Contrasting reactivity of (boryl)(aryl)lithium-amide with electrophiles: N- vs. p-aryl-C-nucleophilic substitution.
Dhara, Debabrata; Vijayakanth, Thangavel; Nayak, Mithilesh Kumar; Kalita, Pankaj; Boomishankar, Ramamoorthy; Yildiz, Cem Burak; Chandrasekhar, Vadapalli; Jana, Anukul; Dalton transactions (Cambridge, England : 2003) 47 (2018) 14411–14415; doi:10.1039/c8dt03201g

data_7047500
_publ_section_title
;
 Contrasting reactivity of (boryl)(aryl)lithium-amide with electrophiles:
 N- vs. p-aryl-C-nucleophilic substitution.
;
_journal_issue                   41
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              14411
_journal_page_last               14415
_journal_paper_doi               10.1039/c8dt03201g
_journal_volume                  47
_journal_year                    2018
_chemical_formula_moiety         'C31 H43 B Cl N Si'
_chemical_formula_sum            'C31 H43 B Cl N Si'
_chemical_formula_weight         504.01
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_symmetry_space_group_name_Hall  'P 2c -2ac'
_symmetry_space_group_name_H-M   'P c a 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-09-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-09-05 deposited with the CCDC.
2018-09-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.030(2)
_cell_length_b                   10.4822(13)
_cell_length_c                   16.225(2)
_cell_measurement_reflns_used    9979
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      27.07
_cell_measurement_theta_min      2.39
_cell_volume                     2896.4(6)
_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      100.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_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  0.0447
_diffrn_reflns_av_unetI/netI     0.0305
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            50208
_diffrn_reflns_point_group_measured_fraction_full 0.833
_diffrn_reflns_point_group_measured_fraction_max 0.806
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.161
_diffrn_reflns_theta_min         1.943
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.193
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.7203
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0576 before and 0.0545 after correction. The Ratio of minimum to maximum transmission is 0.9659. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.156
_exptl_crystal_description       block
_exptl_crystal_F_000             1088
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.206
_refine_diff_density_min         -0.222
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 1542 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     338
_refine_ls_number_reflns         5726
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0410
_refine_ls_R_factor_gt           0.0335
_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^)+(0.0474P)^2^+0.3059P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0815
_refine_ls_wR_factor_ref         0.0854
_reflns_Friedel_coverage         0.559
_reflns_Friedel_fraction_full    0.652
_reflns_Friedel_fraction_max     0.600
_reflns_number_gt                5100
_reflns_number_total             5726
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8dt03201g2.cif
_cod_data_source_block           6
_cod_depositor_comments
'Adding full bibliography for 7047497--7047501.cif.'
_cod_original_cell_volume        2896.3(6)
_cod_database_code               7047500
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.964
_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. Restrained distances
 Cl0A-Si1 \\sim Cl1-Si1
 with sigma of 0.02
 Si1-C1AA \\sim Si1-C0AA
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Cl0A) = Uanis(C0AA)
Uanis(C1AA) = Uanis(Cl1)
4. Others
 Sof(Cl0A)=Sof(C1AA)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=1-FVAR(1)
 Sof(Cl1)=Sof(C0AA)=Sof(H0AA)=Sof(H0AB)=Sof(H0AC)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C1(H1A), C4(H4)
5.b Me refined with riding coordinates:
 C1AA(H1AA,H1AB,H1AC)
5.c Aromatic/amide H refined with riding coordinates:
 C3P(H3P), C4P(H4P), C5P(H5P), C9P(H9P), C11P(H11P), C15P(H15P), C17P(H17P)
5.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C2(H2A,H2B,H2C), C7(H7A,H7B,H7C), C6(H6A,H6B,H6C), C5(H5A,
 H5B,H5C), C9(H9A,H9B,H9C), C8(H8A,H8B,H8C), C12(H12A,H12B,H12C), C11(H11A,H11B,
 H11C), C10(H10A,H10B,H10C), C0AA(H0AA,H0AB,H0AC)
;
_shelx_res_checksum              24439
_olex2_submission_special_instructions 'No special instructions were received'