Synthesis of planar chiral biferrocenes by iridium-catalyzed [2+2+2] cycloadition of a biferrocene-linked diyne with nitriles: asymmetric desymmetrization and kinetic resolution
Sawano, Takahiro; Murata, Kayo; Suzaki, Tomoaki; Urasawa, Kazuki; Kobayashi, Manami; Aso, Ryota; Ozasa, Kazuki; Ishikawa, Eri; Takeuchi, Ryo; Chemical Communications  (2026) –; doi:10.1039/D6CC00435K

data_7135700
_publ_section_title
;
 Synthesis of planar chiral biferrocenes by iridium-catalyzed [2+2+2]
 cycloaddition of biferrocene-linked diynes with nitriles: asymmetric
 desymmetrization and kinetic resolution.
;
_journal_issue                   33
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              8451
_journal_page_last               8455
_journal_paper_doi               10.1039/d6cc00435k
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety         'C36 H26 Fe2'
_chemical_formula_sum            'C36 H26 Fe2'
_chemical_formula_weight         570.27
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2026-03-08
_audit_creation_method
;
Olex2 1.5-ac7-018
(compiled 2025.08.06 svn.rb7424aed for Rigaku Oxford Diffraction, GUI svn.r7314)
;
_audit_update_record
;
2026-03-23 deposited with the CCDC.	2026-04-02 downloaded from the CCDC.
;
_cell_angle_alpha                72.804(2)
_cell_angle_beta                 86.667(2)
_cell_angle_gamma                76.572(2)
_cell_formula_units_Z            2
_cell_length_a                   7.2414(2)
_cell_length_b                   12.4389(3)
_cell_length_c                   15.5403(4)
_cell_measurement_reflns_used    9086
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.4290
_cell_measurement_theta_min      4.1030
_cell_volume                     1300.58(6)
_computing_cell_refinement       'CrysAlisPro 1.171.44.128a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.128a 64-bit (release 04-11-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.128a (Rigaku OD, 2025)'
_computing_molecular_graphics    'Olex2 1.5-ac7-018 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac7-018 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.932
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     58.00 105.00   0.50    0.51    --  113.25 -99.00  30.00   94
  2  \w     42.00 105.00   0.50    0.51    --  113.25 -99.00   0.00  126
  3  \w     57.00 104.00   0.50    0.51    --  113.25 -99.00 -90.00   94
  4  \w     76.00 101.00   0.50    0.51    --  113.25-125.00-150.00   50
  5  \w     53.00 105.00   0.50    0.51    --  113.25 -99.00-180.00  104
  6  \w     55.00  80.00   0.50    0.51    --  113.25 -99.00-150.00   50
  7  \w     43.00  92.00   0.50    0.51    --  113.25 -99.00-120.00   98
  8  \w     42.00  68.00   0.50    0.51    --  113.25 -99.00 -60.00   52
  9  \w     74.00 105.00   0.50    0.51    --  113.25 -99.00 -30.00   62
 10  \w    -17.00  71.00   0.50    0.13    --   48.61 -82.00  18.00  176
 11  \w    -19.00  21.00   0.50    0.13    --   48.61 -19.00  90.00   80
 12  \w     58.00 106.00   0.50    0.51    --  113.25 -99.00 120.00   96
 13  \w     72.00 120.00   0.50    0.51    --  113.25 -82.00  18.00   96
 14  \w    101.00 170.00   0.50    0.51    --  113.25  19.00  60.00  138
 15  \w    102.00 178.00   0.50    0.51    --  113.25  82.00 139.00  152
 16  \w    101.00 169.00   0.50    0.51    --  113.25  38.00 -90.00  136
 17  \w    -65.00 -19.00   0.50    0.51    --  -91.75  57.00-120.00   92
 18  \w    -71.00 -19.00   0.50    0.51    --  -91.75  77.00 -30.00  104
 19  \w    -64.00 -39.00   0.50    0.51    --  -91.75  57.00 -30.00   50
 20  \w    -66.00 -26.00   0.50    0.51    --  -91.75  57.00-150.00   80
 21  \w    -21.00  25.00   0.50    0.13    --  -48.61  19.00  60.00   92
 22  \w    -65.00 -39.00   0.50    0.51    --  -91.75  57.00  60.00   52
 23  \w    -63.00 -20.00   0.50    0.51    --  -91.75  57.00  90.00   86
 24  \w    -49.00 -20.00   0.50    0.51    --  -91.75  57.00 150.00   58
 25  \w    -51.00 -19.00   0.50    0.51    --  -91.75  82.00 139.00   64
 26  \w    -80.00 -27.00   0.50    0.13    --  -48.61 125.00-180.00  106
 27  \w    -72.00  22.00   0.50    0.13    --  -48.61  82.00 139.00  188
 28  \w    -59.00 -20.00   0.50    0.51    --  -91.75 125.00 -90.00   78
 29  \w   -108.00 -79.00   0.50    0.51    --  -91.75 -19.00-180.00   58
 30  \w   -155.00-126.00   0.50    0.51    --  -91.75 -19.00-180.00   58
 31  \w   -139.00-113.00   0.50    0.51    --  -91.75 -57.00 -30.00   52
 32  \w   -106.00 -77.00   0.50    0.51    --  -91.75 -57.00  60.00   58
 33  \w   -164.00 -93.00   0.50    0.51    --  -91.75 -38.00  90.00  142
 34  \w   -163.00-130.00   0.50    0.51    --  -91.75 -57.00  60.00   66
 35  \w   -143.00-104.00   0.50    0.51    --  -91.75 -82.00  18.00   78
 36  \w   -106.00 -74.00   0.50    0.13    --  -48.61-125.00 120.00   64
 37  \w   -119.00 -73.00   0.50    0.13    --  -48.61-125.00-180.00   92
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0747225000
_diffrn_orient_matrix_UB_12      0.1107644000
_diffrn_orient_matrix_UB_13      -0.0173649000
_diffrn_orient_matrix_UB_21      -0.1147134000
_diffrn_orient_matrix_UB_22      0.0528317000
_diffrn_orient_matrix_UB_23      -0.0888924000
_diffrn_orient_matrix_UB_31      -0.1705981000
_diffrn_orient_matrix_UB_32      0.0514609000
_diffrn_orient_matrix_UB_33      0.0506619000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0317
_diffrn_reflns_av_unetI/netI     0.0329
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.932
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            15564
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.932
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.321
_diffrn_reflns_theta_min         2.977
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.112
_exptl_absorpt_correction_T_max  0.865
_exptl_absorpt_correction_T_min  0.360
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.128a (Rigaku Oxford Diffraction, 2025)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.456
_exptl_crystal_description       block
_exptl_crystal_F_000             588
_exptl_crystal_preparation       recrystalization
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.442
_refine_diff_density_min         -0.388
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     343
_refine_ls_number_reflns         5256
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0325
_refine_ls_R_factor_gt           0.0297
_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^)+(0.0279P)^2^+0.9021P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0741
_refine_ls_wR_factor_ref         0.0755
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4876
_reflns_number_total             5256
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc00435k2.cif
_cod_data_source_block           exp_141_autored
_cod_depositor_comments
'Adding full bibliography for 7135696--7135704.cif.'
_cod_database_code               7135700
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C36H26Fe2
_chemical_oxdiff_usercomment     DCM
_shelx_estimated_absorpt_t_max   0.659
_shelx_estimated_absorpt_t_min   0.323
_diffrn_oxdiff_digest_hkl
;
43f525be2d9470670e7eacaca2a49777126473
;
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name exp_141.par
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C003(H003), C004(H004), C00A(H00A), C00C(H00C), C00D(H00D), C00G(H00G),
 C00H(H00H), C00I(H00I), C00J(H00J), C00L(H00L), C00N(H00N), C00O(H00O),
 C00P(H00P), C00Q(H00Q), C00R(H00R), C00S(H00S), C00T(H00T), C00U(H00U),
 C00V(H00V), C00W(H00W), C00X(H00X), C00Y(H00Y), C00Z(H00Z), C010(H010),
 C011(H011), C012(H012)
;
_shelx_res_checksum              44229
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.348
_oxdiff_exptl_absorpt_empirical_full_min 0.826