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_1553939
_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         'C22 H22 Si'
_chemical_formula_sum            'C22 H22 Si'
_chemical_formula_weight         314.49
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-04-12
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_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                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   8.8464(4)
_cell_length_b                   13.6195(6)
_cell_length_c                   30.1026(12)
_cell_measurement_reflns_used    19225
_cell_measurement_temperature    180.00(10)
_cell_measurement_theta_max      29.6840
_cell_measurement_theta_min      4.0160
_cell_volume                     3626.9(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.7e (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.7e (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.7e (Rigaku OD, 2015)'
_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_environment      N~2~
_diffrn_ambient_temperature      180.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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    -26.00  22.00   0.25    1.51    --   -1.00 -38.00   0.00  192
  2  \w    -11.00  16.00   0.25    1.51    --   -1.00 -82.00  60.00  108
  3  \w      8.00  35.00   0.25    1.51    --    1.40 -82.00   0.00  108
  4  \w     -8.00  33.00   0.25    1.51    --    1.40 -77.00-120.00  164
  5  \w    -25.00  35.00   0.25    1.51    --    1.40 -82.00 -60.00  240
  6  \w    -32.00  35.00   0.25    1.51    --    1.40 -82.00 120.00  268
  7  \w    -32.00   6.00   0.25    1.51    --   -1.00  19.00 -60.00  152
  8  \w     43.00  87.00   0.25    1.51    --   -1.00  19.00 -60.00  176
  9  \w    -45.00 -20.00   0.25    1.51    --    1.40 -77.00-120.00  100
 10  \w    -90.00 -16.00   0.25    1.51    --   -1.00 -69.00  10.00  296
 11  \w    -88.00 -31.00   0.25    1.51    --   -1.00 -38.00 -60.00  228
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro: Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0132093000
_diffrn_orient_matrix_UB_12      -0.0505010000
_diffrn_orient_matrix_UB_13      -0.0042663000
_diffrn_orient_matrix_UB_21      0.0483346000
_diffrn_orient_matrix_UB_22      0.0127628000
_diffrn_orient_matrix_UB_23      -0.0178672000
_diffrn_orient_matrix_UB_31      0.0626148000
_diffrn_orient_matrix_UB_32      0.0007666000
_diffrn_orient_matrix_UB_33      0.0147389000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0442
_diffrn_reflns_av_unetI/netI     0.0170
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            60476
_diffrn_reflns_theta_full        26.02
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.55
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.127
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67173
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.7e (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic whiteish colourless'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.152
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1344
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.238
_refine_diff_density_min         -0.207
_refine_diff_density_rms         0.036
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     212
_refine_ls_number_reflns         3555
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0400
_refine_ls_R_factor_gt           0.0365
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0502P)^2^+1.5922P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0977
_refine_ls_wR_factor_ref         0.1005
_reflns_number_gt                3246
_reflns_number_total             3555
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c7qo00927e2.cif
_cod_data_source_block           exp_374
_cod_database_code               1553939
_chemical_oxdiff_formula         'C1 H1 Si1'
_reflns_odcompleteness_completeness 99.55
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_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:
 C3(H3), C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C14(H14), C15(H15), C17(H17),
 C18(H18)
2.b Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C)
;
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.393
_oxdiff_exptl_absorpt_empirical_full_min 0.706