The role of the stabilizing/leaving group in palladium catalysed cross-coupling reactions.
Palio, Lorenzo; Bru, Francis; Ruggiero, Tommaso; Bourda, Laurens; Van Hecke, Kristof; Cazin, Catherine; Nolan, Steven P.; Dalton transactions (Cambridge, England : 2003) 53 (2024) 18013–18020; doi:10.1039/d4dt02533d

data_7717252
_publ_section_title
;
 The role of the stabilizing/leaving group in palladium catalysed
 cross-coupling reactions.
;
_journal_issue                   44
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              18013
_journal_page_last               18020
_journal_paper_doi               10.1039/d4dt02533d
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C81 H71 Cl N2 Pd, C H2 Cl2'
_chemical_formula_sum            'C82 H73 Cl3 N2 Pd'
_chemical_formula_weight         1299.17
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-06-20
_audit_creation_method
;
Olex2 1.5
(compiled 2024.01.12 svn.r2f8d729c for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-07-03 deposited with the CCDC.	2024-10-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.6950(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.7772(2)
_cell_length_b                   17.3254(2)
_cell_length_c                   27.9020(3)
_cell_measurement_reflns_used    59061
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      73.7910
_cell_measurement_theta_min      2.9680
_cell_volume                     6497.27(14)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 10.4839
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_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    -70.00  32.00   1.00    1.00    --  -41.53  57.00  60.00  102
  2  \w   -130.00  47.00   1.00    1.00    --  -41.53   0.00   0.00  177
  3  \w      6.00  81.00   1.00    1.00    --   41.53 -99.00 -90.00   75
  4  \w     39.00 114.00   1.00    1.00    --   41.53-150.00 177.00   75
  5  \w     23.00 107.00   1.00    1.83    --  106.03 -94.00 -90.00   84
  6  \w     24.00 159.00   1.00    1.83    --  106.03 -15.00-150.00  135
  7  \w    103.00 178.00   1.00    1.83    --  106.03  77.00  30.00   75
  8  \w    103.00 178.00   1.00    1.83    --  106.03  77.00-120.00   75
  9  \w     23.00 107.00   1.00    1.83    --  106.03 -94.00 -30.00   84
 10  \w     97.00 177.00   1.00    1.83    --  106.03 125.00-180.00   80
 11  \w     33.00 132.00   1.00    1.83    --  106.03 -45.00  90.00   99
 12  \w     33.00 109.00   1.00    1.83    --  106.03-113.00  64.00   76
 13  \w     30.00 134.00   1.00    1.83    --  106.03 -30.00 150.00  104
 14  \w     23.00 107.00   1.00    1.83    --  106.03 -94.00 150.00   84
 15  \w     23.00 107.00   1.00    1.83    --  106.03 -94.00-150.00   84
 16  \w     33.00 132.00   1.00    1.83    --  106.03 -45.00 -90.00   99
 17  \w     23.00 107.00   1.00    1.83    --  106.03 -94.00  90.00   84
 18  \w   -114.00 -13.00   1.00    1.00    --  -41.53 -57.00 -90.00  101
 19  \w   -114.00 -13.00   1.00    1.00    --  -41.53 -57.00 120.00  101
 20  \w   -116.00 -17.00   1.00    1.00    --  -41.53 -37.00 -90.00   99
 21  \w   -114.00 -13.00   1.00    1.00    --  -41.53 -57.00  30.00  101
 22  \w   -114.00 -13.00   1.00    1.00    --  -41.53 -57.00-180.00  101
 23  \w     80.00 178.00   1.00    1.83    --  106.03  45.00-120.00   98
 24  \w     80.00 178.00   1.00    1.83    --  106.03  45.00   0.00   98
 25  \w     78.00 178.00   1.00    1.83    --  106.03  30.00 -30.00  100
 26  \w     77.00 178.00   1.00    1.83    --  106.03  61.00-180.00  101
 27  \w     77.00 178.00   1.00    1.83    --  106.03  61.00  90.00  101
 28  \w     77.00 178.00   1.00    1.83    --  106.03  61.00 150.00  101
 29  \w     77.00 178.00   1.00    1.83    --  106.03  61.00 -90.00  101
 30  \w     77.00 151.00   1.00    1.83    --  106.03  61.00 120.00   74
 31  \w     53.00 178.00   1.00    1.83    --  106.03  15.00  90.00  125
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0462
_diffrn_reflns_av_unetI/netI     0.0209
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            121712
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.904
_diffrn_reflns_theta_min         3.023
_exptl_absorpt_coefficient_mu    3.798
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.487
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.328
_exptl_crystal_description       block
_exptl_crystal_F_000             2704
_exptl_crystal_preparation       synthesis
_exptl_crystal_recrystallization_method 'vapour diffusion'
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.755
_refine_diff_density_min         -1.501
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     805
_refine_ls_number_reflns         13090
_refine_ls_number_restraints     25
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0426
_refine_ls_R_factor_gt           0.0385
_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^)+(0.0590P)^2^+8.5109P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1046
_refine_ls_wR_factor_ref         0.1078
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11902
_reflns_number_total             13090
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt02533d2.cif
_cod_data_source_block           tr38_thf_et
_cod_depositor_comments
'Adding full bibliography for 7717248--7717252.cif.'
_cod_database_code               7717252
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.517
_shelx_estimated_absorpt_t_min   0.334
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C72B-C73
 1.475 with sigma of 0.01
 C72A-C71A = C72B-C71B
 1.386 with sigma of 0.01
 C74-C72B = C78-C72B
 2.5 with sigma of 0.02
 C74-C72A = C78-C72A
 2.5 with sigma of 0.02
 C73-C71A = C73-C71B
 2.532 with sigma of 0.02
 C72A-C70 = C72B-C70
 2.416 with sigma of 0.02
3. Restrained planarity
 C73, C74, C78, C72A, C72B
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C72A) \\sim Ueq, Uanis(C72B) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.006
Uanis(C72A) = Uanis(C72B)
Uanis(C71A) = Uanis(C71B)
5. Others
 Sof(H70C)=Sof(H70D)=Sof(C71B)=Sof(H71B)=Sof(C72B)=Sof(H72B)=1-FVAR(1)
 Sof(H70A)=Sof(H70B)=Sof(C71A)=Sof(H71A)=Sof(C72A)=Sof(H72A)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C10(H10), C23(H23), C43(H43), C56(H56), C71A(H71A), C71B(H71B)
6.b Secondary CH2 refined with riding coordinates:
 C82(H82A,H82B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C8(H8), C12(H12), C13(H13), C14(H14), C15(H15),
 C16(H16), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C25(H25), C26(H26),
  C27(H27), C28(H28), C29(H29), C31(H31), C32(H32), C33(H33), C34(H34),
 C35(H35), C39(H39), C41(H41), C45(H45), C46(H46), C47(H47), C48(H48), C49(H49),
  C51(H51), C52(H52), C53(H53), C54(H54), C55(H55), C58(H58), C59(H59),
 C60(H60), C61(H61), C62(H62), C64(H64), C65(H65), C66(H66), C67(H67), C68(H68),
  C75(H75), C77(H77), C72A(H72A), C72B(H72B)
6.d X=CH2 refined with riding coordinates:
 C70(H70A,H70B), C70(H70C,H70D)
6.e Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C69(H69A,H69B,H69C), C79(H79A,H79B,H79C), C80(H80A,H80B,
 H80C), C81(H81A,H81B,H81C)
;
_shelx_res_checksum              24352
_shelx_hkl_checksum              94859
_olex2_exptl_crystal_mounting_method 'mounted on a LithoLoop'
_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
- B-factor correction
;