Iron-Catalyzed Regiodivergent Hydrostannation of Alkynes: Intermediacy of Fe(IV)–H versus Fe(II)–Vinylidene
Liu, Jianguo; Song, Heng; Wang, Tianlin; Jia, Jiong; Tong, Qing-Xiao; Tung, Chen-Ho; Wang, Wenguang; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c11448

data_4135496
_publ_section_title
;
 Iron-Catalyzed Regiodivergent Hydrostannation of Alkynes: Intermediacy of
 Fe(IV)--H versus Fe(II)--Vinylidene
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c11448
_journal_year                    2020
_chemical_formula_moiety         'C36 H47 Fe O P'
_chemical_formula_sum            'C36 H47 Fe O P'
_chemical_formula_weight         582.55
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.910(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.5741(2)
_cell_length_b                   17.7274(3)
_cell_length_c                   33.2179(5)
_cell_measurement_reflns_used    14296
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      75.5890
_cell_measurement_theta_min      3.6210
_cell_volume                     6218.71(18)
_computing_cell_refinement       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      172.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.975
_diffrn_measured_fraction_theta_max 0.920
_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   -100.00 -74.00   1.00    0.42    --  -48.45-119.00  32.00   26
  2  \w   -108.00 -82.00   1.00    0.42    --  -48.45-157.00-121.00   26
  3  \w    -65.00  -6.00   1.00    0.42    --  -48.45 119.00 118.00   59
  4  \w     58.00  83.00   1.00    0.42    --   48.45-157.00-121.00   25
  5  \w     71.00  96.00   1.00    0.42    --   48.45 157.00 -87.00   25
  6  \w     46.00  92.00   1.00    0.42    --   48.45-119.00  32.00   46
  7  \w    -75.00 -49.00   1.00    2.20    --  -86.25 119.00 118.00   26
  8  \w   -110.00 -58.00   1.00    2.20    --  -86.25-157.00-121.00   52
  9  \w    112.00 162.00   1.00    2.20    --  106.49 157.00 -87.00   50
 10  \w    113.00 138.00   1.00    2.20    --  106.49-157.00-121.00   25
 11  \w     49.00 113.00   1.00    2.20    --  106.49-119.00  32.00   64
 12  \w   -120.00 -26.00   1.00    0.42    --  -48.45 -77.00  30.00   94
 13  \w   -157.00 -80.00   1.00    2.20    --  -86.25 -15.00 -90.00   77
 14  \w     36.00 119.00   1.00    2.20    --  106.49 -45.00   0.00   83
 15  \w     47.00  79.00   1.00    2.20    --  106.49 -15.00 -60.00   32
 16  \w     86.00 113.00   1.00    2.20    --  106.49 -15.00 -60.00   27
 17  \w     35.00 117.00   1.00    2.20    --  106.49 -45.00  90.00   82
 18  \w     37.00 118.00   1.00    2.20    --  106.49 -45.00-180.00   81
;
_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      0.0428561000
_diffrn_orient_matrix_UB_12      -0.0217758000
_diffrn_orient_matrix_UB_13      0.0434944000
_diffrn_orient_matrix_UB_21      0.0078741000
_diffrn_orient_matrix_UB_22      -0.0833770000
_diffrn_orient_matrix_UB_23      -0.0127258000
_diffrn_orient_matrix_UB_31      0.1391396000
_diffrn_orient_matrix_UB_32      0.0113193000
_diffrn_orient_matrix_UB_33      -0.0102179000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0690
_diffrn_reflns_av_unetI/netI     0.0657
_diffrn_reflns_Laue_measured_fraction_full 0.975
_diffrn_reflns_Laue_measured_fraction_max 0.920
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            37325
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.920
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.378
_diffrn_reflns_theta_min         3.649
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.561
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.10220
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.25a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.244
_exptl_crystal_description       block
_exptl_crystal_F_000             2496
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.750
_refine_diff_density_min         -1.776
_refine_diff_density_rms         0.158
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     713
_refine_ls_number_reflns         12005
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0917
_refine_ls_R_factor_gt           0.0728
_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^)+(0.1727P)^2^+3.7369P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1936
_refine_ls_wR_factor_ref         0.2412
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9756
_reflns_number_total             12005
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c11448_si_002.cif
_cod_data_source_block           8
_cod_depositor_comments
;

2025-07-29
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C72 H94 Fe2 O2 P2'
_cod_original_formula_weight         1165.11
_cod_original_formula_moiety         '2(C36 H47 Fe O P)'
_cod_original_formula_units_Z            4
_cod_database_code               4135496
_shelxl_version_number           2013-4
_reflns_odcompleteness_completeness 97.58
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C17(H17), C23(H23), C53(H53), C59(H59)
2.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,
 H22B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B),
 C28(H28A,H28B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B),
  C58(H58A,H58B), C60(H60A,H60B), C61(H61A,H61B), C62(H62A,H62B), C63(H63A,
 H63B), C64(H64A,H64B)
2.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C30(H30), C32(H32), C33(H33),
 C34(H34), C35(H35), C36(H36), C48(H48), C49(H49), C50(H50), C51(H51), C66(H66),
  C68(H68), C69(H69), C70(H70), C71(H71), C72(H72)
2.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C),
 C45(H45A,H45B,H45C), C46(H46A,H46B,H46C)
;
_shelx_res_checksum              9849
_shelx_hkl_checksum              3443
_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 3.685
_oxdiff_exptl_absorpt_empirical_full_min 0.543