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_7047498
_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         'C42 H49 B N P'
_chemical_formula_sum            'C42 H49 B N P'
_chemical_formula_weight         609.60
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-09-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-09-04 deposited with the CCDC.
2018-09-10 downloaded from the CCDC.
;
_cell_angle_alpha                68.521(12)
_cell_angle_beta                 66.763(11)
_cell_angle_gamma                88.970(12)
_cell_formula_units_Z            2
_cell_length_a                   12.418(7)
_cell_length_b                   12.623(7)
_cell_length_c                   13.822(7)
_cell_measurement_reflns_used    4656
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      24.76
_cell_measurement_theta_min      2.30
_cell_volume                     1832.2(17)
_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 APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0598
_diffrn_reflns_av_unetI/netI     0.0507
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            27556
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         1.742
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.104
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6763
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0721 before and 0.0623 after correction.
The Ratio of minimum to maximum transmission is 0.9072.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.105
_exptl_crystal_description       block
_exptl_crystal_F_000             656
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.392
_refine_diff_density_min         -0.527
_refine_diff_density_rms         0.045
_refine_ls_extinction_coef       0.0103(15)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     460
_refine_ls_number_reflns         6444
_refine_ls_number_restraints     188
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.1074
_refine_ls_R_factor_gt           0.0684
_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^)+(0.0597P)^2^+1.5921P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1568
_refine_ls_wR_factor_ref         0.1848
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4166
_reflns_number_total             6444
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8dt03201g2.cif
_cod_data_source_block           7
_cod_depositor_comments
'Adding full bibliography for 7047497--7047501.cif.'
_cod_original_cell_volume        1832.2(16)
_cod_database_code               7047498
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.983
_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
 P1A-C37A \\sim P1B-C37B
 with sigma of 0.02
 P1B-C4 \\sim P1A-C4
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(P1A) = Uanis(P1B)
Uanis(C42A) = Uanis(C42B)
Uanis(C41B) = Uanis(C41A)
Uanis(C37A) = Uanis(C37B)
Uanis(C38A) = Uanis(C38B)
Uanis(C39B) = Uanis(C39A)
Uanis(C40B) = Uanis(C40A)
Uanis(C36B) = Uanis(C36A)
Uanis(C32A) = Uanis(C32B)
Uanis(C33B) = Uanis(C33A)
Uanis(C34B) = Uanis(C34A)
Uanis(C35B) = Uanis(C35A)
Uanis(C31B) = Uanis(C31A)
4. Rigid body (RIGU) restrains
 P1B, C37B, C38B, C39B, C40B, C42B, C41B, C31B, C32B, C33B, C34B, C35B, C36B,
 P1A, C31A, C36A, C35A, C34A, C33A, C32A, C38A, C37A, C42A, C41A, C40A, C39A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: P1B(0.5) C37B(0.5) C38B(0.5) H38B(0.5) C39B(0.5) H39B(0.5)
 C40B(0.5) H40B(0.5) C42B(0.5) H42B(0.5) C41B(0.5) H41B(0.5) C31B(0.5)
 C32B(0.5) H32B(0.5) C33B(0.5) H33B(0.5) C34B(0.5) H34B(0.5) C35B(0.5)
 H35B(0.5) C36B(0.5) H36B(0.5) P1A(0.5) C31A(0.5) C36A(0.5) H36A(0.5) C35A(0.5)
 H35A(0.5) C34A(0.5) H34A(0.5) C33A(0.5) H33A(0.5) C32A(0.5) H32A(0.5)
 C38A(0.5) H38A(0.5) C37A(0.5) C42A(0.5) H42A(0.5) C41A(0.5) H41A(0.5)
 C40A(0.5) H40A(0.5) C39A(0.5) H39A(0.5)
6.a Ternary CH refined with riding coordinates:
 C25(H25), C28(H28)
6.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C15(H15), C9(H9), C17(H17), C3(H3), C11(H11), C38B(H38B), C39B(H39B),
 C40B(H40B), C42B(H42B), C41B(H41B), C32B(H32B), C33B(H33B), C34B(H34B),
 C35B(H35B), C36B(H36B), C36A(H36A), C35A(H35A), C34A(H34A), C33A(H33A),
 C32A(H32A), C38A(H38A), C42A(H42A), C41A(H41A), C40A(H40A), C39A(H39A)
6.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C24(H24A,H24B,H24C), C29(H29A,H29B,
 H29C), C22(H22A,H22B,H22C), C27(H27A,H27B,H27C), C30(H30A,H30B,H30C), C23(H23A,
 H23B,H23C), C26(H26A,H26B,H26C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              21542
_olex2_submission_special_instructions 'No special instructions were received'