Ligand Redox Non-Innocence in [Co<sup>III</sup>(TAML)]<sup>0/–</sup> Complexes Affects Nitrene Formation.
van Leest, Nicolaas P.; Tepaske, Martijn A.; Oudsen, Jean-Pierre H; Venderbosch, Bas; Rietdijk, Niels R.; Siegler, Maxime A.; Tromp, Moniek; van der Vlugt, Jarl Ivar; de Bruin, Bas; Journal of the American Chemical Society  (2019) –; doi:10.1021/jacs.9b11715

data_4133876
_publ_section_title
;
 Ligand Redox Non-Innocence in [Co<sup>III</sup>(TAML)]<sup>0/--</sup>
 Complexes Affects Nitrene Formation.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b11715
_journal_year                    2019
_chemical_formula_sum            'C19 H24 Cl2 N4 O4'
_chemical_formula_weight         443.32
_chemical_name_common            'ligand hexane-THF'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           43
_space_group_name_Hall           'F 2 -2d'
_space_group_name_H-M_alt        'F d d 2'
_atom_sites_solution_hydrogens   mixed
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   21.4066(19)
_cell_length_b                   43.288(3)
_cell_length_c                   10.1268(7)
_cell_measurement_reflns_used    202
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      28.0020
_cell_measurement_theta_min      2.1444
_cell_volume                     9384.0(12)
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_diffrn_ambient_temperature      150(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type
'Bruker ApexII Triumph monochromator sealed tube'
_diffrn_measurement_method       'Photon 50 CMOS detector'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0274
_diffrn_reflns_av_unetI/netI     0.0109
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       51
_diffrn_reflns_limit_k_min       -51
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            66510
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        24.988
_diffrn_reflns_theta_max         24.987
_diffrn_reflns_theta_min         2.677
_exptl_absorpt_coefficient_mu    0.307
_exptl_absorpt_correction_T_max  0.95
_exptl_absorpt_correction_T_min  0.89
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS V2014/5 (Bruker AXS Inc.)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.255
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3712
_exptl_crystal_size_max          0.517
_exptl_crystal_size_mid          0.231
_exptl_crystal_size_min          0.170
_exptl_transmission_factor_max   0.7465
_exptl_transmission_factor_min   0.6997
_refine_diff_density_max         0.216
_refine_diff_density_min         -0.236
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 1849 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.012(8)
_refine_ls_extinction_coef       0.00066(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     281
_refine_ls_number_reflns         4111
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0237
_refine_ls_R_factor_gt           0.0227
_refine_ls_shift/su_max          0.015
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0350P)^2^+9.7116P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0595
_refine_ls_wR_factor_ref         0.0602
_reflns_Friedel_coverage         0.884
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                4010
_reflns_number_total             4111
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b11715_si_001.cif
_cod_data_source_block           KvL_NR005_0ma_a
_cod_original_cell_volume        9384.1(13)
_cod_database_code               4133876
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.858
_shelx_estimated_absorpt_t_max   0.950
_shelx_res_checksum              967
_shelx_hkl_checksum              45594
_shelx_fab_checksum              43790