Operando Spectroscopic and Kinetic Characterization of Aerobic Allylic C-H Acetoxylation Catalyzed by Pd(OAc)<sub>2</sub>/4,5-Diazafluoren-9-one.
Jaworski, Jonathan N.; Kozack, Caitlin V.; Tereniak, Stephen J.; Knapp, Spring Melody M.; Landis, Clark R.; Miller, Jeffrey T.; Stahl, Shannon S.; Journal of the American Chemical Society 141 (2019) 10462–10474; doi:10.1021/jacs.9b04699

data_4128024
_publ_section_title
;
 Operando Spectroscopic and Kinetic Characterization of Aerobic Allylic
 C-H Acetoxylation Catalyzed by
 Pd(OAc)<sub>2</sub>/4,5-Diazafluoren-9-one.
;
_journal_issue                   26
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10462
_journal_page_last               10474
_journal_paper_doi               10.1021/jacs.9b04699
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C22 H24 O4 Pd2'
_chemical_formula_sum            'C22 H24 O4 Pd2'
_chemical_formula_weight         565.21
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-02-17
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2016.02.16 svn.r3264 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.804(3)
_cell_length_b                   13.105(3)
_cell_length_c                   16.366(5)
_cell_measurement_reflns_used    9731
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.421
_cell_measurement_theta_min      2.421
_cell_volume                     2102.7(10)
_computing_cell_refinement       'SAINT+ Ver. 2015.9-0 (Bruker-AXS, 2015)'
_computing_data_collection       'APEX3 Ver. 2015.9-0 (Bruker-AXS, 2015)'
_computing_data_reduction        'SAINT+ Ver. 2015.9-0 (Bruker-AXS, 2015)'
_computing_molecular_graphics    'OLEX2 (Dolomanov et al., 2009)'
_computing_publication_material  'OLEX2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2015b)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '0.5\% \w and 0.5\% \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0354
_diffrn_reflns_av_unetI/netI     0.0229
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            56285
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         30.570
_diffrn_reflns_theta_min         1.991
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    1.735
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6680
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Krause et al., 2015) was used for absorption correction.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.786
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1120
_exptl_crystal_size_max          0.131
_exptl_crystal_size_mid          0.089
_exptl_crystal_size_min          0.07
_refine_diff_density_max         1.725
_refine_diff_density_min         -0.752
_refine_diff_density_rms         0.093
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.42(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     276
_refine_ls_number_reflns         6420
_refine_ls_number_restraints     8
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0307
_refine_ls_R_factor_gt           0.0270
_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^)+(0.0361P)^2^+1.1421P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0636
_refine_ls_wR_factor_ref         0.0646
_reflns_Friedel_coverage         0.787
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                5882
_reflns_number_total             6420
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b04699_si_002.cif
_cod_data_source_block           stahl222
_cod_original_cell_volume        2102.5(11)
_cod_database_code               4128024
_shelx_estimated_absorpt_t_max   0.888
_shelx_estimated_absorpt_t_min   0.805
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.58(4) 0.42(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C2A-C1 = C2-C1 = C15A-C14 = C15-C14
 1.40075 with sigma of 0.005
 C3A-C2A = C3-C2 = C16-C15 = C16A-C15A
 1.40911 with sigma of 0.005
4. Others
 Sof(H1BC)=Sof(H1BD)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=1-FVAR(1)
 Sof(H1AA)=Sof(H1AB)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=FVAR(1)
 Sof(H14C)=Sof(H14D)=Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(H16A)=1-FVAR(2)
 Sof(H14A)=Sof(H14B)=Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C15(H15), C16(H16), C2A(H2A), C3A(H3A), C15A(H15A), C16A(H16A)
5.b Secondary CH2 refined with riding coordinates:
 C1(H1AA,H1AB), C1(H1BC,H1BD), C14(H14A,H14B), C14(H14C,H14D)
5.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C18(H18), C19(H19), C20(H20),
 C21(H21), C22(H22)
5.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C13(H13A,H13B,H13C)
;
_shelx_res_checksum              85320
_shelx_hkl_checksum              81280
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'