Non-Metal-Catalyzed Heterodehydrocoupling of Phosphines and Hydrosilanes: Mechanistic Studies of B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>-Mediated Formation of P-Si Bonds.
Wu, Lipeng; Chitnis, Saurabh S.; Jiao, Haijun; Annibale, Vincent T.; Manners, Ian; Journal of the American Chemical Society 139 (2017) 16780–16790; doi:10.1021/jacs.7b09175

data_4131711
_publ_section_title
;
 Non-Metal-Catalyzed Heterodehydrocoupling of Phosphines and Hydrosilanes:
 Mechanistic Studies of B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>-Mediated
 Formation of P-Si Bonds.
;
_journal_issue                   46
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16780
_journal_page_last               16790
_journal_paper_doi               10.1021/jacs.7b09175
_journal_volume                  139
_journal_year                    2017
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C36 H33 P3 Si3'
_chemical_formula_sum            'C36 H33 P3 Si3'
_chemical_formula_weight         642.80
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-07-11
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.606(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.0012(6)
_cell_length_b                   6.1504(3)
_cell_length_c                   22.4927(11)
_cell_measurement_reflns_used    1466
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      22.19
_cell_measurement_theta_min      3.03
_cell_volume                     1645.63(14)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker Apex suite'
_computing_data_reduction        'SAINT v8.37A (Bruker, 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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'Bruker Apex II kappa CCD area detector'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0677
_diffrn_reflns_av_unetI/netI     0.0998
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            14743
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         0.913
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.315
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5975
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0710 before and 0.0569 after correction. The Ratio of minimum to maximum transmission is 0.8014. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.297
_exptl_crystal_description       needle
_exptl_crystal_F_000             672
_exptl_crystal_size_max          0.41
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.025
_refine_diff_density_max         0.370
_refine_diff_density_min         -0.343
_refine_diff_density_rms         0.070
_refine_ls_abs_structure_details
;
 Flack x determined using 1615 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.05(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     433
_refine_ls_number_reflns         6525
_refine_ls_number_restraints     61
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0957
_refine_ls_R_factor_gt           0.0589
_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^)+(0.0423P)^2^+1.0079P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1118
_refine_ls_wR_factor_ref         0.1258
_reflns_Friedel_coverage         0.768
_reflns_Friedel_fraction_full    0.952
_reflns_Friedel_fraction_max     0.934
_reflns_number_gt                4681
_reflns_number_total             6525
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b09175_si_002.cif
_cod_data_source_block           3g
_cod_database_code               4131711
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.882
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All Si(H) groups
2. Uiso/Uaniso restraints and constraints
P1 \\sim P2 \\sim P3 \\sim Si1 \\sim Si2 \\sim Si3 \\sim Si3A \\sim P2A \\sim
Si2A \\sim P1A \\sim Si1A \\sim P3A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
3. Others
 Fixed Sof: P1(0.75548) P2(0.75548) P3(0.75548) Si1(0.75548) H1(0.75548)
 Si2(0.75548) H2(0.75548) Si3(0.75548) H3(0.75548) Si3A(0.24452) H3AA(0.24452)
 P2A(0.24452) Si2A(0.24452) H2AA(0.24452) P1A(0.24452) Si1A(0.24452)
 H1A(0.24452) P3A(0.24452)
4.a Ternary CH refined with riding coordinates:
 Si1(H1), Si2(H2), Si3(H3), Si3A(H3AA), Si2A(H2AA), Si1A(H1A)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2A), C3(H3A), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C20(H20), C21(H21),
  C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), C28(H28), C29(H29),
 C30(H30), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36)
;
_shelx_res_checksum              1163
_shelx_hkl_checksum              23772
_olex2_submission_special_instructions 'No special instructions were received'