Chiral iron porphyrin (+)-D4-(por)FeCl catalyzes highly enantioselective cyclopropanation of alkenes using in situ generated diazoacetonitrile with up to 35 000 product turnover
Tan, Hao-Chong; Shing, Ka-Pan; Wang, Hua-Hua; Liu, Yungen; Che, Chi-Ming; Chemical Science 16 (2025) 7191–7202; doi:10.1039/D5SC00461F

data_1574406
_publ_section_title
;
 Chiral iron porphyrin (+)-D4-(por)FeCl catalyzes highly enantioselective
 cyclopropanation of alkenes using in situ generated diazoacetonitrile
 with up to 35&#x2009;000 product turnover
;
_journal_issue                   17
_journal_name_full               'Chemical Science'
_journal_page_first              7191
_journal_page_last               7202
_journal_paper_doi               10.1039/D5SC00461F
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C14 H13 Fe N'
_chemical_formula_sum            'C14 H13 Fe N'
_chemical_formula_weight         251.10
_chemical_name_systematic
(1S,2S)-2-(Ferrocenyl)cyclopropane-1-carbonitrile
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2023-08-22
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-04-20 deposited with the CCDC.	2025-03-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.504(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.4077(10)
_cell_length_b                   7.4147(8)
_cell_length_c                   14.8363(16)
_cell_measurement_reflns_used    9914
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      73.03
_cell_measurement_theta_min      3.70
_cell_volume                     1143.8(2)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Apex3 (Bruker 2018)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT 2014'
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Bruker PHOTON III area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34138
_diffrn_reflns_av_R_equivalents  0.0407
_diffrn_reflns_av_unetI/netI     0.0373
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            25521
_diffrn_reflns_point_group_measured_fraction_full 0.964
_diffrn_reflns_point_group_measured_fraction_max 0.916
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         73.445
_diffrn_reflns_theta_min         2.593
_diffrn_source                   'microfocus Metaljet'
_diffrn_source_current           3.57
_diffrn_source_power             0.24947159999999996
_diffrn_source_type              'Incoatec Metaljet'
_diffrn_source_voltage           69.88
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    7.123
_exptl_absorpt_correction_T_max  0.7537
_exptl_absorpt_correction_T_min  0.5502
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1088 before and 0.0713 after correction.
The Ratio of minimum to maximum transmission is 0.7300.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.458
_exptl_crystal_description       bulk
_exptl_crystal_F_000             520
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.757
_refine_diff_density_min         -0.483
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.128(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     308
_refine_ls_number_reflns         6412
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0416
_refine_ls_R_factor_gt           0.0376
_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^)+(0.0362P)^2^+1.0065P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0961
_refine_ls_wR_factor_ref         0.0990
_reflns_Friedel_coverage         0.762
_reflns_Friedel_fraction_full    0.934
_reflns_Friedel_fraction_max     0.852
_reflns_number_gt                5810
_reflns_number_total             6412
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc00461f2.cif
_cod_data_source_block           20230814thc_ferrocenecyclocn_0_a
_cod_depositor_comments
;

2025-06-02
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel

 Adding full bibliography for 1574403--1574407.cif.
;
_cod_original_formula_moiety     '2(C14 H13 Fe N)'
_cod_original_formula_sum        'C28 H26 Fe2 N2'
_cod_original_formula_units_Z    2
_cod_original_formula_weight     502.21
_cod_database_code               1574406
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.435
_shelx_estimated_absorpt_t_min   0.330
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.872(12)
 0.128(12)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3.a Ternary CH refined with riding coordinates:
 C6(H6), C7(H7), C16(H16), C18(H18)
3.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C17(H17A,H17B)
3.c Aromatic/amide H refined with riding coordinates:
 C28(H28), C2(H2), C3(H3), C4(H4), C5(H5), C12(H12), C13(H13), C14(H14),
 C15(H15), C22(H22), C23(H23), C24(H24)
;
_shelx_res_checksum              45037
_olex2_submission_special_instructions 'No special instructions were received'