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_7063054
_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         'C39 H36 N4 P Pd, C2 F3 O2, C7 H8'
_chemical_formula_sum            'C48 H44 F3 N4 O2 P Pd'
_chemical_formula_weight         903.24
_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             2023-01-25
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-09-24 deposited with the CCDC.	2024-02-23 downloaded from the CCDC.
;
_cell_angle_alpha                94.143(2)
_cell_angle_beta                 109.681(2)
_cell_angle_gamma                90.228(2)
_cell_formula_units_Z            2
_cell_length_a                   10.8143(3)
_cell_length_b                   14.5146(3)
_cell_length_c                   14.5400(4)
_cell_measurement_reflns_used    18893
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      29.1930
_cell_measurement_theta_min      3.3020
_cell_volume                     2142.36(10)
_computing_cell_refinement       'CrysAlisPro 1.171.42.69a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.69a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.69a (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 2016/4 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_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 0.997
_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    -32.00  -5.00   0.50    5.07    --   -5.68  94.00  53.00   54
  2  \w    -31.00  33.00   0.50    5.07    --    5.83 -94.00 -56.00  128
  3  \w    -11.00  33.00   0.50    5.07    --    5.83  94.00  53.00   88
  4  \w    -80.00   1.00   0.50    5.07    --   -5.68 -19.00-120.00  162
  5  \w    -63.00   1.00   0.50    5.07    --   -5.68 -57.00-180.00  128
  6  \w    -11.00  15.00   0.50    5.07    --   -5.68 -99.00  90.00   52
  7  \w    -22.00   4.00   0.50    5.07    --   -5.68 -38.00-180.00   52
  8  \w    -12.00  67.00   0.50    5.07    --   -5.68  38.00  30.00  158
  9  \w    -67.00 -41.00   0.50    5.07    --    5.83 -38.00 -30.00   52
 10  \w      2.00  29.00   0.50    5.07    --    5.83 -99.00-180.00   54
;
_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      -0.0265915000
_diffrn_orient_matrix_UB_12      -0.0452542000
_diffrn_orient_matrix_UB_13      -0.0026166000
_diffrn_orient_matrix_UB_21      0.0248858000
_diffrn_orient_matrix_UB_22      0.0007253000
_diffrn_orient_matrix_UB_23      0.0518534000
_diffrn_orient_matrix_UB_31      -0.0594159000
_diffrn_orient_matrix_UB_32      0.0188244000
_diffrn_orient_matrix_UB_33      0.0022888000
_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  0.0543
_diffrn_reflns_av_unetI/netI     0.0510
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            31624
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         3.120
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.527
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87325
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.69a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.400
_exptl_crystal_description       BLOCK
_exptl_crystal_F_000             928
_exptl_crystal_size_max          0.10
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.733
_refine_diff_density_min         -0.608
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     476
_refine_ls_number_reflns         8745
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0644
_refine_ls_R_factor_gt           0.0502
_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^)+(0.0820P)^2^+1.0964P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1378
_refine_ls_wR_factor_ref         0.1481
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7098
_reflns_number_total             8745
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3nj05516g3.cif
_cod_data_source_block           Complex-10
_cod_depositor_comments
'Adding full bibliography for 7063048--7063056.cif.'
_cod_database_code               7063054
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         'C H N F Pd P'
_chemical_oxdiff_usercomment     24.01.2023
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C35(H35), C21(H21), C20(H20), N2(H2), C4(H4), C6(H6), C33(H33),
 C23(H23), C5(H5), C19(H19), C36(H36), C18(H18), C27(H27), C29(H29), C39(H39),
 C37(H37), C38(H38), C24(H24), C10(H10), C11(H11), C12(H12), C13(H13), C32(H32),
  C31(H31), C30(H30), C25(H25), C26(H26), C43(H43), C44(H44), C45(H45),
 C46(H46), C47(H47)
2.c Fitted hexagon refined as free rotating group:
 C14(C9,C10,C11,C12,C13), C42(C43,C44,C45,C46,C47)
2.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C15(H15A,H15B,H15C), C48(H48A,H48B,H48C)
;
_shelx_res_checksum              52174
_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 1.786
_oxdiff_exptl_absorpt_empirical_full_min 0.794