"Bulky-Yet-Flexible" α-Diimine Palladium-Catalyzed Reductive Heck Cross-Coupling: Highly Anti-Markovnikov-Selective Hydroarylation of Alkene in Air.
Yang, Xu-Wen; Li, Dong-Hui; Song, A-Xiang; Liu, Feng-Shou; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c01509

data_4038726
_publ_section_title
;
 &quot;Bulky-Yet-Flexible&quot; \a-Diimine Palladium-Catalyzed Reductive
 Heck Cross-Coupling: Highly Anti-Markovnikov-Selective Hydroarylation of
 Alkene in Air.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c01509
_journal_year                    2020
_chemical_formula_moiety         'C78 H60 Cl2 N2 Pd, 2(C H2 Cl2)'
_chemical_formula_sum            'C80 H64 Cl6 N2 Pd'
_chemical_formula_weight         1372.43
_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     dual
_audit_creation_date             2019-06-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                96.356(2)
_cell_angle_beta                 92.889(5)
_cell_angle_gamma                91.174(5)
_cell_formula_units_Z            2
_cell_length_a                   12.0249(9)
_cell_length_b                   14.3002(4)
_cell_length_c                   21.4777(5)
_cell_measurement_reflns_used    10092
_cell_measurement_temperature    100.02(10)
_cell_measurement_theta_max      73.4620
_cell_measurement_theta_min      3.5030
_cell_volume                     3664.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.02(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.963
_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    -67.00  28.00   1.00    1.00    --  -40.98  57.00  60.00   95
  2  \w    -90.00  -8.00   1.00    1.00    --  -40.98 -77.00 -90.00   82
  3  \w    -94.00 -54.00   1.00    1.00    --  -40.98 125.00   0.00   40
  4  \w     32.00  59.00   1.00    2.00    --  106.95 -77.00-120.00   27
  5  \w     38.00 127.00   1.00    2.00    --  106.95 -36.00-140.00   89
  6  \w     98.00 178.00   1.00    2.00    --  106.95  61.00   0.00   80
  7  \w     95.00 168.00   1.00    2.00    --  106.95 125.00 -60.00   73
  8  \w     35.00 141.00   1.00    2.00    --  106.95 -15.00   0.00  106
  9  \w     26.00 107.00   1.00    2.00    --  106.95 -94.00 150.00   81
 10  \w    -65.00   3.00   1.00    1.00    --  -41.23  38.00 150.00   68
 11  \w   -113.00 -13.00   1.00    1.00    --  -41.23 -57.00 150.00  100
 12  \w     42.00  99.00   1.00    2.00    --  106.95 -94.00-120.00   57
 13  \w    152.00 178.00   1.00    2.00    --  106.95  45.00  30.00   26
 14  \w    126.00 176.00   1.00    2.00    --  106.95 125.00-150.00   50
 15  \w     47.00  73.00   1.00    2.00    --  106.95-125.00  90.00   26
 16  \w     81.00 145.00   1.00    2.00    --  106.95  45.00  30.00   64
 17  \w     94.00 121.00   1.00    2.00    --  106.95-125.00  90.00   27
 18  \w     37.00  76.00   1.00    2.00    --  106.95 -45.00  90.00   39
 19  \w     84.00 110.00   1.00    2.00    --  106.95 -45.00  90.00   26
 20  \w     69.00 104.00   1.00    2.00    --  106.95 -94.00 -90.00   35
 21  \w     61.00 136.00   1.00    2.00    --  106.95 -77.00 -60.00   75
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0280468000
_diffrn_orient_matrix_UB_12      -0.0688864000
_diffrn_orient_matrix_UB_13      0.0475975000
_diffrn_orient_matrix_UB_21      0.0521036000
_diffrn_orient_matrix_UB_22      -0.0804991000
_diffrn_orient_matrix_UB_23      -0.0415738000
_diffrn_orient_matrix_UB_31      0.1138636000
_diffrn_orient_matrix_UB_32      0.0230765000
_diffrn_orient_matrix_UB_33      0.0350654000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0852
_diffrn_reflns_av_unetI/netI     0.0974
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            27478
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.790
_diffrn_reflns_theta_min         2.073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.378
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.28874
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.244
_exptl_crystal_description       block
_exptl_crystal_F_000             1412
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         3.836
_refine_diff_density_min         -3.066
_refine_diff_density_rms         0.354
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     804
_refine_ls_number_reflns         14263
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.919
_refine_ls_R_factor_all          0.0951
_refine_ls_R_factor_gt           0.0833
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1504
_refine_ls_wR_factor_ref         0.2050
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12059
_reflns_number_total             14263
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01509_si_001.cif
_cod_data_source_block           pdcl3
_cod_database_code               4038726
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.669
_shelx_estimated_absorpt_t_min   0.622
_reflns_odcompleteness_completeness 99.48
_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. Rigid bond restraints
 C023, C01U
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C023 \\sim C01U: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004
Uanis(C02G) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
4.a Ternary CH refined with riding coordinates:
 C00I(H00I), C012(H012), C01H(H01H), C01I(H01I)
4.b Secondary CH2 refined with riding coordinates:
 C028(H02A,H02G), C02G(H02J,H02O)
4.c Aromatic/amide H refined with riding coordinates:
 C00D(H00D), C00F(H00F), C00H(H00H), C00T(H00T), C00U(H00U), C00W(H00W),
 C00Y(H00Y), C00Z(H00Z), C013(H013), C015(H015), C016(H016), C017(H017),
 C018(H018), C01C(H01C), C01D(H01D), C01E(H01E), C01F(H01F), C01J(H01J),
 C01L(H01L), C01M(H01M), C01N(H01N), C01P(H01P), C01Q(H01Q), C01R(H01R),
 C01S(H01S), C01T(H01T), C01U(H01U), C01W(H01W), C01X(H01X), C01Y(H01Y),
 C01Z(H01Z), C020(H020), C021(H021), C022(H022), C024(H024), C025(H025),
 C026(H026), C027(H027), C029(H029), C02B(H02B), C02C(H02C), C02D(H02D),
 C02E(H02E), C02F(H02F), C02H(H02H), C02I(H02I), C02K(H02K), C02L(H02L),
 C02M(H02M), C02N(H02N)
4.d Idealised Me refined as rotating group:
 C00N(H00A,H00B,H00C), C00S(H00E,H00G,H00J)
;
_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 2.815
_oxdiff_exptl_absorpt_empirical_full_min 0.623