Three-Coordinate Cobalt(IV) and Cobalt(V) Imido Complexes with N-Heterocyclic Carbene Ligation: Synthesis, Structure, and Their Distinct Reactivity in C-H Bond Amination.
Zhang, Long; Liu, Yuesheng; Deng, Liang; Journal of the American Chemical Society 136 (2014) 15525–15528; doi:10.1021/ja509731z

data_4122838
_publ_section_title
;
 Three-Coordinate Cobalt(IV) and Cobalt(V) Imido Complexes with
 N-Heterocyclic Carbene Ligation: Synthesis, Structure, and Their Distinct
 Reactivity in C-H Bond Amination.
;
_journal_issue                   44
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              15525
_journal_page_last               15528
_journal_paper_doi               10.1021/ja509731z
_journal_volume                  136
_journal_year                    2014
_chemical_formula_moiety         'C45 H58 Co N4'
_chemical_formula_sum            'C45 H58 Co N4'
_chemical_formula_weight         713.88
_chemical_name_systematic
;
 ?
;
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2014-08-18
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                110.953(3)
_cell_angle_beta                 94.896(3)
_cell_angle_gamma                102.582(2)
_cell_formula_units_Z            4
_cell_length_a                   12.0254(16)
_cell_length_b                   17.359(2)
_cell_length_c                   21.162(3)
_cell_measurement_reflns_used    4744
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      25.46
_cell_measurement_theta_min      2.40
_cell_volume                     3961.3(9)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXD (Sheldrick, 2008)'
_diffrn_ambient_temperature      173(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0562
_diffrn_reflns_av_unetI/netI     0.1271
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            40361
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.745
_diffrn_reflns_theta_min         1.047
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.469
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6266
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0640 before and 0.0487 after correction.
The Ratio of minimum to maximum transmission is 0.8398.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    1.197
_exptl_crystal_description       block
_exptl_crystal_F_000             1532
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.591
_refine_diff_density_min         -0.654
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.954
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     927
_refine_ls_number_reflns         24288
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.954
_refine_ls_R_factor_all          0.1293
_refine_ls_R_factor_gt           0.0602
_refine_ls_shift/su_max          0.025
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0731P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1369
_refine_ls_wR_factor_ref         0.1719
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13121
_reflns_number_total             24288
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja509731z_si_001.cif
_cod_data_source_block           4
_cod_depositor_comments
'Adding full bibliography for 4122835--4122838.cif.'
_cod_original_cell_volume        3961.2(9)
_cod_database_code               4122838
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.872
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C28(H28), C31(H31), C40(H40), C43(H43), C73(H73), C76(H76), C85(H85), C88(H88)
2.b Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C66(H66A,H66B)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C2(H2), C3(H3), C6(H6), C8(H8), C15(H15), C17(H17), C24(H24),
 C25(H25), C26(H26), C36(H36), C37(H37), C38(H38), N5(H5), C47(H47), C48(H48),
 C51(H51), C53(H53), C60(H60), C62(H62), C69(H69), C70(H70), C71(H71), C81(H81),
  C82(H82), C83(H83)
2.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C32(H32A,
 H32B,H32C), C33(H33A,H33B,H33C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C),
 C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C55(H55A,H55B,H55C), C56(H56A,H56B,
 H56C), C57(H57A,H57B,H57C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C74(H74A,
 H74B,H74C), C75(H75A,H75B,H75C), C77(H77A,H77B,H77C), C78(H78A,H78B,H78C),
 C86(H86A,H86B,H86C), C87(H87A,H87B,H87C), C89(H89A,H89B,H89C), C90(H90A,H90B,
 H90C)
;
_shelx_res_checksum              54429
_shelx_hkl_checksum              68076
_olex2_submission_special_instructions 'No special instructions were received'