Mechanistic Basis for Efficient, Site-Selective, Aerobic Catalytic Turnover in Pd-Catalyzed C-H Imidoylation of Heterocycle-Containing Molecules.
Tereniak, Stephen J.; Stahl, Shannon S.; Journal of the American Chemical Society 139 (2017) 14533–14541; doi:10.1021/jacs.7b07359

data_4131600
_publ_section_title
;
 Mechanistic Basis for Efficient, Site-Selective, Aerobic Catalytic
 Turnover in Pd-Catalyzed C-H Imidoylation of Heterocycle-Containing
 Molecules.
;
_journal_issue                   41
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14533
_journal_page_last               14541
_journal_paper_doi               10.1021/jacs.7b07359
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety         'C48 H56 N4 O8 Pd4'
_chemical_formula_sum            'C48 H56 N4 O8 Pd4'
_chemical_formula_weight         1242.56
_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     direct
_audit_creation_date             2015-09-22
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                103.971(5)
_cell_angle_beta                 99.063(7)
_cell_angle_gamma                92.649(11)
_cell_formula_units_Z            2
_cell_length_a                   10.628(3)
_cell_length_b                   11.7410(17)
_cell_length_c                   19.964(3)
_cell_measurement_reflns_used    9883
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      70.150
_cell_measurement_theta_min      27.912
_cell_volume                     2378.1(8)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      99.91
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0283
_diffrn_reflns_av_unetI/netI     0.0154
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            66589
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.000
_diffrn_reflns_theta_max         70.254
_diffrn_reflns_theta_min         2.316
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    12.471
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.5819
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0748 before and 0.0334 after correction.
The Ratio of minimum to maximum transmission is 0.7725.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.735
_exptl_crystal_description       block
_exptl_crystal_F_000             1240
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.074
_refine_diff_density_max         0.420
_refine_diff_density_min         -0.449
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     605
_refine_ls_number_reflns         9030
_refine_ls_number_restraints     54
_refine_ls_restrained_S_all      1.108
_refine_ls_R_factor_all          0.0210
_refine_ls_R_factor_gt           0.0199
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0286P)^2^+1.9470P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0536
_refine_ls_wR_factor_ref         0.0542
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8553
_reflns_number_total             9030
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07359_si_004.cif
_cod_data_source_block           stahl219
_cod_original_cell_volume        2378.0(7)
_cod_database_code               4131600
_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. Uiso/Uaniso restraints and constraints
C45 \\sim C46 \\sim C47 \\sim C48: within 1.7A with sigma of 0.002 and sigma
for terminal atoms of 0.004
C35 \\sim C36 \\sim C37 \\sim C38: within 1.7A with sigma of 0.002 and sigma
for terminal atoms of 0.004
3. Same fragment restrains
{C45, C46, C47, C48} sigma for 1-2: 0.005, 1-3: 0.01
{C45, C46A, C47A, C48A} sigma for 1-2: 0.005, 1-3: 0.01
as
{C35, C36, C37, C38}
4. Others
 Sof(C46A)=Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(C47A)=Sof(H47A)=Sof(H47B)=
 Sof(H47C)=Sof(C48A)=Sof(H48A)=Sof(H48B)=Sof(H48C)=1-FVAR(1)
 Sof(C46)=Sof(H46D)=Sof(H46E)=Sof(H46F)=Sof(C47)=Sof(H47D)=Sof(H47E)=Sof(H47F)=
 Sof(C48)=Sof(H48D)=Sof(H48E)=Sof(H48F)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C10(H10), C11(H11), C12(H12),
 C13(H13), C14(H14), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C24(H24),
  C25(H25), C26(H26), C27(H27), C28(H28)
5.b Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C36(H36A,H36B,
 H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C41(H41A,H41B,H41C), C42(H42A,
 H42B,H42C), C43(H43A,H43B,H43C), C46A(H46A,H46B,H46C), C47A(H47A,H47B,H47C),
 C48A(H48A,H48B,H48C), C46(H46D,H46E,H46F), C47(H47D,H47E,H47F), C48(H48D,H48E,
 H48F)
;
_shelx_res_checksum              31126
_shelx_hkl_checksum              95874
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'