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_4135494
_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         'C37 H48 Fe N O P Sn'
_chemical_formula_sum            'C37 H48 Fe N O P Sn'
_chemical_formula_weight         728.27
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-08-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                68.552(4)
_cell_angle_beta                 73.770(4)
_cell_angle_gamma                72.278(4)
_cell_formula_units_Z            2
_cell_length_a                   11.1311(5)
_cell_length_b                   12.5609(6)
_cell_length_c                   14.3749(5)
_cell_measurement_reflns_used    7756
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      75.7140
_cell_measurement_theta_min      3.8370
_cell_volume                     1749.54(14)
_computing_cell_refinement       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.976
_diffrn_measured_fraction_theta_max 0.987
_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     93.00 172.00   1.00    1.67    --  106.49  43.00 -65.00   79
  2  \w     53.00 121.00   1.00    0.27    --   48.45  43.00 -65.00   68
  3  \w     94.00 160.00   1.00    1.67    --  106.49  19.00  90.00   66
  4  \w    121.00 146.00   1.00    1.67    --  106.49   0.00  90.00   25
  5  \w     37.00 120.00   1.00    1.67    --  106.49   0.00  90.00   83
  6  \w     69.00 102.00   1.00    1.67    --  106.49 -77.00  30.00   33
  7  \w    -23.00  40.00   1.00    0.27    --   48.45 -43.00 143.00   63
  8  \w     34.00  66.00   1.00    1.67    --  106.49 -77.00  30.00   32
  9  \w     34.00  63.00   1.00    1.67    --  106.49 -57.00-150.00   29
 10  \w     39.00  66.00   1.00    1.67    --  106.49 -57.00-180.00   27
 11  \w     45.00 111.00   1.00    1.67    --  106.49-125.00  30.00   66
 12  \w     40.00 111.00   1.00    1.67    --  106.49-125.00 150.00   71
 13  \w     36.00 111.00   1.00    1.67    --  106.49-125.00   0.00   75
 14  \w     40.00 102.00   1.00    1.67    --  106.49 -99.00 -90.00   62
 15  \w     34.00  65.00   1.00    1.67    --  106.49 -99.00-150.00   31
 16  \w     71.00 106.00   1.00    1.67    --  106.49 -99.00-150.00   35
 17  \w     80.00 105.00   1.00    1.67    --  106.49 -99.00-180.00   25
 18  \w     36.00  69.00   1.00    1.67    --  106.49 -99.00-180.00   33
 19  \w     35.00 104.00   1.00    1.67    --  106.49 -99.00 150.00   69
 20  \w    -27.00  22.00   1.00    0.27    --  -48.45  19.00  90.00   49
 21  \w    -84.00 -15.00   1.00    1.67    --  -86.25 125.00   0.00   69
 22  \w    -40.00 -14.00   1.00    1.67    --  -86.25  43.00 -65.00   26
 23  \w    -46.00  24.00   1.00    0.27    --  -48.45  43.00 -65.00   70
 24  \w   -155.00 -76.00   1.00    1.67    --  -86.25 -43.00 143.00   79
 25  \w   -113.00 -46.00   1.00    0.27    --  -48.45 -43.00 143.00   67
 26  \w   -115.00 -75.00   1.00    0.27    --  -48.45-125.00  90.00   40
 27  \w   -156.00 -90.00   1.00    1.67    --  -86.25 -99.00-120.00   66
;
_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      -0.0709886000
_diffrn_orient_matrix_UB_12      0.0978776000
_diffrn_orient_matrix_UB_13      0.0493929000
_diffrn_orient_matrix_UB_21      -0.1195246000
_diffrn_orient_matrix_UB_22      -0.0528994000
_diffrn_orient_matrix_UB_23      0.0400346000
_diffrn_orient_matrix_UB_31      0.0507320000
_diffrn_orient_matrix_UB_32      -0.0769598000
_diffrn_orient_matrix_UB_33      0.0985432000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0818
_diffrn_reflns_av_unetI/netI     0.0819
_diffrn_reflns_Laue_measured_fraction_full 0.976
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            16782
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.072
_diffrn_reflns_theta_min         3.882
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.639
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55516
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.68a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic intense yellow'
_exptl_crystal_density_diffrn    1.382
_exptl_crystal_description       plate
_exptl_crystal_F_000             752
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.012
_refine_diff_density_min         -0.920
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     389
_refine_ls_number_reflns         6177
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0550
_refine_ls_R_factor_gt           0.0468
_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^)+(0.0525P)^2^+1.2049P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1127
_refine_ls_wR_factor_ref         0.1169
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5379
_reflns_number_total             6177
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c11448_si_002.cif
_cod_data_source_block           Me5CpFe(CO)(P-NHSnBu2)
_cod_original_cell_volume        1749.54(15)
_cod_database_code               4135494
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         FeSnPNCO
_shelx_estimated_absorpt_t_max   0.910
_shelx_estimated_absorpt_t_min   0.446
_diffrn_oxdiff_digest_frames
;
01f9252f1262b9adb2c62845e7c13408c901438313e
;
_diffrn_oxdiff_digest_hkl
;
01019816364185eff920b1c4ece279811eba94
;
_reflns_odcompleteness_completeness 98.72
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
C36 \\sim C35 \\sim C37: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.008
C32 \\sim C33 \\sim C31: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.008
3.a Secondary CH2 refined with riding coordinates:
 C34(H34A,H34B), C30(H30A,H30B), C31(H31A,H31B), C35(H35A,H35B), C32(H32A,
 H32B), C36(H36A,H36B)
3.b Aromatic/amide H refined with riding coordinates:
 C18(H18), C22(H22), C15(H15), C14(H14), C12(H12), C21(H21), C24(H24),
 C20(H20), C19(H19), C13(H13), C25(H25), C28(H28), C26(H26), C27(H27)
3.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C7(H7A,H7B,H7C), C6(H6A,H6B,H6C), C9(H9A,H9B,H9C),
 C8(H8A,H8B,H8C), C33(H33A,H33B,H33C), C37(H37A,H37B,H37C)
;
_shelx_res_checksum              19951
_shelx_hkl_checksum              37651
_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 2.836
_oxdiff_exptl_absorpt_empirical_full_min 0.438