Synergy of redox-activity and hemilability in thioamidato cobalt(III) complexes for the chemoselective reduction of nitroarenes to anilines: catalytic and mechanistic investigation.
Gioftsidou, Dimitra K.; Kallitsakis, Michael G.; Kavaratzi, Konstantina; Hatzidimitriou, Antonios G.; Terzidis, Michael A.; Lykakis, Ioannis N.; Angaridis, Panagiotis A.; Dalton transactions (Cambridge, England : 2003) 53 (2024) 1469–1481; doi:10.1039/d3dt02923a

data_7714802
_publ_section_title
;
 Synergy of redox-activity and hemilability in thioamidato cobalt(III)
 complexes for the chemoselective reduction of nitroarenes to anilines:
 catalytic and mechanistic investigation.
;
_journal_issue                   4
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              1469
_journal_page_last               1481
_journal_paper_doi               10.1039/d3dt02923a
_journal_volume                  53
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C9.50 H11.25 Co0.50 N3.25 S1.50'
_chemical_formula_sum            'C9.5 H11.25 Co0.5 N3.25 S1.5'
_chemical_formula_weight         248.53
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   'P n a 21'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_audit_update_record
;
2020-04-09 deposited with the CCDC.	2023-12-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.4562(8)
_cell_length_b                   19.4479(14)
_cell_length_c                   8.1889(4)
_cell_measurement_reflns_used    177
_cell_measurement_temperature    295
_cell_measurement_theta_max      20
_cell_measurement_theta_min      10
_cell_volume                     2461.5(2)
_computing_cell_refinement       'Apex2 (Bruker AXS, 2006)'
_computing_data_collection       'Apex2 (Bruker AXS, 2006)'
_computing_data_reduction        'USER DEFINED DATA REDUCTION'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'SIR92 (Altomare et al., 1994)'
_diffrn_ambient_temperature      295
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Bruker Kappa Apex2'
_diffrn_measurement_method       '\f & \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.022
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            15406
_diffrn_reflns_theta_full        26.405
_diffrn_reflns_theta_max         26.405
_diffrn_reflns_theta_min         1.683
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.969
_exptl_absorpt_correction_T_max  0.88
_exptl_absorpt_correction_T_min  0.85
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
; 
 Analytical Absorption (De Meulenaer & Tompa, 1965) 
;
_exptl_crystal_colour            pink
_exptl_crystal_density_diffrn    1.341
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1028
_exptl_crystal_size_max          0.190
_exptl_crystal_size_mid          0.170
_exptl_crystal_size_min          0.130
_refine_diff_density_max         0.24
_refine_diff_density_min         -0.22
_refine_ls_abs_structure_details 'Flack (1983), 3743 Friedel-pairs'
_refine_ls_abs_structure_Flack   0.045(13)
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   0.9999
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     266
_refine_ls_number_reflns         3258
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.0426
_refine_ls_R_factor_gt           0.0233
_refine_ls_shift/su_max          0.0003152
_refine_ls_shift/su_mean         0.0000341
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) 
 [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] 
 where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax 
 Method = Robust Weighting (Prince, 1982) 
 W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ 
 A~i~ are: 
 2.08 2.36 1.14 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0524
_refine_ls_wR_factor_gt          0.0491
_refine_ls_wR_factor_ref         0.0491
_reflns_limit_h_max              19
_reflns_limit_h_min              0
_reflns_limit_k_max              24
_reflns_limit_k_min              0
_reflns_limit_l_max              10
_reflns_limit_l_min              -10
_reflns_number_gt                3258
_reflns_number_total             4989
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   3.43
_oxford_diffrn_Wilson_scale      58.21
_oxford_refine_ls_r_factor_ref   0.0233
_oxford_refine_ls_scale          0.15190(4)
_oxford_reflns_number_all        4972
_oxford_reflns_threshold_expression_ref I>2.0\s(I)
_cod_data_source_file            d3dt02923a2.cif
_cod_data_source_block           I_CCDC3
_cod_depositor_comments
'Adding full bibliography for 7714799--7714804.cif.'
_cod_original_sg_symbol_H-M      'P n a 21 '
_cod_original_formula_sum        'C9.50 H11.25 Co0.50 N3.25 S1.50'
_cod_database_code               7714802