Enolizable Ketones as Activators of Palladium(II) Precatalysts in Amine Arylation Reactions
Hu, Huaiyuan; Gilliam, Ashley M.; Qu, Fengrui; Shaughnessy, Kevin H.; ACS Catalysis 10 (2020) 4127–4135; doi:10.1021/acscatal.0c00221

data_4517502
_publ_section_title
;
 Enolizable Ketones as Activators of Palladium(II) Precatalysts in Amine
 Arylation Reactions
;
_journal_issue                   7
_journal_name_full               'ACS Catalysis'
_journal_page_first              4127
_journal_page_last               4135
_journal_paper_doi               10.1021/acscatal.0c00221
_journal_volume                  10
_journal_year                    2020
_chemical_formula_moiety         'C20 H37 Cl3 N P Pd'
_chemical_formula_sum            'C20 H37 Cl3 N P Pd'
_chemical_formula_weight         535.27
_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_Int_Tables_number      15
_atom_sites_solution_primary     iterative
_audit_creation_date             2019-04-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.4920(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.8460(3)
_cell_length_b                   15.0741(2)
_cell_length_c                   18.2288(3)
_cell_measurement_reflns_used    26335
_cell_measurement_temperature    101(2)
_cell_measurement_theta_max      33.5510
_cell_measurement_theta_min      2.1250
_cell_volume                     4888.71(13)
_computing_cell_refinement       'CrysAlisPro 1.171.40.36a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.36a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.36a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      101(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9997
_diffrn_measured_fraction_theta_max 0.9997
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w     23.00  48.00   0.50    1.00    --   13.00-128.00-152.00   50
  2  \w    -62.00 -37.00   0.50    1.00    --  -13.62 128.00 -78.00   50
  3  \w    -70.00 -45.00   0.50    1.00    --  -13.62 142.00  92.00   50
  4  \w     -3.00  72.00   0.50    1.00    --   13.00  57.00 -60.00  150
  5  \w    -10.00  83.00   0.50    1.00    --   13.00  77.00  30.00  186
  6  \w     25.00  74.00   0.50    1.00    --   13.00  57.00-180.00   98
  7  \w     54.00  84.00   0.50    1.00    --   13.00-178.00  60.00   60
  8  \w    -86.00 -39.00   0.50    1.00    --  -13.62-178.00  30.00   94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0359997000
_diffrn_orient_matrix_UB_12      -0.0201993000
_diffrn_orient_matrix_UB_13      -0.0014030000
_diffrn_orient_matrix_UB_21      0.0169761000
_diffrn_orient_matrix_UB_22      -0.0424445000
_diffrn_orient_matrix_UB_23      -0.0014463000
_diffrn_orient_matrix_UB_31      0.0024593000
_diffrn_orient_matrix_UB_32      -0.0022856000
_diffrn_orient_matrix_UB_33      0.0389615000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0184
_diffrn_reflns_av_unetI/netI     0.0168
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            31885
_diffrn_reflns_theta_full        30.0339
_diffrn_reflns_theta_max         30.03
_diffrn_reflns_theta_min         1.77
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.158
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73178
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.36a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear orange'
_exptl_crystal_density_diffrn    1.4544
_exptl_crystal_description       block
_exptl_crystal_F_000             2204.9692
_exptl_crystal_size_max          0.506
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.134
_refine_diff_density_max         0.4588
_refine_diff_density_min         -0.4288
_refine_diff_density_rms         0.0560
_refine_ls_d_res_high            0.7100
_refine_ls_d_res_low             11.5010
_refine_ls_goodness_of_fit_ref   1.0368
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    63
_refine_ls_number_parameters     283
_refine_ls_number_reflns         7172
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0368
_refine_ls_R_factor_all          0.0176
_refine_ls_R_factor_gt           0.0160
_refine_ls_shift/su_max          0.0008
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0162P)^2^+3.9686P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0393
_refine_ls_wR_factor_ref         0.0398
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              25
_reflns_limit_h_min              -25
_reflns_limit_k_max              21
_reflns_limit_k_min              0
_reflns_limit_l_max              25
_reflns_limit_l_min              0
_reflns_number_gt                6728
_reflns_number_total             7172
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            cs0c00221_si_002.cif
_cod_data_source_block           HHY01
_cod_depositor_comments
;Adding full bibliography for 4517502.cif.

 Adding full bibliography for 4517502.cif.
;
_cod_database_code               4517502
_chemical_oxdiff_formula         'C20 H35 Cl3 N1 P1 Pd1'
_diffrn_oxdiff_digest_frames
;
019ed46cc8fe6f3ea98f2dc5e153ee235e0073841b3
;
_diffrn_oxdiff_digest_hkl
;
01c0d29e0d20fa06453f15b662a1918fa99d99
;
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     29.97
_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. Same fragment restrains
{C13, C14, C15} sigma for 1-2: 0.02, 1-3: 0.04
as
{C13A, C14A, C15A}
3. Others
 Sof(C13A)=Sof(H13d)=Sof(H13e)=Sof(H13f)=Sof(C14A)=Sof(H14d)=Sof(H14e)=
 Sof(H14f)=Sof(C15A)=Sof(H15d)=Sof(H15e)=Sof(H15f)=1-FVAR(1)
 Sof(C13)=Sof(H13a)=Sof(H13b)=Sof(H13c)=Sof(C14)=Sof(H14a)=Sof(H14b)=Sof(H14c)=
 Sof(C15)=Sof(H15a)=Sof(H15b)=Sof(H15c)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C1(H1a,H1b), C6(H6a,H6b)
4.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C17(H17), C18(H18), C20(H20)
4.c Idealised Me refined as rotating group:
 C3(H3a,H3b,H3c), C4(H4a,H4b,H4c), C5(H5a,H5b,H5c), C8(H8a,H8b,H8c), C9(H9a,
 H9b,H9c), C10(H10a,H10b,H10c), C13(H13a,H13b,H13c), C14(H14a,H14b,H14c),
 C15(H15a,H15b,H15c), C13A(H13d,H13e,H13f), C14A(H14d,H14e,H14f), C15A(H15d,
 H15e,H15f)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.411
_oxdiff_exptl_absorpt_empirical_full_min 0.751