Oxidation of Mixed-Valence CoIII/FeII Complexes Reversed at High pH: A Kinetico-Mechanistic Study of Water Oxidation
Paul V. Bernhardt; Fernando Bozoglian; Brendan P. Macpherson; Manuel Martínez; André E. Merbach; Gabriel González; Beatriz Sienra; Inorganic Chemistry 43 (2004) 7187–7195; doi:10.1021/ic0493191

data_4311934
_publ_section_title
;
 Oxidation of Mixed-Valence CoIII/FeII Complexes Reversed at High pH: A
 Kinetico-Mechanistic Study of Water Oxidation
;
_journal_name_full               'Inorganic Chemistry'
_journal_page_first              7187
_journal_page_last               7195
_journal_paper_doi               10.1021/ic0493191
_journal_volume                  43
_journal_year                    2004
_chemical_compound_source        'synthesis as described'
_chemical_formula_moiety         'C16 H25 Co1 Fe1 N9 S2'
_chemical_formula_structural     'C16 H25 FE CO N9 S2'
_chemical_formula_sum            'C17 H29 Co Fe N9 O2 S2'
_chemical_formula_weight         570.39
_chemical_name_systematic
;
 ?
;
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_conform_dict_location     ftp://ftp.iucr.org/cifdics/cif_core.dic
_audit_conform_dict_name         cif_core.dic
_audit_conform_dict_version      2.1
_audit_creation_date             2004-05-16T20:43:46-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 90.763(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.6307(7)
_cell_length_b                   14.6590(10)
_cell_length_c                   14.6130(10)
_cell_measurement_reflns_used    25
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      14.086
_cell_measurement_theta_min      11.279
_cell_measurement_wavelength     0.71073
_cell_volume                     2491.2(3)
_computing_cell_refinement       'CAD4 Express (Enraf Nonius, 1994)'
_computing_data_collection       'CAD4 Express (Enraf Nonius, 1994)'
_computing_data_reduction        'XCAD4 (Harms & Wocadlo, 1995)'
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 1997)'
_computing_publication_material  'WinGX publication routines (Farrugia, 1999)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_diffrn_ambient_temperature      296(2)
_diffrn_detector                 'scintillation LiI'
_diffrn_detector_dtime           1.195
_diffrn_measured_fraction_theta_full 1
_diffrn_measured_fraction_theta_max 1
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Enraf Nonius CAD4'
_diffrn_measurement_method       'non-profiled omega/2theta scans'
_diffrn_orient_matrix_type
;
  x-axis points to radiation source
  the matrix is specified in reciprocal space
;
_diffrn_orient_matrix_UB_11      0.38389E-1
_diffrn_orient_matrix_UB_12      0.44772E-1
_diffrn_orient_matrix_UB_13      0.42001E-1
_diffrn_orient_matrix_UB_21      0.29726E-1
_diffrn_orient_matrix_UB_22      -0.51379E-1
_diffrn_orient_matrix_UB_23      0.38609E-1
_diffrn_orient_matrix_UB_31      0.70975E-1
_diffrn_orient_matrix_UB_32      -0.2685E-2
_diffrn_orient_matrix_UB_33      -0.37822E-1
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0154
_diffrn_reflns_av_unetI/netI     0.0272
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            4598
_diffrn_reflns_theta_full        24.98
_diffrn_reflns_theta_max         24.98
_diffrn_reflns_theta_min         1.97
_diffrn_source                   'Enraf Nonius FR590'
_diffrn_standards_decay_%        24
_diffrn_standards_interval_time  120
_diffrn_standards_number         3
_exptl_absorpt_coefficient_mu    1.448
_exptl_absorpt_correction_T_max  0.8659
_exptl_absorpt_correction_T_min  0.7049
_exptl_absorpt_correction_type   psi-scan
_exptl_absorpt_process_details
;
North A.C.T., Phillips D.C. & Mathews F.S. (1968) Acta. Cryst. A24, 351
        Number of psi-scan sets used was   5
        Theta correction was applied.
        Averaged transmission function was used.
        No Fourier smoothing was applied.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.521
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1180
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.839
_refine_diff_density_min         -0.665
_refine_diff_density_rms         0.135
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.991
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     290
_refine_ls_number_reflns         4370
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.991
_refine_ls_R_factor_all          0.0524
_refine_ls_R_factor_gt           0.0335
_refine_ls_shift/su_max          0
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0664P)^2^+1.1993P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0889
_refine_ls_wR_factor_ref         0.0982
_reflns_number_gt                3464
_reflns_number_total             4370
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic0493191si20040526_060836.cif
_cod_data_source_block           mm8270
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               4311934
_exptl_absorpt_factor_mur        0.144
_exptl_absorpt_correction_t_ave  0.8204
_diffrn_standards_decay_corr_max 1.794
_diffrn_standards_decay_corr_min 0.964