Iron-Catalyzed H/D Exchange of Primary Silanes, Secondary Silanes, and Tertiary Siloxanes
Linford-Wood, Thomas G.; Mahon, Mary F.; Grayson, Matthew N.; Webster, Ruth L.; ACS Catalysis  (2022) 2979–2985; doi:10.1021/acscatal.2c00224

data_4519336
_publ_section_title
;
 Iron-Catalyzed H/D Exchange of Primary Silanes, Secondary Silanes, and
 Tertiary Siloxanes
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              2979
_journal_page_last               2985
_journal_paper_doi               10.1021/acscatal.2c00224
_journal_year                    2022
_chemical_formula_moiety         '0.5(C50 H72 Fe2 N4 Si2)'
_chemical_formula_sum            'C25 H36 Fe N2 Si'
_chemical_formula_weight         448.50
_space_group_crystal_system      orthorhombic
_space_group_IT_number           64
_space_group_name_Hall           '-C 2ac 2'
_space_group_name_H-M_alt        'C m c e'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     heavy
_audit_creation_date             2021-10-28
_audit_creation_method
;
Olex2 1.5
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.7305(7)
_cell_length_b                   14.4274(7)
_cell_length_c                   17.8945(7)
_cell_measurement_reflns_used    11615
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.6230
_cell_measurement_theta_min      4.9300
_cell_volume                     4835.7(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1150
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.880
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_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  0.0368
_diffrn_reflns_av_unetI/netI     0.0170
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.880
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            24539
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.880
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         89.528
_diffrn_reflns_theta_min         4.590
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.557
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60450
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.232
_exptl_crystal_description       block
_exptl_crystal_F_000             1920
_exptl_crystal_size_max          0.231
_exptl_crystal_size_mid          0.174
_exptl_crystal_size_min          0.063
_refine_diff_density_max         0.600
_refine_diff_density_min         -1.001
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.107
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     163
_refine_ls_number_reflns         2517
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.0433
_refine_ls_R_factor_gt           0.0419
_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^)+(0.0629P)^2^+6.4628P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1149
_refine_ls_wR_factor_ref         0.1161
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2421
_reflns_number_total             2517
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs2c00224_si_002.cif
_cod_data_source_block           s21rlw25
_cod_original_sg_symbol_Hall     '-C 2bc 2'
_cod_database_code               4519336
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.732
_shelx_estimated_absorpt_t_min   0.361
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups, H13 of C13
 At 1.2 times of:
  H5 of C5, H4 of C4, H3 of C3
2. Restrained distances
 C12-H12A = C12-H12B
 0.98 with sigma of 0.005
 H12A-H12B
 1.6 with sigma of 0.005
 C13-H13A = C13-H13
 0.98 with sigma of 0.005
3. Others
 Fixed Sof: C12(0.5) H12A(0.5) H12B(0.5)
4.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5)
4.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C11(H11A,H11B,H11C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              66323
_shelx_hkl_checksum              45311