Ion mobility mass spectrometry uncovers regioselectivity in the carboxylate-assisted C-H activation of palladium N-heterocyclic carbene complexes.
Ibáñez-Ibáñez, Laura; Mollar-Cuni, Andres; Apaloo-Messan, Edmond; Sharma, Akhilesh K.; Mata, Jose A.; Maseras, Feliu; Vicent, Cristian; Dalton transactions (Cambridge, England : 2003) 53 (2024) 656–665; doi:10.1039/d3dt02793g

data_7714560
_publ_section_title
;
 Ion mobility mass spectrometry uncovers regioselectivity in the
 carboxylate-assisted C-H activation of palladium N-heterocyclic carbene
 complexes.
;
_journal_issue                   2
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              656
_journal_page_last               665
_journal_paper_doi               10.1039/d3dt02793g
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C16 H25 Br2 N3 Pd'
_chemical_formula_sum            'C16 H25 Br2 N3 Pd'
_chemical_formula_weight         525.619
_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'
_symmetry_Int_Tables_number      14
_atom_sites_solution_primary     dual
_audit_creation_date             2023-08-01
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-08-17 deposited with the CCDC.	2023-11-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.415(1)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.8237(2)
_cell_length_b                   8.7247(1)
_cell_length_c                   16.4465(2)
_cell_measurement_reflns_used    23589
_cell_measurement_temperature    200.0(3)
_cell_measurement_theta_max      71.6960
_cell_measurement_theta_min      4.5870
_cell_volume                     1944.34(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (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  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      200.0(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4051
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.0000
_diffrn_measured_fraction_theta_max 0.9989
_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     -5.00  37.00   0.30    1.00    --  -42.87  19.00 120.00  140
  2  \w     -5.00  37.00   0.30    1.00    --  -42.87  19.00-150.00  140
  3  \w     -5.00  37.00   0.30    1.00    --  -42.87  19.00 -60.00  140
  4  \w     -5.00  37.00   0.30    1.00    --  -42.87  19.00 -90.00  140
  5  \w     -5.00  37.00   0.30    1.00    --  -42.87  19.00   0.00  140
  6  \w     -5.00  37.00   0.30    1.00    --  -42.87  19.00-120.00  140
  7  \w     -5.00  37.00   0.30    1.00    --  -42.87  19.00-180.00  140
  8  \w     -5.00  37.00   0.30    1.00    --  -42.87  19.00 150.00  140
  9  \w     -5.00  37.00   0.30    1.00    --  -42.87  19.00 -30.00  140
 10  \w      9.00  42.00   0.30    1.00    --   42.87  82.00  -3.99  110
 11  \w     10.00  40.90   0.30    1.00    --   42.87  79.00 -48.65  103
 12  \w     74.00 174.20   0.30    1.00    --  102.61  61.00 -90.00  334
 13  \w     77.00 176.00   0.30    1.00    --  102.61  45.00 -30.00  330
 14  \w     74.00 177.20   0.30    1.00    --  102.61  30.00 120.00  344
 15  \w     75.00 174.00   0.30    1.00    --  102.61  55.00 -28.68  330
 16  \w    103.00 178.00   0.30    1.00    --  102.61  77.00 120.00  250
 17  \w     26.00  56.00   0.30    1.00    --  102.61 -30.00 -90.00  100
 18  \w     74.00 174.20   0.30    1.00    --  102.61  60.00-133.46  334
 19  \w    103.00 178.00   0.30    1.00    --  102.61  77.00-180.00  250
 20  \w     74.00 174.20   0.30    1.00    --  102.61  61.00 -60.00  334
 21  \w     30.00  72.00   0.30    1.00    --  102.61 -45.00 150.00  140
 22  \w     77.00 176.00   0.30    1.00    --  102.61  45.00 -90.00  330
 23  \w     30.00  93.00   0.30    1.00    --  102.61 -61.00  90.00  210
 24  \w     30.00  72.00   0.30    1.00    --  102.61 -45.00 120.00  140
 25  \w     30.00  93.00   0.30    1.00    --  102.61 -61.00-120.00  210
 26  \w     29.00 113.00   0.30    1.00    --  102.61-125.00  60.00  280
 27  \w     74.00 174.20   0.30    1.00    --  102.61  57.00 -72.35  334
 28  \w     -5.00  37.00   0.30    1.00    --  -42.87  19.00  30.00  140
 29  \w     -5.00  37.00   0.30    1.00    --  -42.87  19.00  60.00  140
 30  \w     27.00  99.00   0.30    1.00    --   42.87-125.00 -30.00  240
 31  \w     10.00  40.90   0.30    1.00    --   42.87  80.00 -87.07  103
 32  \w     10.00  40.90   0.30    1.00    --   42.87  80.00  76.30  103
 33  \w      9.00  42.00   0.30    1.00    --   42.87  82.00  38.39  110
 34  \w     10.00  40.90   0.30    1.00    --   42.87  78.00 166.48  103
 35  \w     10.00  40.90   0.30    1.00    --   42.87  80.00-133.76  103
 36  \w     20.00 105.20   0.30    1.00    --  102.61 -94.00  90.00  284
 37  \w     74.00 174.20   0.30    1.00    --  102.61  61.00   0.00  334
 38  \w     29.00 113.00   0.30    1.00    --  102.61-125.00 -90.00  280
 39  \w     73.00 175.00   0.30    1.00    --  102.61  63.00 159.39  340
 40  \w     73.00 175.00   0.30    1.00    --  102.61  66.00  38.60  340
 41  \w     74.00 174.20   0.30    1.00    --  102.61  59.00 131.70  334
 42  \w     26.00  56.00   0.30    1.00    --  102.61 -30.00-180.00  100
 43  \w     74.00 137.00   0.30    1.00    --  102.61  61.00  60.00  210
 44  \w     73.00 175.00   0.30    1.00    --  102.61  63.00-171.06  340
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0116836000
_diffrn_orient_matrix_UB_12      0.0586599000
_diffrn_orient_matrix_UB_13      0.0858608000
_diffrn_orient_matrix_UB_21      0.0878768000
_diffrn_orient_matrix_UB_22      -0.1000286000
_diffrn_orient_matrix_UB_23      0.0413663000
_diffrn_orient_matrix_UB_31      0.0711969000
_diffrn_orient_matrix_UB_32      0.1331815000
_diffrn_orient_matrix_UB_33      -0.0067684000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0261
_diffrn_reflns_av_unetI/netI     0.0108
_diffrn_reflns_Laue_measured_fraction_full 1.0000
_diffrn_reflns_Laue_measured_fraction_max 0.9989
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            34828
_diffrn_reflns_point_group_measured_fraction_full 1.0000
_diffrn_reflns_point_group_measured_fraction_max 0.9989
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         71.65
_diffrn_reflns_theta_min         3.82
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.503
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56495
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.796
_exptl_crystal_description       needle
_exptl_crystal_F_000             1029.819
_exptl_crystal_preparation
'slow diffusion of n-hexanes into a concentrated solution of the palladium complex in diclhoromethane'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.9093
_refine_diff_density_min         -0.5712
_refine_diff_density_rms         0.0807
_refine_ls_d_res_high            0.8122
_refine_ls_d_res_low             11.5608
_refine_ls_extinction_coef       0.00077(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.0386
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    40
_refine_ls_number_parameters     202
_refine_ls_number_reflns         3785
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0386
_refine_ls_R_factor_all          0.0239
_refine_ls_R_factor_gt           0.0234
_refine_ls_shift/su_max          -0.0045
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0295P)^2^+3.0906P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0584
_refine_ls_wR_factor_ref         0.0588
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              11
_reflns_limit_h_min              -16
_reflns_limit_k_max              10
_reflns_limit_k_min              0
_reflns_limit_l_max              20
_reflns_limit_l_min              -11
_reflns_number_gt                3703
_reflns_number_total             3785
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d3dt02793g2.cif
_cod_data_source_block           str2251_auto
_cod_depositor_comments          'Adding full bibliography for 7714560.cif.'
_cod_original_sg_symbol_Hall     '-P 2ybc (x-z,y,z)'
_cod_database_code               7714560
_chemical_oxdiff_formula         'C16 H25 N3 Br2 Pd'
_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 Secondary CH2 refined with riding coordinates:
 C19(H19a,H19b), C16(H16a,H16b), C15(H15a,H15b), C17(H17a,H17b), C20(H20a,
 H20b), C21(H21a,H21b)
2.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C6(H6), C7(H7), C14(H14), C11(H11), C13(H13), C12(H12)
2.c Idealised Me refined as rotating group:
 C18(H18a,H18b,H18c), C22(H22a,H22b,H22c)
;
_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 1.400
_oxdiff_exptl_absorpt_empirical_full_min 0.704