Versatile halogenation <i>via</i> a C<sub>NHC</sub>^C<sub>sp3</sub> palladacycle intermediate.
Teng, Qiaoqiao; Liu, Ziwei; Song, Haobin; Liu, Jiayu; Zhao, Yaru; Jiang, Weihua; Huynh, Han Vinh; Meng, Qi; Dalton transactions (Cambridge, England : 2003) 52 (2023) 2223–2226; doi:10.1039/d3dt00113j

data_7712302
_publ_section_title
;
 Versatile halogenation <i>via</i> a C<sub>NHC</sub>^C<sub>sp3</sub>
 palladacycle intermediate.
;
_journal_issue                   8
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              2223
_journal_page_last               2226
_journal_paper_doi               10.1039/d3dt00113j
_journal_volume                  52
_journal_year                    2023
_chemical_formula_moiety         'C32 H36 Br2 N4 O Pd, C4 H8 O'
_chemical_formula_sum            'C36 H44 Br2 N4 O2 Pd'
_chemical_formula_weight         830.97
_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             2021-12-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-12-14 deposited with the CCDC.	2023-02-06 downloaded from the CCDC.
;
_cell_angle_alpha                93.233(2)
_cell_angle_beta                 92.079(2)
_cell_angle_gamma                110.721(2)
_cell_formula_units_Z            2
_cell_length_a                   9.5373(5)
_cell_length_b                   12.3311(7)
_cell_length_c                   16.2241(9)
_cell_measurement_reflns_used    3336
_cell_measurement_temperature    150
_cell_measurement_theta_max      25.342
_cell_measurement_theta_min      2.288
_cell_volume                     1778.55(17)
_computing_cell_refinement       'SAINT V8.40A (?, 2016)'
_computing_data_reduction        'SAINT V8.40A (?, 2016)'
_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      150.0
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0
_diffrn_reflns_av_unetI/netI     0.0598
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            6404
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.368
_diffrn_reflns_theta_min         2.096
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.805
_exptl_absorpt_correction_T_max  0.5623
_exptl_absorpt_correction_T_min  0.1523
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
TWINABS-2012/1 (Bruker,2012) was used for absorption correction.

Final HKLF 4 output contains 26454 reflections, Rint = 0.0553
 (14069 with I > 3sig(I), Rint = 0.0453)
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.552
_exptl_crystal_description       block
_exptl_crystal_F_000             840
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.882
_refine_diff_density_min         -0.557
_refine_diff_density_rms         0.114
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.990
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     428
_refine_ls_number_reflns         6404
_refine_ls_number_restraints     455
_refine_ls_restrained_S_all      0.962
_refine_ls_R_factor_all          0.0614
_refine_ls_R_factor_gt           0.0414
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0314P)^2^+3.3150P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0855
_refine_ls_wR_factor_ref         0.0958
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5080
_reflns_number_total             6404
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00113j2.cif
_cod_data_source_block           12083_0m_4
_cod_depositor_comments
'Adding full bibliography for 7712302--7712304.cif.'
_cod_original_cell_volume        1778.54(17)
_cod_database_code               7712302
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.872
_shelx_estimated_absorpt_t_min   0.730
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(O2) \\sim Ueq, Uanis(C33) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(O3) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Others
 Fixed Sof: O3(0.5) H36A(0.5) H36B(0.5) H36C(0.5) H36D(0.5) O2(0.5) C33(0.5)
 H33A(0.5) H33B(0.5) H34C(0.5) H34D(0.5) H34A(0.5) H34B(0.5) C37(0.5) H37A(0.5)
 H37B(0.5)
5.a Ternary CH refined with riding coordinates:
 C11(H11), C8(H8)
5.b Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C25(H25A,H25B), C36(H36A,H36B), C36(H36C,H36D), C17(H17A,
 H17B), C33(H33A,H33B), C34(H34C,H34D), C34(H34A,H34B), C35(H35A,H35B),
 C37(H37A,H37B)
5.c Aromatic/amide H refined with riding coordinates:
 C16(H16), C6(H6), C5(H5), C30(H30), C32(H32), C31(H31), C28(H28), C3(H3),
 C22(H22), C4(H4), C19(H19), C15(H15), C29(H29), C23(H23), C20(H20), C21(H21)
5.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C12(H12A,H12B,H12C), C10(H10A,H10B,H10C), C9(H9A,H9B,H9C)
;
_olex2_submission_special_instructions 'No special instructions were received'