"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_4038725
_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         'C52 H38 Cl2 F2 N2 Pd, 0.75(C H2 Cl2)'
_chemical_formula_sum            'C52.75 H39.5 Cl3.5 F2 N2 Pd'
_chemical_formula_weight         969.84
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 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                90
_cell_angle_beta                 96.956(2)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   18.9995(4)
_cell_length_b                   26.2060(8)
_cell_length_c                   35.3740(9)
_cell_measurement_reflns_used    16109
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      28.5600
_cell_measurement_theta_min      2.1500
_cell_volume                     17483.1(8)
_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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5368
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -63.00  40.00   1.00    9.00    --   11.74 -19.00  30.00  103
  2  \w    -10.00  22.00   1.00    9.00    --  -11.59 -99.00   0.00   32
  3  \w    -17.00  28.00   1.00    9.00    --  -11.59 -99.00-120.00   45
  4  \w     64.00  89.00   1.00    9.00    --   11.74-178.00 -90.00   25
;
_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      -0.0076865000
_diffrn_orient_matrix_UB_12      0.0237668000
_diffrn_orient_matrix_UB_13      -0.0091857000
_diffrn_orient_matrix_UB_21      -0.0066769000
_diffrn_orient_matrix_UB_22      0.0108443000
_diffrn_orient_matrix_UB_23      0.0175879000
_diffrn_orient_matrix_UB_31      0.0361947000
_diffrn_orient_matrix_UB_32      0.0070580000
_diffrn_orient_matrix_UB_33      0.0038391000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0666
_diffrn_reflns_av_unetI/netI     0.0998
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            80980
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.892
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.687
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88273
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.474
_exptl_crystal_description       block
_exptl_crystal_F_000             7896
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.798
_refine_diff_density_min         -1.136
_refine_diff_density_rms         0.118
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2214
_refine_ls_number_reflns         30761
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0970
_refine_ls_R_factor_gt           0.0523
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0367P)^2^+20.2230P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1028
_refine_ls_wR_factor_ref         0.1278
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20317
_reflns_number_total             30761
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01509_si_001.cif
_cod_data_source_block           pdcl2
_cod_original_formula_sum        'C52.75 H39.50 Cl3.50 F2 N2 Pd'
_cod_database_code               4038725
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.a Ternary CH refined with riding coordinates:
 C01E(H01E), C01T(H01T), C02D(H02D), C02Q(H02Q), C02U(H02U), C03I(H03I),
 C041(H041), C049(H049)
2.b Secondary CH2 refined with riding coordinates:
 C05I(H3AA,H), C06I(H06V,H06W), C1(H1A,H1B)
2.c Aromatic/amide H refined with riding coordinates:
 C01A(H01A), C01B(H01B), C01C(H01C), C01H(H01H), C01K(H01K), C01P(H01P),
 C01S(H01S), C01U(H01U), C01Z(H01Z), C025(H025), C026(H026), C029(H029),
 C02G(H02G), C02J(H02J), C02M(H02M), C02N(H02N), C02S(H02S), C02T(H02T),
 C02W(H02W), C02Z(H02Z), C030(H030), C031(H031), C036(H036), C038(H038),
 C039(H039), C03A(H03A), C03D(H03X), C03E(H03Y), C03F(H03), C03G(H03H),
 C03J(H03J), C03L(H03L), C03O(H03O), C03P(H03P), C03R(H03R), C03S(H03S),
 C03T(H03T), C03V(H03V), C03Y(H0AA), C03Z(H03Z), C040(H040), C042(H042),
 C043(H043), C045(H045), C047(H047), C048(H048), C04C(H04D), C04F(H04F),
 C04G(H04G), C04H(H04H), C04I(H04I), C04K(H04K), C04M(H04M), C04O(H04O),
 C04Q(H04Q), C04T(H04T), C04U(H04U), C04V(H04V), C04X(H04X), C04Y(H04Y),
 C04Z(H04Z), C050(H050), C051(H051), C052(H052), C053(H053), C054(H054),
 C056(H056), C057(H057), C058(H058), C059(H059), C05A(H05D), C05B(H05H),
 C05C(H05I), C05D(H05J), C05E(H05E), C05F(H05F), C05G(H05G), C05H(H05L),
 C05J(H05M), C05K(H05K), C05N(H05N), C05O(H05O), C05P(H05), C05Q(H1AA),
 C05R(H05R), C05S(H05S), C05T(H05T), C05U(H05U), C05V(H05V), C05W(H05W),
 C05X(H05X), C05Y(H2AA), C05Z(H05Z), C060(H060), C061(H061), C063(H063),
 C064(H064), C065(H065), C066(H066), C067(H067), C068(H068), C069(H069),
 C06A(H06E), C06B(H06I), C06C(H06F), C06D(H06D), C06E(H06T), C06F(H06U),
 C06G(H06G), C06H(H06H), C06J(H06J), C06K(H06K), C06L(H06L), C06M(H06M),
 C06N(H06N), C06O(H06O), C06P(H06P), C06Q(H06Q), C06R(H06R), C06S(H06S)
2.d Idealised Me refined as rotating group:
 C03B(H03Q,H03U,H03W), C03M(H03B,H03C,H03D), C03N(H03K,H03M,H03N), C03X(H03E,
 H03F,H03G), C04J(H04A,H04B,H04C), C05L(H05A,H05B,H05C), C05M(H05P,H05Q,H05Y),
 C062(H06A,H06B,H06C)
;
_olex2_date_sample_data_collection 2019-06-06
_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 1.182
_oxdiff_exptl_absorpt_empirical_full_min 0.778