Cross-Dehydrogenative Couplings between Indoles and β-Keto Esters: Ligand-Assisted Ligand Tautomerization and Dehydrogenation via a Proton-Assisted Electron Transfer to Pd(II).
Leskinen, Mikko V.; Madarász, Adám; Yip, Kai-Tai; Vuorinen, Aini; Pápai, Imre; Neuvonen, Antti J.; Pihko, Petri M.; Journal of the American Chemical Society 136 (2014) 6453–6462; doi:10.1021/ja501681y

data_4121694
_publ_section_title
;
 Cross-Dehydrogenative Couplings between Indoles and \b-Keto Esters:
 Ligand-Assisted Ligand Tautomerization and Dehydrogenation via a
 Proton-Assisted Electron Transfer to Pd(II).
;
_journal_issue                   17
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6453
_journal_page_last               6462
_journal_paper_doi               10.1021/ja501681y
_journal_volume                  136
_journal_year                    2014
_chemical_formula_moiety         'C38 H36 F6 N2 O10 Pd2'
_chemical_formula_sum            'C38 H36 F6 N2 O10 Pd2'
_chemical_formula_weight         1007.54
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_primary     direct
_audit_creation_date             2014-01-13
_audit_creation_method
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Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
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_cell_angle_alpha                90
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_cell_formula_units_Z            4
_cell_length_a                   10.61764(9)
_cell_length_b                   18.45055(17)
_cell_length_c                   24.5248(2)
_cell_measurement_reflns_used    14469
_cell_measurement_temperature    123.01(10)
_cell_measurement_theta_max      73.4230
_cell_measurement_theta_min      3.6400
_cell_volume                     4741.05(7)
_computing_cell_refinement
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
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_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
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_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
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_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      123.01(10)
_diffrn_detector_area_resol_mean 10.3953
_diffrn_measured_fraction_theta_full 0.9764
_diffrn_measured_fraction_theta_max 0.9756
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0914130000
_diffrn_orient_matrix_UB_12      -0.0384440000
_diffrn_orient_matrix_UB_13      0.0462355000
_diffrn_orient_matrix_UB_21      0.0247944000
_diffrn_orient_matrix_UB_22      0.0725513000
_diffrn_orient_matrix_UB_23      0.0309909000
_diffrn_orient_matrix_UB_31      -0.1123644000
_diffrn_orient_matrix_UB_32      -0.0152152000
_diffrn_orient_matrix_UB_33      0.0309463000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0289
_diffrn_reflns_av_unetI/netI     0.0278
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            29808
_diffrn_reflns_theta_full        74.0000
_diffrn_reflns_theta_max         74.00
_diffrn_reflns_theta_min         3.01
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.767
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68382
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.4114
_exptl_crystal_description       block
_exptl_crystal_F_000             2024.5970
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.7624
_refine_diff_density_min         -0.9716
_refine_diff_density_rms         0.0904
_refine_ls_d_res_high            0.8020
_refine_ls_d_res_low             14.6728
_refine_ls_goodness_of_fit_ref   1.0500
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    59
_refine_ls_number_parameters     554
_refine_ls_number_reflns         9388
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0500
_refine_ls_R_factor_all          0.0362
_refine_ls_R_factor_gt           0.0339
_refine_ls_shift/su_max          0.0261
_refine_ls_shift/su_mean         0.0008
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0283P)^2^+9.7983P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0817
_refine_ls_wR_factor_ref         0.0829
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              10
_reflns_limit_h_min              -13
_reflns_limit_k_max              22
_reflns_limit_k_min              0
_reflns_limit_l_max              30
_reflns_limit_l_min              -9
_reflns_number_gt                8720
_reflns_number_total             9388
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            ja501681y_si_002.cif
_cod_data_source_block           OEK-1025_20140106-4
_cod_depositor_comments
'Adding full bibliography for 4121693--4121694.cif.'
_cod_original_cell_volume        4741.06(7)
_cod_database_code               4121694
_chemical_oxdiff_formula         'C20 H20 N1 O9 F6 Pd'
_reflns_odcompleteness_completeness 99.57
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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(F4A)=Sof(F6A)=Sof(F5A)=1-FVAR(1)
 Sof(F2A)=Sof(F1A)=Sof(F3A)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C8B(H8B), C8A(H8A), C16A(H16A), C16B(H16B)
3.b Secondary CH2 refined with riding coordinates:
 C6B(H6BA,H6BB), C7A(H7AA,H7AB), C6A(H6AA,H6AB), C2A(H2AA,H2AB), C7B(H7BA,
 H7BB), C2B(H2BA,H2BB)
3.c Aromatic/amide H refined with riding coordinates:
 C11A(H11A), C14B(H14B), C13A(H13A), C12A(H12A), C14A(H14A), C13B(H13B),
 C12B(H12B), C11B(H11B)
3.d Idealised Me refined as rotating group:
 C17A(H17A,H17B,H17C), C17B(H17D,H17E,H17F), C1A(H1AA,H1AB,H1AC), C1B(H1BA,
 H1BB,H1BC)
;