Intermolecular C-H silylations of arenes and heteroarenes with mono-, bis-, and tris(trimethylsiloxy)hydrosilanes: control of silane redistribution under operationally diverse approaches.
Swann, Noah; Tang, Kiki; Nam, Jihyeon; Lee, Jooyeon; Domin, Marek; Shaw, Thomas E.; Kozimor, Stosh A.; Som, Salina; Lee, Kangsang L.; Chemical science 15 (2024) 11912–11918; doi:10.1039/d4sc03394a

data_1572023
_publ_section_title
;
 Intermolecular C-H silylations of arenes and heteroarenes with mono-,
 bis-, and tris(trimethylsiloxy)hydrosilanes: control of silane
 redistribution under operationally diverse approaches.
;
_journal_issue                   30
_journal_name_full               'Chemical science'
_journal_page_first              11912
_journal_page_last               11918
_journal_paper_doi               10.1039/d4sc03394a
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C104 H96 Cl2 P4 Rh2'
_chemical_formula_sum            'C104 H96 Cl2 P4 Rh2'
_chemical_formula_weight         1746.40
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-25
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-04-25 deposited with the CCDC.	2024-06-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.3389(8)
_cell_length_b                   23.8027(13)
_cell_length_c                   24.6313(13)
_cell_measurement_reflns_used    9865
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      23.40
_cell_measurement_theta_min      2.18
_cell_volume                     8406.8(8)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1133
_diffrn_reflns_av_unetI/netI     0.0674
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            148406
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.515
_diffrn_reflns_theta_min         2.180
_diffrn_source_current           0.0
_diffrn_source_power             0.0
_diffrn_source_voltage           0.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.582
_exptl_absorpt_correction_T_max  0.8919
_exptl_absorpt_correction_T_min  0.8056
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1052 before and 0.0813 after correction.
The Ratio of minimum to maximum transmission is 0.9237.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear orangish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.380
_exptl_crystal_description       plate
_exptl_crystal_F_000             3616
_exptl_crystal_size_max          0.179
_exptl_crystal_size_mid          0.089
_exptl_crystal_size_min          0.062
_refine_diff_density_max         1.147
_refine_diff_density_min         -0.449
_refine_diff_density_rms         0.076
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   -0.03(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1026
_refine_ls_number_reflns         19287
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0625
_refine_ls_R_factor_gt           0.0434
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0452P)^2^+1.8324P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0945
_refine_ls_wR_factor_ref         0.1035
_reflns_Friedel_coverage         0.843
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                15629
_reflns_number_total             19287
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03394a2.cif
_cod_data_source_block           ms1442_1
_cod_depositor_comments          'Adding full bibliography for 1572023.cif.'
_cod_database_code               1572023
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.965
_shelx_estimated_absorpt_t_min   0.903
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 1.03(3)
 -0.03(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Aromatic/amide H refined with riding coordinates:
 C009(H009), C00A(H00A), C00C(H00C), C00D(H00D), C00E(H00E), C00H(H00H),
 C00I(H00I), C00J(H00J), C00N(H00N), C00O(H00O), C00U(H00U), C00V(H00V),
 C00W(H00W), C00X(H00X), C00Y(H00Y), C00Z(H00Z), C016(H016), C017(H017),
 C019(H019), C01D(H01G), C01F(H01H), C01H(H01I), C01K(H01K), C01L(H01L),
 C01M(H01M), C01N(H01N), C01R(H01R), C01V(H01V), C01W(H01W), C01X(H01X),
 C01Z(H01Z), C022(H022), C023(H023), C024(H024), C02A(H02G), C02B(H02H),
 C02C(H02I), C02D(H02J), C02G(H02N), C02I(H02O), C02K(H02P), C02M(H02T),
 C02P(H02X), C02Q(H02Y), C02R(H02Z), C02T(H1), C02Y(H4), C032(H032)
3.b Idealised Me refined as rotating group:
 C012(H01A,H01B,H01C), C018(H01D,H01E,H01F), C01O(H01J,H01O,H01P), C01Y(H01Q,
 H01S,H01T), C021(H02A,H02B,H02C), C026(H02D,H02E,H02F), C02E(H02K,H02L,H02M),
 C02L(H02Q,H02R,H02S), C02N(H02U,H02V,H02W), C02S(H02,H,HA), C02W(H2,HB,HC),
 C02X(H3,HD,HE), C02Z(H5,HF,HG), C031(H03A,H03B,H03C), C033(H03D,H03E,H03F),
 C034(H03G,H03H,H03I)
;
_shelx_res_checksum              71233
_olex2_submission_special_instructions 'No special instructions were received'