Late-Stage Diversification by Selectivity Switch in meta-C–H Activation: Evidence for Singlet Stabilization
Korvorapun, Korkit; Kuniyil, Rositha; Ackermann, Lutz; ACS Catalysis  (2019) 435–; doi:10.1021/acscatal.9b04592

data_4517179
_publ_section_title
;
 Late-Stage Diversification by Selectivity Switch in meta-C--H Activation:
 Evidence for Singlet Stabilization
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              435
_journal_paper_doi               10.1021/acscatal.9b04592
_journal_year                    2019
_chemical_formula_moiety         'C34 H33 B F2 N6'
_chemical_formula_sum            'C34 H33 B F2 N6'
_chemical_formula_weight         574.47
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-07-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                94.418(2)
_cell_angle_beta                 94.020(3)
_cell_angle_gamma                90.953(3)
_cell_formula_units_Z            4
_cell_length_a                   10.4593(10)
_cell_length_b                   16.8136(17)
_cell_length_c                   16.9094(11)
_cell_measurement_reflns_used    2955
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      27.80
_cell_measurement_theta_min      2.28
_cell_volume                     2956.8(5)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0389
_diffrn_reflns_av_unetI/netI     0.0271
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            108206
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.670
_diffrn_reflns_theta_min         2.323
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.086
_exptl_absorpt_correction_T_max  0.8749
_exptl_absorpt_correction_T_min  0.8261
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1121 before and 0.0587 after correction. The Ratio of minimum to maximum transmission is 0.9442. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.290
_exptl_crystal_description       block
_exptl_crystal_F_000             1208
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of DCM and hexane  by solvent layering'
_exptl_crystal_size_max          0.607
_exptl_crystal_size_mid          0.465
_exptl_crystal_size_min          0.242
_refine_diff_density_max         0.409
_refine_diff_density_min         -0.389
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     787
_refine_ls_number_reflns         18151
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0569
_refine_ls_R_factor_gt           0.0464
_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^)+(0.0644P)^2^+1.1926P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1217
_refine_ls_wR_factor_ref         0.1302
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15227
_reflns_number_total             18151
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b04592_si_010.cif
_cod_data_source_block           0408_cg_0m
_cod_database_code               4517179
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.979
_shelx_estimated_absorpt_t_min   0.949
_olex2_refinement_description
;
1. 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
2.a Ternary CH refined with riding coordinates:
 C32(H32), C66(H66)
2.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C46(H46A,H46B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C13(H13), C14(H14), C16(H16), C17(H17), C20(H20), C25(H25),
 C26(H26), C27(H27), C30(H30), C31(H31), C36(H36), C41(H41), C42(H42), C44(H44),
  C45(H45), C48(H48), C53(H53), C54(H54), C55(H55), C58(H58), C64(H64), C65(H65)
2.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C60(H60A,H60B,H60C), C61(H61A,
 H61B,H61C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C67(H67A,H67B,H67C),
 C68(H68A,H68B,H68C)
;
_shelx_res_checksum              78926
_shelx_hkl_checksum              68297
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 800'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_special_instructions 'No special instructions were received'