How Innocent are Potentially Redox Non-Innocent Ligands? Electronic Structure and Metal Oxidation States in Iron-PNN Complexes as a Representative Case Study.
Butschke, Burkhard; Fillman, Kathlyn L.; Bendikov, Tatyana; Shimon, Linda J. W.; Diskin-Posner, Yael; Leitus, Gregory; Gorelsky, Serge I.; Neidig, Michael L.; Milstein, David; Inorganic chemistry 54 (2015) 4909–4926; doi:10.1021/acs.inorgchem.5b00509

data_4342923
_publ_section_title
;
 How Innocent are Potentially Redox Non-Innocent Ligands? Electronic
 Structure and Metal Oxidation States in Iron-PNN Complexes as a
 Representative Case Study.
;
_journal_issue                   10
_journal_name_full               'Inorganic chemistry'
_journal_page_first              4909
_journal_page_last               4926
_journal_paper_doi               10.1021/acs.inorgchem.5b00509
_journal_volume                  54
_journal_year                    2015
_chemical_formula_moiety         'C25 H37 Br2 Fe N2 P, C6 H6'
_chemical_formula_sum            'C31 H43 Br2 Fe N2 P'
_chemical_formula_weight         690.31
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_space_group_name_Hall  'P 2c -2n'
_symmetry_space_group_name_H-M   'P n a 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.7448(11)
_cell_length_b                   18.5471(13)
_cell_length_c                   12.5107(9)
_cell_measurement_reflns_used    31950
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.48
_cell_measurement_theta_min      1.8
_cell_volume                     3189.3(4)
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker KappaApexII CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0376
_diffrn_reflns_av_unetI/netI     0.0459
_diffrn_reflns_laue_measured_fraction_full 0.998
_diffrn_reflns_laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            31950
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         3.110
_exptl_absorpt_coefficient_mu    3.051
_exptl_absorpt_correction_T_max  0.852
_exptl_absorpt_correction_T_min  0.741
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Bruker Apex2'
_exptl_crystal_colour            blue
_exptl_crystal_density_diffrn    1.438
_exptl_crystal_description       prism
_exptl_crystal_F_000             1416
_exptl_crystal_size_max          0.100
_exptl_crystal_size_mid          0.080
_exptl_crystal_size_min          0.050
_refine_diff_density_max         0.877
_refine_diff_density_min         -0.520
_refine_diff_density_rms         0.061
_refine_ls_abs_structure_details
;
 Flack x determined using 2814 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.011(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     332
_refine_ls_number_reflns         7116
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0314
_refine_ls_R_factor_gt           0.0270
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0177P)^2^+0.2173P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0576
_refine_ls_wR_factor_ref         0.0587
_reflns_Friedel_coverage         0.869
_reflns_friedel_fraction_full    0.984
_reflns_friedel_fraction_max     0.951
_reflns_number_gt                6584
_reflns_number_total             7116
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b00509_si_002.cif
_cod_data_source_block           compound1
_cod_depositor_comments
'Adding full bibliography for 4342923--4342928.cif.'
_cod_database_code               4342923
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.750
_shelx_estimated_absorpt_t_max   0.862
_shelx_res_checksum              7299
_shelx_hkl_checksum              52291