Guanidine-centred reactivity of CNN Pd(ii) pincer complexes including carboxylate-assisted N–H activation and –CH2– → –C(O)– oxygenation
Sinha, Nitish Kumar; Khan, Hilal Ahmad; Sivasankar, Chinnappan; Thirupathi, Natesan; New Journal of Chemistry 48 (2024) 5710–5720; doi:10.1039/D3NJ05516G

data_7063049
_publ_section_title
;
 Guanidine-centred reactivity of CNN Pd(ii) pincer complexes including
 carboxylate-assisted N--H activation and --CH2-- \\rightarrow --C(O)--
 oxygenation
;
_journal_issue                   13
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              5710
_journal_page_last               5720
_journal_paper_doi               10.1039/D3NJ05516G
_journal_volume                  48
_journal_year                    2024
_chemical_formula_moiety         'C30 H21 F6 N5 O Pd'
_chemical_formula_sum            'C30 H21 F6 N5 O Pd'
_chemical_formula_weight         687.92
_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             2024-02-16
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-02-21 deposited with the CCDC.	2024-02-23 downloaded from the CCDC.
;
_cell_angle_alpha                82.430(2)
_cell_angle_beta                 74.423(4)
_cell_angle_gamma                72.257(4)
_cell_formula_units_Z            2
_cell_length_a                   8.4101(5)
_cell_length_b                   11.9592(3)
_cell_length_c                   14.4653(3)
_cell_measurement_reflns_used    10124
_cell_measurement_temperature    204(60)
_cell_measurement_theta_max      30.6640
_cell_measurement_theta_min      3.3060
_cell_volume                     1332.82(10)
_computing_cell_refinement       'CrysAlisPro 1.171.43.106a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.106a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.106a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/4 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      204(60)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -14.00  63.00   0.50    2.00    --   -5.53  57.00 150.00  154
  2  \w     -3.00  23.00   0.50    2.00    --   -5.53 -99.00-120.00   52
  3  \w    -19.00  13.00   0.50    2.00    --   -5.53 -99.00-150.00   64
  4  \w    -61.00  17.00   0.50    2.00    --   -5.53 -77.00   0.00  156
  5  \w     -8.00  32.00   0.50    2.00    --    5.69 -99.00  90.00   80
  6  \w    -23.00  38.00   0.50    2.00    --    5.69 -99.00-180.00  122
  7  \w     12.00  76.00   0.50    2.00    --    5.69  57.00 -90.00  128
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0350454000
_diffrn_orient_matrix_UB_12      0.0079866000
_diffrn_orient_matrix_UB_13      -0.0499745000
_diffrn_orient_matrix_UB_21      -0.0767789000
_diffrn_orient_matrix_UB_22      0.0441464000
_diffrn_orient_matrix_UB_23      -0.0039646000
_diffrn_orient_matrix_UB_31      0.0347200000
_diffrn_orient_matrix_UB_32      0.0433199000
_diffrn_orient_matrix_UB_33      0.0092611000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0734
_diffrn_reflns_av_unetI/netI     0.0689
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            16195
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         3.297
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.774
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74241
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.106a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            Orange
_exptl_crystal_density_diffrn    1.714
_exptl_crystal_description       BLOCK
_exptl_crystal_F_000             688
_exptl_crystal_size_max          0.02
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.005
_refine_diff_density_max         0.962
_refine_diff_density_min         -0.809
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.992
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     390
_refine_ls_number_reflns         5443
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.992
_refine_ls_R_factor_all          0.0498
_refine_ls_R_factor_gt           0.0417
_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^)+(0.0435P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0946
_refine_ls_wR_factor_ref         0.0995
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4517
_reflns_number_total             5443
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3nj05516g3.cif
_cod_data_source_block           Complex-16
_cod_depositor_comments
'Adding full bibliography for 7063048--7063056.cif.'
_cod_database_code               7063049
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         'C H N F O Pd'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 N2(H2), C6(H6), C4(H4), C5(H5), C21(H21), C18(H18), C25(H25), C13(H13),
 C19(H19), C20(H20), C27(H27), C26(H26), C10(H10), C12(H12), C11(H11)
2.b Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C29(H29A,H29B,H29C)
;
_shelx_res_checksum              95294
_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 1.470
_oxdiff_exptl_absorpt_empirical_full_min 0.524