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_7047497
_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         'C38 H55 B Li N O2'
_chemical_formula_sum            'C38 H55 B Li N O2'
_chemical_formula_weight         575.58
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-08-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-09-06 deposited with the CCDC.
2018-09-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.399(7)
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   27.854(2)
_cell_length_b                   18.5533(9)
_cell_length_c                   21.3203(12)
_cell_measurement_reflns_used    9467
_cell_measurement_temperature    119.97(10)
_cell_measurement_theta_max      24.3660
_cell_measurement_theta_min      3.0250
_cell_volume                     10513.9(12)
_computing_cell_refinement       'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_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_environment      N~2~
_diffrn_ambient_temperature      119.97(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.987
_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     68.00 100.00   1.00  171.20    --   13.40  82.00 150.00   32
  2  \w     55.00  98.00   1.00  171.20    --   13.40  77.00  90.00   43
  3  \w    -42.00  53.00   1.00  171.20    --   13.40 -82.00-150.00   95
  4  \w     55.00  91.00   1.00  171.20    --   13.40  77.00 -30.00   36
  5  \w    -44.00 -17.00   1.00  171.20    --  -13.80 -82.00 120.00   27
  6  \w    -63.00  17.00   1.00  171.20    --  -13.80 -82.00  60.00   80
  7  \w    -54.00   8.00   1.00  171.20    --  -13.80 -82.00 -60.00   62
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0237080000
_diffrn_orient_matrix_UB_12      -0.0170153000
_diffrn_orient_matrix_UB_13      -0.0130709000
_diffrn_orient_matrix_UB_21      0.0094029000
_diffrn_orient_matrix_UB_22      -0.0312970000
_diffrn_orient_matrix_UB_23      0.0187815000
_diffrn_orient_matrix_UB_31      -0.0079485000
_diffrn_orient_matrix_UB_32      0.0138009000
_diffrn_orient_matrix_UB_33      0.0262703000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1474
_diffrn_reflns_av_unetI/netI     0.1870
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            21559
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.544
_diffrn_reflns_theta_min         2.592
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.064
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53653
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.29d (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.091
_exptl_crystal_description       block
_exptl_crystal_F_000             3768
_exptl_crystal_size_max          0.401
_exptl_crystal_size_mid          0.331
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.405
_refine_diff_density_min         -0.363
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1193
_refine_ls_number_reflns         21559
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.2397
_refine_ls_R_factor_gt           0.1441
_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^)+(0.1470P)^2^+45.4214P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3650
_refine_ls_wR_factor_ref         0.4063
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10298
_reflns_number_total             21559
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8dt03201g2.cif
_cod_data_source_block           4
_cod_depositor_comments
'Adding full bibliography for 7047497--7047501.cif.'
_cod_original_cell_volume        10513.7(12)
_cod_database_code               7047497
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C55H57N2BLiO2
_shelx_estimated_absorpt_t_max   0.986
_shelx_estimated_absorpt_t_min   0.975
_reflns_odcompleteness_completeness 98.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.860(3)
 0.140(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Ternary CH refined with riding coordinates:
 C25C(H25C), C27A(H27G), C25B(H25B), C28C(H28C), C28A(H28A), C28B(H28B)
3.b Secondary CH2 refined with riding coordinates:
 C34C(H34A,H34B), C31A(H31E,H31F), C34B(H34C,H34D), C31B(H31C,H31D), C31C(H31A,
 H31B), C34A(H34E,H34F), C35B(H35C,H35D), C32A(H32E,H32F), C38C(H38A,H38B),
 C38B(H38C,H38D), C35C(H35A,H35B), C37C(H37A,H37B), C33B(H33C,H33D), C33A(H33E,
 H33F), C33C(H33A,H33B), C38A(H38E,H38F), C32C(H32A,H32B), C32B(H32C,H32D),
 C36B(H36C,H36D), C35A(H35E,H35F), C36C(H36A,H36B), C37B(H37C,H37D), C36A(H36E,
 H36F), C37A(H37E,H37F)
3.c Aromatic/amide H refined with riding coordinates:
 C12B(H12B), C14B(H14B), C3C(H3C), C3B(H3B), C22C(H22C), C3A(H3A), C14A(H14A),
 C5B(H5B), C23B(H23B), C21B(H21B), C22B(H22B), C12C(H12C), C21C(H21C),
 C21A(H21A), C5C(H5C), C12A(H12A), C14C(H14C), C5A(H5A), C23C(H23C), C22A(H22A),
  C23A(H23A)
3.d Idealised Me refined as rotating group:
 C7C(H7CA,H7CB,H7CC), C16B(H16D,H16E,H16F), C18A(H18G,H18H,H18I), C7A(H7AA,
 H7AB,H7AC), C7B(H7BA,H7BB,H7BC), C26B(H26D,H26E,H26F), C9C(H9CA,H9CB,H9CC),
 C26A(H26G,H26H,H26I), C18C(H18A,H18B,H18C), C26C(H26A,H26B,H26C), C25A(H25A,
 H25D,H25E), C18B(H18D,H18E,H18F), C9B(H9BA,H9BB,H9BC), C27C(H27A,H27B,H27C),
 C29C(H29A,H29B,H29C), C27B(H27D,H27E,H27F), C16C(H16A,H16B,H16C), C9A(H9AA,
 H9AB,H9AC), C30A(H30G,H30H,H30I), C29B(H29D,H29E,H29F), C8A(H8AA,H8AB,H8AC),
 C8C(H8CA,H8CB,H8CC), C30C(H30A,H30B,H30C), C17B(H17D,H17E,H17F), C8B(H8BA,H8BB,
 H8BC), C29A(H29G,H29H,H29I), C17A(H17G,H17H,H17I), C16A(H16G,H16H,H16I),
 C30B(H30D,H30E,H30F), C17C(H17A,H17B,H17C)
;
_shelx_res_checksum              50856
_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 2.603
_oxdiff_exptl_absorpt_empirical_full_min 0.583