C(sp3)–H oxygenation via alkoxypalladium(ii) species: an update for the mechanism
Zhang, Shuaizhong; Zhang, Jinquan; Zou, Hongbin; Chemical Science 13 (2022) 1298–1306; doi:10.1039/D1SC06907A

data_1566079
_publ_section_title
;
 C(sp3)--H oxygenation via alkoxypalladium(ii) species: an update for the
 mechanism
;
_journal_issue                   5
_journal_name_full               'Chemical Science'
_journal_page_first              1298
_journal_page_last               1306
_journal_paper_doi               10.1039/D1SC06907A
_journal_volume                  13
_journal_year                    2022
_chemical_formula_moiety         '2(C26 H30 N6 O4 Pd2), 2.5(C H2 Cl2)'
_chemical_formula_sum            'C54.5 H65 Cl5 N12 O8 Pd4'
_chemical_formula_weight         1619.03
_chemical_name_systematic        'dimer 5,6-membered palladacycle'
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-01-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-01-26 deposited with the CCDC.	2022-01-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.411(6)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   39.352(5)
_cell_length_b                   14.1869(16)
_cell_length_c                   22.175(2)
_cell_measurement_reflns_used    9906
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      27.10
_cell_measurement_theta_min      2.63
_cell_volume                     12303(2)
_computing_cell_refinement       'SAINT V8.40B (Bruker Nano, Inc., 2019)'
_computing_data_collection       'Bruker Instrument Service vV6.2.14'
_computing_data_reduction        'SAINT V8.40B (Bruker Nano, Inc., 2019)'
_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      170.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'zju Bruker D8 Venture Ims3.0'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0330
_diffrn_reflns_av_unetI/netI     0.0184
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       49
_diffrn_reflns_limit_h_min       -50
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            100301
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.064
_diffrn_reflns_theta_min         2.018
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.430
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6601
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1578 before and 0.0472 after correction.
The Ratio of minimum to maximum transmission is 0.8854.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.748
_exptl_crystal_description       block
_exptl_crystal_F_000             6472
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.23
_refine_diff_density_max         1.092
_refine_diff_density_min         -0.989
_refine_diff_density_rms         0.075
_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     789
_refine_ls_number_reflns         13447
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0290
_refine_ls_R_factor_gt           0.0242
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0253P)^2^+31.2743P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0574
_refine_ls_wR_factor_ref         0.0596
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12095
_reflns_number_total             13447
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc06907a2.cif
_cod_data_source_block           mo_210112_zjq210112_0m
_cod_depositor_comments          'Adding full bibliography for 1566079.cif.'
_cod_original_cell_volume        12302(2)
_cod_original_formula_sum        'C54.50 H65 Cl5 N12 O8 Pd4'
_cod_database_code               1566079
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.734
_shelx_estimated_absorpt_t_min   0.613
_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. Others
 Sof(Cl3)=Sof(Cl4)=Sof(C54)=Sof(H54A)=Sof(H54B)=1-FVAR(1)
 Sof(Cl5)=Sof(Cl6)=Sof(C55)=Sof(H55A)=Sof(H55B)=FVAR(1)
 Fixed Sof: H56A(0.5) H56B(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C23(H23A,H23B), C24(H24A,H24B), C36(H36A,
 H36B), C37(H37A,H37B), C49(H49A,H49B), C50(H50A,H50B), C53(H53A,H53B),
 C56(H56A,H56B), C55(H55A,H55B), C54(H54A,H54B)
3.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C14(H14), C15(H15), C16(H16),
 C17(H17), C20(H20), C27(H27), C28(H28), C29(H29), C30(H30), C33(H33), C40(H40),
  C41(H41), C42(H42), C43(H43), C46(H46)
3.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C51(H51A,H51B,H51C), C52(H52A,
 H52B,H52C)
;
_shelx_res_checksum              54845
_shelx_hkl_checksum              7546
_olex2_submission_special_instructions 'No special instructions were received'