An Iron Bis(carbene) Catalyst for Low Overpotential CO2 Electroreduction to CO: Mechanistic Insights from Kinetic Zone Diagrams, Spectroscopy, and Theory
Gonell, Sergio; Assaf, Eric A.; Lloret-Fillol, Julio; Miller, Alexander J. M.; ACS Catalysis 11 (2021) 15212–15222; doi:10.1021/acscatal.1c04414

data_4519249
_publ_section_title
;
 An Iron Bis(carbene) Catalyst for Low Overpotential CO2 Electroreduction
 to CO: Mechanistic Insights from Kinetic Zone Diagrams, Spectroscopy, and
 Theory
;
_journal_issue                   24
_journal_name_full               'ACS Catalysis'
_journal_page_first              15212
_journal_page_last               15222
_journal_paper_doi               10.1021/acscatal.1c04414
_journal_volume                  11
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_sum            'C26 H26 F12 Fe N8 P2'
_chemical_formula_weight         796.34
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2018/3
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.1567(14)
_cell_length_b                   10.4245(19)
_cell_length_c                   35.595(6)
_cell_measurement_reflns_used    9565
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.72
_cell_measurement_theta_min      2.26
_cell_volume                     3026.6(9)
_computing_cell_refinement       'Bruker APEX3 v2015.9-0'
_computing_data_collection       'Bruker APEX3 v2015.9-0'
_computing_data_reduction        'Bruker APEX3 v2015.9-0'
_computing_molecular_graphics
;
 SHELXle: C.B. Huebschle, G.M. Sheldrick & B. Dittrich
 J.Appl.Cryst. (2011) 44, 1281-1284.
;
_computing_publication_material  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution
;
  SHELXT V2018/2 (Sheldrick 2018); G.M. Sheldrick (2015)
 "SHELXT - Integrated space-group and crystal-structure
 determination", Acta Cryst., A71, 3-8. 
;
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 512
_diffrn_detector_type            '4K CCD area detector APEX II'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'APEX DUO Kappa 4-axis goniometer'
_diffrn_measurement_method
;
 Fullsphere data collection, phi and omega scans
;
_diffrn_radiation_monochromator  'Quazar MX Multilayer Optics'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0586
_diffrn_reflns_av_unetI/netI     0.0361
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       49
_diffrn_reflns_limit_l_min       -49
_diffrn_reflns_number            93669
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.946
_diffrn_reflns_theta_min         2.036
_diffrn_source                   'Microfocus source E025 IuS'
_diffrn_source_current           0.6
_diffrn_source_power             50
_diffrn_source_size              '0.2 mm x 0.2 mm fine focus'
_diffrn_source_type              'Bruker APEX DUO'
_exptl_absorpt_coefficient_mu    0.714
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.6523
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS-2016/2
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    1.748
_exptl_crystal_description       block
_exptl_crystal_F_000             1608
_exptl_crystal_size_max          0.400
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.040
_refine_diff_density_max         1.158
_refine_diff_density_min         -0.910
_refine_diff_density_rms         0.146
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.50(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.209
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     501
_refine_ls_number_reflns         8571
_refine_ls_number_restraints     441
_refine_ls_restrained_S_all      1.197
_refine_ls_R_factor_all          0.0828
_refine_ls_R_factor_gt           0.0762
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0315P)^2^+19.3599P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1746
_refine_ls_wR_factor_ref         0.1771
_reflns_Friedel_coverage         0.752
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.956
_reflns_number_gt                7972
_reflns_number_total             8571
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c04414_si_002.cif
_cod_data_source_block           mo_SG30c_0m
_cod_database_code               4519249
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.763
_shelx_estimated_absorpt_t_max   0.972
_shelx_res_checksum              9549
_shelx_hkl_checksum              34154