Mild cross-coupling of tertiary alkoxides with aryl chlorides enabled by a shelf-stable methylnaphthyl palladium NHC complex
Tzouras, Nikolaos V.; Fleischer, Ruben; Satta, Pierpaolo; Manna, Sourav; Doppiu, Angelino; Goossen, Lukas J.; Chemical Communications  (2025) –; doi:10.1039/D5CC05726D

data_7135155
_publ_section_title
;
 Mild cross-coupling of tertiary alkoxides with aryl chlorides enabled by
 a shelf-stable methylnaphthyl palladium NHC complex
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D5CC05726D
_journal_year                    2025
_chemical_formula_sum            'C46 H59 Br Cl2 N2 Pd'
_chemical_formula_weight         897.16
_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     direct
_audit_creation_date             2025-01-20
_audit_creation_method           SHELXL-2019/3
_audit_update_record
;
2025-09-28 deposited with the CCDC.	2025-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.2670(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.04080(10)
_cell_length_b                   15.09390(10)
_cell_length_c                   21.63080(10)
_cell_measurement_reflns_used    38543
_cell_measurement_temperature    106(2)
_cell_measurement_theta_max      76.6350
_cell_measurement_theta_min      3.3890
_cell_volume                     4239.75(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_structure_refinement  'SHELXL-2019/2 (Sheldrick, 2019)'
_computing_structure_solution    'SHELXT (G.M. Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      106(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.979
_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    147.00 178.00   0.50    0.23    --  105.91 125.00 120.00   62
  2  \w    129.00 155.00   0.50    0.23    --  105.91 111.00 131.00   52
  3  \w     97.00 135.00   0.50    0.23    --  105.91 125.00 120.00   76
  4  \w    142.00 168.00   0.50    0.23    --  105.91 125.00 -30.00   52
  5  \w     97.00 123.00   0.50    0.23    --  105.91 125.00 -30.00   52
  6  \w     95.00 177.00   0.50    0.23    --  105.91  15.00-120.00  164
  7  \w     77.00 106.00   0.50    0.23    --  105.91 -94.00-150.00   58
  8  \w     42.00 119.00   0.50    0.23    --  105.91-134.00-143.76  154
  9  \w     85.00 130.00   0.50    0.23    --  105.91-151.00 -67.19   90
 10  \w     52.00  81.00   0.50    0.23    --  105.91-151.00 -67.19   58
 11  \w     62.00  99.00   0.50    0.23    --  105.91-125.00   0.00   74
 12  \w     66.00 108.00   0.50    0.23    --  105.91-111.00  38.00   84
 13  \w     38.00  71.00   0.50    0.23    --  105.91-125.00 150.00   66
 14  \w     84.00 112.00   0.50    0.23    --  105.91-125.00 150.00   56
 15  \w     35.00 105.00   0.50    0.23    --  105.91-101.00  82.77  140
 16  \w     35.00  94.00   0.50    0.06    --   47.28-125.00 120.00  118
 17  \w     32.00  57.00   0.50    0.06    --   47.28-111.00  38.00   50
 18  \w     54.00 105.00   0.50    0.23    --  105.91 -94.00 -90.00  102
 19  \w     68.00 106.00   0.50    0.23    --  105.91 -94.00 -30.00   76
 20  \w     34.00  65.00   0.50    0.23    --  105.91 -61.00   0.00   62
 21  \w     39.00  65.00   0.50    0.23    --  105.91 -61.00 120.00   52
 22  \w     42.00  68.00   0.50    0.23    --  105.91 -61.00  90.00   52
 23  \w     33.00  74.00   0.50    0.23    --  105.91 -61.00 -90.00   82
 24  \w     35.00  72.00   0.50    0.23    --  105.91 -61.00-120.00   74
 25  \w    -62.00  24.00   0.50    0.06    --  -47.28  57.00  30.00  172
 26  \w    -22.00  27.00   0.50    0.06    --  -47.28  19.00 -30.00   98
 27  \w    -22.00  28.00   0.50    0.06    --  -47.28  19.00-150.00  100
 28  \w    -78.00 -52.00   0.50    0.23    --  -91.75 125.00  30.00   52
 29  \w    -44.00 -19.00   0.50    0.23    --  -91.75 125.00  30.00   50
 30  \w    -70.00  -2.00   0.50    0.06    --  -47.28 111.00 131.00  136
 31  \w    -81.00 -55.00   0.50    0.23    --  -91.75 111.00 131.00   52
 32  \w    -65.00 -33.00   0.50    0.23    --  -91.75  61.00  90.00   64
 33  \w    -47.00 -20.00   0.50    0.23    --  -91.75  45.00 120.00   54
 34  \w    -46.00 -21.00   0.50    0.23    --  -91.75  45.00  30.00   50
 35  \w    -48.00 -20.00   0.50    0.23    --  -91.75  45.00 150.00   56
 36  \w    -48.00 -23.00   0.50    0.23    --  -91.75  45.00   0.00   50
 37  \w    -46.00 -20.00   0.50    0.23    --  -91.75  45.00 -30.00   52
 38  \w    -47.00 -21.00   0.50    0.23    --  -91.75  45.00 -90.00   52
 39  \w    -48.00 -22.00   0.50    0.23    --  -91.75  45.00-120.00   52
 40  \w    -48.00 -23.00   0.50    0.23    --  -91.75  45.00-180.00   50
 41  \w   -119.00 -30.00   0.50    0.06    --  -47.28 -77.00 -30.00  178
 42  \w   -155.00 -81.00   0.50    0.23    --  -91.75 -61.00 -60.00  148
 43  \w   -140.00-105.00   0.50    0.23    --  -91.75 -45.00 -60.00   70
 44  \w   -162.00-111.00   0.50    0.23    --  -91.75 -15.00 -30.00  102
 45  \w   -166.00-124.00   0.50    0.23    --  -91.75 -15.00  90.00   84
 46  \w   -107.00 -78.00   0.50    0.23    --  -91.75 -15.00  90.00   58
 47  \w   -137.00 -83.00   0.50    0.23    --  -91.75-111.00  38.00  108
 48  \w   -116.00 -74.00   0.50    0.06    --  -47.28-125.00 120.00   84
 49  \w   -118.00 -76.00   0.50    0.06    --  -47.28-125.00-120.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1084856000
_diffrn_orient_matrix_UB_12      -0.0086162000
_diffrn_orient_matrix_UB_13      0.0222184000
_diffrn_orient_matrix_UB_21      0.0183506000
_diffrn_orient_matrix_UB_22      -0.0996726000
_diffrn_orient_matrix_UB_23      0.0116212000
_diffrn_orient_matrix_UB_31      0.0444117000
_diffrn_orient_matrix_UB_32      0.0201721000
_diffrn_orient_matrix_UB_33      0.0669769000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0537
_diffrn_reflns_av_sigmaI/netI    0.0666
_diffrn_reflns_av_unetI/netI     0.0299
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            58829
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.804
_diffrn_reflns_theta_min         3.403
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.038
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.375
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
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            yellow
_exptl_crystal_density_diffrn    1.406
_exptl_crystal_description       block
_exptl_crystal_F_000             1856
_exptl_crystal_recrystallization_method
'Single crystals (yellow blocks) of suitable quality for X-ray diffraction analysis were grown by slow evaporation of a saturated solution of the complex in pentane at 5 \%C.'
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.130
_exptl_crystal_size_min          0.120
_refine_diff_density_max         1.080
_refine_diff_density_min         -1.810
_refine_diff_density_rms         0.108
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     483
_refine_ls_number_reflns         8762
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0433
_refine_ls_R_factor_gt           0.0412
_refine_ls_shift/su_max          0.024
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0728P)^2^+6.5430P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1178
_refine_ls_wR_factor_ref         0.1199
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8174
_reflns_number_total             8762
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc05726d2.cif
_cod_data_source_block           tzn338_auto_a
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               7135155
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_min   0.378
_shelx_estimated_absorpt_t_max   0.531
_cell_oxdiff_length_a            13.03883(12)
_cell_oxdiff_length_b            15.09493(17)
_cell_oxdiff_length_c            21.63222(12)
_cell_oxdiff_angle_alpha         90.0105(7)
_cell_oxdiff_angle_beta          95.2569(6)
_cell_oxdiff_angle_gamma         90.0058(8)
_cell_oxdiff_volume              4239.75(7)
_cell_oxdiff_measurement_reflns_used 38543
_oxdiff_exptl_absorpt_empirical_full_min 0.841
_oxdiff_exptl_absorpt_empirical_full_max 1.225
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_diffrn_oxdiff_digest_frames
;
014b54b143e889043745f5c57694a29cbb03962c47b
;
_diffrn_oxdiff_digest_hkl
;
019b2a1e17c3afbeb403b4c17de39a93bf4060
;
_reflns_odcompleteness_completeness 99.99
_reflns_odcompleteness_theta     66.97
_reflns_odcompleteness_iscentric 1
_chemical_oxdiff_formula         PdC46H59BrCl2N2
_shelx_res_checksum              33956
_shelx_hkl_checksum              97325