Synthesis of hydrosilylboronates via the monoborylation of a dihydrosilane Si‒H bond and their application for the generation of dialkylhydrosilyl anions
Takeuchi, Takumi; Shishido, Ryosuke; Kubota, Koji; Ito, Hajime; Chemical Science  (2021) –; doi:10.1039/D1SC01440D

data_1564337
_publ_section_title
;
 Synthesis of hydrosilylboronates via the monoborylation of a
 dihydrosilane Si--H bond and their application for the generation of
 dialkylhydrosilyl anions
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC01440D
_journal_year                    2021
_chemical_formula_moiety         'C8 H19 B Si, 2(C3 H6 O)'
_chemical_formula_sum            'C14 H31 B O2 Si'
_chemical_formula_weight         270.29
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-11-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-02-25 deposited with the CCDC.	2021-08-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.7304(6)
_cell_length_b                   14.6636(6)
_cell_length_c                   9.7331(4)
_cell_measurement_reflns_used    7744
_cell_measurement_temperature    173
_cell_measurement_theta_max      29.4210
_cell_measurement_theta_min      2.7110
_cell_volume                     1816.91(14)
_computing_cell_refinement       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_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      173
_diffrn_detector                 'PLATUS 200K area detector'
_diffrn_detector_area_resol_mean 5.811
_diffrn_detector_type            'HPC area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.915
_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    -71.00  56.00   0.50   70.19    --   -1.80  29.00-180.00  254
  2  \w     62.00  88.00   0.50   70.19    --   -1.80  29.00-180.00   52
  3  \w    -65.00  22.00   0.50   70.19    --    1.80  60.00 -30.00  174
  4  \w     20.00  67.00   0.50   70.19    --    1.80  29.00 -90.00   94
  5  \w    -88.00  17.00   0.50   70.19    --    1.80  29.00 -90.00  210
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB P200'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0018029000
_diffrn_orient_matrix_UB_12      0.0284876000
_diffrn_orient_matrix_UB_13      -0.0415851000
_diffrn_orient_matrix_UB_21      0.0353066000
_diffrn_orient_matrix_UB_22      -0.0422501000
_diffrn_orient_matrix_UB_23      -0.0210999000
_diffrn_orient_matrix_UB_31      -0.0637256000
_diffrn_orient_matrix_UB_32      -0.0225686000
_diffrn_orient_matrix_UB_33      -0.0128096000
_diffrn_radiation_monochromator  'multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0841
_diffrn_reflns_av_unetI/netI     0.0524
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.915
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            25184
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.915
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.209
_diffrn_reflns_theta_min         2.634
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_type              micromax007
_exptl_absorpt_coefficient_mu    0.124
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62825
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.45a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    0.988
_exptl_crystal_description       plate
_exptl_crystal_F_000             600
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.269
_refine_diff_density_min         -0.593
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     236
_refine_ls_number_reflns         2333
_refine_ls_number_restraints     449
_refine_ls_restrained_S_all      0.975
_refine_ls_R_factor_all          0.0948
_refine_ls_R_factor_gt           0.0772
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1862P)^2^+0.1943P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2346
_refine_ls_wR_factor_ref         0.2568
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1771
_reflns_number_total             2333
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01440d2.cif
_cod_data_source_block           t4
_cod_database_code               1564337
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'Si C H O B'
_shelx_estimated_absorpt_t_max   0.998
_shelx_estimated_absorpt_t_min   0.964
_reflns_odcompleteness_completeness 99.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All Si(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 Si01, Si02, C003, C003, C10, C10, C005, C005, B1, O007, O007, O008, O008,
 C009, C009, C00A, C00A, C00B, C00B, C00C, C00C, C00D, C00D, C00E, C00E, C00F,
 C00F, C2, C2, C1, C1, B2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O1, Si01, Si02, C003, B1, C00E, B2, C00A, C10, C009, C00F, O007, O008, O0,
 C005, C2, C00D, C1, C00C, C00B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O1, Si01, C003, B1, Si02, C10, C009, C00A, C00E, C00F, O007, O008, B2, C005,
 C2, O0, C00D, C00C, C1, C00B, C2A, C4, C0, C1A, C5, C3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C005, B1, O007, O008, C00B, C00C, C00D, C2, C1, B2, O0, O1, C3, C4, C0, C1A,
 C2A, C5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
Si01 \\sim Si02 \\sim C003 \\sim C003 \\sim C10 \\sim C10 \\sim C005 \\sim C005
\\sim B1 \\sim O007 \\sim O007 \\sim O008 \\sim O008 \\sim C009 \\sim C009
\\sim C00A \\sim C00A \\sim C00B \\sim C00B \\sim C00C \\sim C00C \\sim C00D
\\sim C00D \\sim C00E \\sim C00E \\sim C00F \\sim C00F \\sim C2 \\sim C2 \\sim
C1 \\sim C1 \\sim B2: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
O1 \\sim Si01 \\sim Si02 \\sim C003 \\sim B1 \\sim C00E \\sim B2 \\sim C00A
\\sim C10 \\sim C009 \\sim C00F \\sim O007 \\sim O008 \\sim O0 \\sim C005 \\sim
C2 \\sim C00D \\sim C1 \\sim C00C \\sim C00B: within 1.7A with sigma of 0.04
and sigma for terminal atoms of 0.08
O1 \\sim Si01 \\sim C003 \\sim B1 \\sim Si02 \\sim C10 \\sim C009 \\sim C00A
\\sim C00E \\sim C00F \\sim O007 \\sim O008 \\sim B2 \\sim C005 \\sim C2 \\sim
O0 \\sim C00D \\sim C00C \\sim C1 \\sim C00B \\sim C2A \\sim C4 \\sim C0 \\sim
C1A \\sim C5 \\sim C3: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C005 \\sim B1 \\sim O007 \\sim O008 \\sim C00B \\sim C00C \\sim C00D \\sim C2
\\sim C1 \\sim B2 \\sim O0 \\sim O1 \\sim C3 \\sim C4 \\sim C0 \\sim C1A \\sim
C2A \\sim C5: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
4. Others
 Fixed Sof: Si01(0.25) H01(0.25) Si02(0.25) H02(0.25) C005(0.25) B1(0.25)
 O007(0.25) O008(0.25) C009(0.5) H00A(0.5) H00B(0.5) H00C(0.5) C00A(0.5)
 H00D(0.5) H00E(0.5) H00F(0.5) C00B(0.25) H00P(0.25) H00Q(0.25) H00R(0.25)
 C00C(0.25) H00M(0.25) H00N(0.25) H00O(0.25) C00D(0.25) H00S(0.25) H00T(0.25)
 H00U(0.25) C00E(0.5) H00G(0.5) H00H(0.5) H00I(0.5) C00F(0.5) H00J(0.5)
 H00K(0.5) H00L(0.5) C2(0.25) C1(0.25) H1A(0.25) H1B(0.25) H1C(0.25) B2(0.25)
 O0(0.25) O1(0.25) C3(0.25) H3A(0.25) H3B(0.25) H3C(0.25) C4(0.25) H4A(0.25)
 H4B(0.25) H4C(0.25) C0(0.25) C1A(0.25) H1AA(0.25) H1AB(0.25) H1AC(0.25)
 C2A(0.25) C5(0.25) H5A(0.25) H5B(0.25) H5C(0.25)
5.a Ternary CH refined with riding coordinates:
 Si01(H01), Si02(H02)
5.b Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C009(H00A,H00B,H00C), C00A(H00D,H00E,H00F), C00B(H00P,
 H00Q,H00R), C00C(H00M,H00N,H00O), C00D(H00S,H00T,H00U), C00E(H00G,H00H,H00I),
 C00F(H00J,H00K,H00L), C1(H1A,H1B,H1C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C),
 C1A(H1AA,H1AB,H1AC), C5(H5A,H5B,H5C)
;
_shelx_res_checksum              84467
_shelx_hkl_checksum              88494
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.289
_oxdiff_exptl_absorpt_empirical_full_min 0.540