Enantioselective Diarylcarbene Insertion into Si-H Bonds Induced by Electronic Properties of the Carbenes.
Yang, Liang-Liang; Evans, Declan; Xu, Bin; Li, Wen-Tao; Li, Mao-Lin; Zhu, Shou-Fei; Houk, K. N.; Zhou, Qi-Lin; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c04725

data_4135101
_publ_section_title
;
 Enantioselective Diarylcarbene Insertion into Si-H Bonds Induced by
 Electronic Properties of the Carbenes.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c04725
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C134 H128 O18 P4 Rh2'
_chemical_formula_sum            'C134 H128 O18 P4 Rh2'
_chemical_formula_weight         2356.06
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2018-11-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
????
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.423(3)
_cell_length_b                   28.903(6)
_cell_length_c                   31.726(6)
_cell_measurement_reflns_used    21985
_cell_measurement_temperature    127.15
_cell_measurement_theta_max      28.0470
_cell_measurement_theta_min      1.5509
_cell_volume                     13226(5)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2008)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2008)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2008)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      127.15
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Rigaku Saturn 70 CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  confocal
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1188
_diffrn_reflns_av_unetI/netI     0.1387
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            74686
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.349
_diffrn_reflns_theta_min         1.548
_diffrn_standards_decay_%        0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.358
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7864
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear(Rigaku, 2008)'
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.183
_exptl_crystal_description       prism
_exptl_crystal_F_000             4904
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.947
_refine_diff_density_min         -0.691
_refine_diff_density_rms         0.099
_refine_ls_abs_structure_details
;
 Flack x determined using 4702 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.125
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1447
_refine_ls_number_reflns         23598
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.125
_refine_ls_R_factor_all          0.1192
_refine_ls_R_factor_gt           0.1017
_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^)+(0.0574P)^2^+28.3456P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2024
_refine_ls_wR_factor_ref         0.2163
_reflns_Friedel_coverage         0.815
_reflns_Friedel_fraction_full    0.954
_reflns_Friedel_fraction_max     0.954
_reflns_number_gt                19271
_reflns_number_total             23598
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c04725_si_002.cif
_cod_data_source_block           shelxl_sq
_cod_database_code               4135101
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.945
_shelx_estimated_absorpt_t_min   0.894
_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, All O(H) groups
2. Restrained distances
 O17-H17
 0.87 with sigma of 0.01
 O18-H18
 0.87 with sigma of 0.01
 C133-H17
 1.894631 with sigma of 0.02
 Rh1-H17
 2.935178 with sigma of 0.02
 C134-H18
 1.913743 with sigma of 0.02
 Rh2-H18
 2.928741 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C79) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C16(H16A,H16B), C17(H17A,H17B), C41(H41A,H41B),
 C42(H42A,H42B), C49(H49A,H49B), C50(H50A,H50B), C74(H74A,H74B), C75(H75A,H75B),
  C82(H82A,H82B), C83(H83A,H83B), C107(H10A,H10B), C108(H10C,H10D), C115(H11A,
 H11B), C116(H11C,H11D)
4.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C12(H12), C14(H14), C19(H19), C21(H21), C23(H23), C27(H27),
 C29(H29), C31(H31), C37(H37), C39(H39), C45(H45), C47(H47), C52(H52), C54(H54),
  C56(H56), C60(H60), C62(H62), C64(H64), C70(H70), C72(H72), C78(H78),
 C80(H80), C85(H85), C87(H87), C89(H89), C93(H93), C95(H95), C97(H97),
 C103(H103), C105(H105), C111(H111), C113(H113), C118(H118), C120(H120),
 C122(H122), C126(H126), C128(H128), C130(H130)
4.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C32(H32A,H32B,H32C), C33(H33A,H33B,
 H33C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C65(H65A,H65B,H65C), C66(H66A,
 H66B,H66C), C90(H90A,H90B,H90C), C91(H91A,H91B,H91C), C98(H98A,H98B,H98C),
 C99(H99A,H99B,H99C), C123(H12A,H12B,H12C), C124(H12D,H12E,H12F), C131(H13A,
 H13B,H13C), C132(H13D,H13E,H13F), C133(H13G,H13H,H13I), C134(H13J,H13K,H13L)
;
_shelx_res_checksum              81887
_shelx_hkl_checksum              43648
_shelx_fab_checksum              40902
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'