Rhodium-catalyzed intramolecular carbosilylation of alkynes via C(sp3)–Si bond cleavage
Yang, Qi; Liu, Liang; Chi, Yue; Hao, Wei; Zhang, Wen-Xiong; Xi, Zhenfeng; Organic Chemistry Frontiers 5 (2018) 860–; doi:10.1039/C7QO00927E

data_1553940
_publ_section_title
;
 Rhodium-catalyzed intramolecular carbosilylation of alkynes via
 C(sp3)--Si bond cleavage
;
_journal_issue                   5
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              860
_journal_paper_doi               10.1039/C7QO00927E
_journal_volume                  5
_journal_year                    2018
_chemical_formula_moiety         'C21 H20 Si'
_chemical_formula_sum            'C21 H20 Si'
_chemical_formula_weight         300.46
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-09-06
_audit_creation_method
;
Olex2 1.2
(compiled 2016.08.25 svn.r3337 for OlexSys, GUI svn.r5221)
;
_audit_update_record
;
2017-07-05 deposited with the CCDC.
2017-12-04 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 96.731(6)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   12.2864(7)
_cell_length_b                   9.5206(6)
_cell_length_c                   14.4288(8)
_cell_measurement_reflns_used    5019
_cell_measurement_temperature    180.00(10)
_cell_measurement_theta_max      27.7130
_cell_measurement_theta_min      3.3120
_cell_volume                     1676.16(17)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_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      180.00(10)
_diffrn_detector_area_resol_mean 10.3914
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -26.00   44.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       10.5454  -77.0000 -150.0000 70

  2 omega  -15.00   82.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       10.5454   38.0000   90.0000 97

  3 omega  -52.00   23.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       10.5454  -57.0000  120.0000 75

  4 omega  -16.00   26.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.6392  -99.0000   60.0000 42

  5 omega  -38.00   50.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.6392   38.0000  -30.0000 88

  6 omega -102.00  -77.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.6392 -178.0000  -90.0000 25

  7 omega  -88.00   15.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.6392  -38.0000  150.0000 103
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0276611000
_diffrn_orient_matrix_UB_12      -0.0598414000
_diffrn_orient_matrix_UB_13      -0.0148932000
_diffrn_orient_matrix_UB_21      -0.0151594000
_diffrn_orient_matrix_UB_22      0.0194005000
_diffrn_orient_matrix_UB_23      -0.0471947000
_diffrn_orient_matrix_UB_31      0.0488406000
_diffrn_orient_matrix_UB_32      0.0399005000
_diffrn_orient_matrix_UB_33      0.0006576000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0502
_diffrn_reflns_av_unetI/netI     0.0344
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            19569
_diffrn_reflns_theta_full        26.02
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         2.84
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.135
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57914
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.191
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             640
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.236
_refine_diff_density_min         -0.273
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     202
_refine_ls_number_reflns         3304
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.0575
_refine_ls_R_factor_gt           0.0407
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0415P)^2^+0.7241P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0958
_refine_ls_wR_factor_ref         0.1069
_reflns_number_gt                2605
_reflns_number_total             3304
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c7qo00927e2.cif
_cod_data_source_block           exp_7582
_cod_original_cell_volume        1676.15(17)
_cod_database_code               1553940
_chemical_oxdiff_formula         C22H20N2O3U1
_reflns_odcompleteness_completeness 99.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C15(H15), C16(H16), C17(H17),
 C18(H18), C19(H19)
2.b Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C)
;
_olex2_submission_special_instructions 'No special instructions were received'