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_4128023
_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         'C20 H15 N2 O Pd, B F4'
_chemical_formula_sum            'C20 H15 B F4 N2 O Pd'
_chemical_formula_weight         492.55
_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'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-09-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.6799(14)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.3325(5)
_cell_length_b                   9.5102(3)
_cell_length_c                   20.9624(5)
_cell_measurement_reflns_used    9980
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.867
_cell_measurement_theta_min      2.233
_cell_volume                     3636.76(17)
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      99.92
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0407
_diffrn_reflns_av_unetI/netI     0.0306
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            30039
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.984
_diffrn_reflns_theta_min         1.953
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.074
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6701
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0750 before and 0.0598 after correction.
The Ratio of minimum to maximum transmission is 0.8985.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.799
_exptl_crystal_description       plate
_exptl_crystal_F_000             1952
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.101
_refine_diff_density_min         -1.648
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.200
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     317
_refine_ls_number_reflns         4790
_refine_ls_number_restraints     137
_refine_ls_restrained_S_all      1.197
_refine_ls_R_factor_all          0.0501
_refine_ls_R_factor_gt           0.0442
_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^)+(0.0324P)^2^+14.6165P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1030
_refine_ls_wR_factor_ref         0.1058
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4298
_reflns_number_total             4790
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b04699_si_002.cif
_cod_data_source_block           stahl208
_cod_database_code               4128023
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C2) = Uanis(C1)
Uanis(C2A) = Uanis(C1A)
3. Rigid body (RIGU) restrains
 C1, C2, C3, C4, C5, C6, C7, C8, C9, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Same fragment restrains
{Pd1A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A} sigma for 1-2: 0.02, 1-3:
0.04
as
{Pd1, C1, C2, C3, C4, C5, C6, C7, C8, C9}
5. Others
 Sof(Pd1A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=
 Sof(C4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=
 Sof(H8A)=Sof(C9A)=Sof(H9A)=1-FVAR(1)
 Sof(Pd1)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=
 Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=Sof(C9)=
 Sof(H9)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C2A(H2A), C3A(H3A)
6.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C1A(H1AA,H1AB)
6.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12),
 C16(H16), C17(H17), C18(H18), C5A(H5A), C6A(H6A), C7A(H7A), C8A(H8A), C9A(H9A)
6.d Fitted hexagon refined as free rotating group:
 C4(C5,C6,C7,C8,C9), C4A(C5A,C6A,C7A,C8A,C9A)
;
_shelx_res_checksum              96999
_shelx_hkl_checksum              68797
_olex2_submission_special_instructions 'No special instructions were received'