82
_diffrn_reflns_theta_min         0.96
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.250
_exptl_absorpt_correction_T_max  0.9610
_exptl_absorpt_correction_T_min  0.9155
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2008)'
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    0.997
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             9040
_exptl_crystal_size_max          0.345
_exptl_crystal_size_mid          0.333
_exptl_crystal_size_min          0.154
_refine_diff_density_max         0.520
_refine_diff_density_min         -1.233
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.136
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     728
_refine_ls_number_reflns         13709
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.136
_refine_ls_R_factor_all          0.1467
_refine_ls_R_factor_gt           0.0892
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1390P)^2^+25.9056P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2592
_refine_ls_wR_factor_ref         0.2799
_reflns_number_gt                7614
_reflns_number_total             13709
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja7b08714_si_002.cif
_cod_data_source_block           ArLFeNAr
_cod_original_sg_symbol_H-M      'I 41/a'
_cod_database_code               4131684
_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. Rigid bond restraints
 C1, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C1 \\sim C6: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C62A) = Uanis(C66)
Uanis(C63A) = Uanis(C65)
Uanis(C66A) = Uanis(C62)
Uanis(C65A) = Uanis(C63)
4. Others
 Sof(C62)=Sof(H62)=Sof(C63)=Sof(H63)=Sof(H64A)=Sof(C65)=Sof(H65)=Sof(C66)=
 Sof(H66)=1-FVAR(1)
 Sof(H64)=Sof(C62A)=Sof(H62A)=Sof(C63A)=Sof(H63A)=Sof(C65A)=Sof(H65A)=
 Sof(C66A)=Sof(H66A)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C12(H12), C14(H14), C15(H15),
 C16(H16), C17(H17), C18(H18), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24),
  C26(H26), C27(H27), C33(H33), C36(H36), C40(H40), C41(H41), C45(H45),
 C47(H47), C50(H50), C51(H51), C52(H52), C53(H53), C54(H54), C56(H56), C57(H57),
  C58(H58), C59(H59), C60(H60), C62(H62), C63(H63), C64(H64A), C64(H64),
 C65(H65), C66(H66), C62A(H62A), C63A(H63A), C65A(H65A), C66A(H66A), C68(H68),
 C69(H69), C71(H71), C72(H72)
5.b Fitted hexagon refined as free rotating group:
 C61(C62,C63,C64,C65,C66)
5.c Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C35(H35A,H35B,H35C), C38(H38A,H38B,H38C), C74(H74A,H74B,
 H74C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C)
;
_olex2_submission_special_instructions 'No special instructions were received'