Synthesis, characterization, and reactivity of [Pd(phosphine)(py)Cl2] (PEPPSI) and [Pd(phosphine)Cl2]2 com-plexes
Nolan, Steven P.; Voloshkin, Vladislav; Belis, Marek; Cazin, Catherine; Peng, Min; Liu, Yaxu; Van Hecke, Kristof; Dalton Transactions  (2023) –; doi:10.1039/D3DT00293D

data_7712311
_publ_section_title
;
 Synthesis, characterization, and reactivity of [Pd(phosphine)(py)Cl2]
 (PEPPSI) and [Pd(phosphine)Cl2]2 com-plexes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00293D
_journal_year                    2023
_chemical_formula_moiety         'C38 H54 Cl2 N P Pd, C H Cl3'
_chemical_formula_sum            'C39 H55 Cl5 N P Pd'
_chemical_formula_weight         852.46
_chemical_name_systematic        VL143
_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             2020-03-30
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_audit_update_record
;
2022-11-22 deposited with the CCDC.	2023-02-14 downloaded from the CCDC.
;
_cell_angle_alpha                89.4832(17)
_cell_angle_beta                 79.552(2)
_cell_angle_gamma                74.1193(19)
_cell_formula_units_Z            2
_cell_length_a                   9.5074(2)
_cell_length_b                   10.9513(2)
_cell_length_c                   21.0209(5)
_cell_measurement_reflns_used    17738
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      73.7970
_cell_measurement_theta_min      4.1650
_cell_volume                     2068.32(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4839
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.984
_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   -115.00 -14.00   1.00    1.00    --  -41.68 -57.00   0.00  101
  2  \w   -116.00 -17.00   1.00    1.00    --  -41.68 -38.00  90.00   99
  3  \w    -66.00  33.00   1.00    1.00    --  -41.68  38.00 -90.00   99
  4  \w      6.00  83.00   1.00    1.00    --   41.68 -99.00 -90.00   77
  5  \w      9.00  42.00   1.00    1.00    --   41.68  79.00 100.84   33
  6  \w     97.00 178.00   1.00    2.85    --  106.01 125.00-150.00   81
  7  \w    103.00 178.00   1.00    2.85    --  106.01  77.00 -30.00   75
  8  \w    103.00 178.00   1.00    2.85    --  106.01  77.00-180.00   75
  9  \w     23.00 107.00   1.00    2.85    --  106.01 -94.00-150.00   84
 10  \w     33.00 132.00   1.00    2.85    --  106.01 -45.00 -90.00   99
 11  \w     77.00 178.00   1.00    2.85    --  106.01  62.00-128.81  101
 12  \w     33.00 132.00   1.00    2.85    --  106.01 -45.00 120.00   99
 13  \w     23.00 107.00   1.00    2.85    --  106.01 -94.00 -60.00   84
 14  \w     33.00 112.00   1.00    2.85    --  106.01-125.00  90.00   79
 15  \w     78.00 178.00   1.00    2.85    --  106.01  30.00 -60.00  100
 16  \w     27.00 107.00   1.00    2.85    --  106.01-103.00 153.00   80
 17  \w    -66.00  33.00   1.00    1.00    --  -41.68  38.00 150.00   99
 18  \w   -115.00 -14.00   1.00    1.00    --  -41.68 -57.00-150.00  101
 19  \w      7.00  33.00   1.00    1.00    --   41.68  84.00 -31.23   26
 20  \w      8.00  42.00   1.00    1.00    --   41.68  81.00 -93.17   34
 21  \w     74.00 178.00   1.00    2.85    --  106.01  73.00  58.44  104
 22  \w     77.00 178.00   1.00    2.85    --  106.01  61.00 168.91  101
 23  \w     77.00 178.00   1.00    2.85    --  106.01  61.00  30.00  101
 24  \w     77.00 178.00   1.00    2.85    --  106.01  61.00 120.00  101
 25  \w     53.00 178.00   1.00    2.85    --  106.01  15.00 150.00  125
 26  \w     76.00 178.00   1.00    2.85    --  106.01  68.00-161.73  102
 27  \w     77.00 178.00   1.00    2.85    --  106.01  61.00 -60.00  101
 28  \w     77.00 178.00   1.00    2.85    --  106.01  59.00 -14.79  101
 29  \w      7.00  34.00   1.00    1.00    --   41.68  83.00  24.12   27
 30  \w      6.00  83.00   1.00    1.00    --   41.68 -99.00 -30.00   77
 31  \w      8.00  42.00   1.00    1.00    --   41.68  82.00-159.94   34
 32  \w      7.00  33.00   1.00    1.00    --   41.68  84.00 156.40   26
 33  \w     74.00 178.00   1.00    2.85    --  106.01  74.00  85.43  104
 34  \w     77.00 178.00   1.00    2.85    --  106.01  61.00   0.00  101
 35  \w     77.00 178.00   1.00    2.85    --  106.01  61.00 150.00  101
;
_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      -0.0546541000
_diffrn_orient_matrix_UB_12      0.1459679000
_diffrn_orient_matrix_UB_13      -0.0007080000
_diffrn_orient_matrix_UB_21      -0.0976456000
_diffrn_orient_matrix_UB_22      0.0034663000
_diffrn_orient_matrix_UB_23      0.0673632000
_diffrn_orient_matrix_UB_31      0.1299112000
_diffrn_orient_matrix_UB_32      0.0105729000
_diffrn_orient_matrix_UB_33      0.0320247000
_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  0.0591
_diffrn_reflns_av_unetI/netI     0.0408
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            38851
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.891
_diffrn_reflns_theta_min         4.201
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.155
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.598
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
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            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.369
_exptl_crystal_description       needle
_exptl_crystal_F_000             884
_exptl_crystal_preparation       Synthesis
_exptl_crystal_recrystallization_method 'Slow evaporation DCM'
_exptl_crystal_size_max          0.171
_exptl_crystal_size_mid          0.082
_exptl_crystal_size_min          0.065
_refine_diff_density_max         1.619
_refine_diff_density_min         -1.237
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     443
_refine_ls_number_reflns         8258
_refine_ls_number_restraints     11
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0520
_refine_ls_R_factor_gt           0.0459
_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^)+(0.0690P)^2^+3.2104P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1186
_refine_ls_wR_factor_ref         0.1241
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7344
_reflns_number_total             8258
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00293d2.cif
_cod_data_source_block           vl143
_cod_database_code               7712311
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C38 H54 Cl2 N P Pd'
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Restrained distances
 C39A-Cl3A = C39A-Cl4A = C39A-Cl5A
 1.746 with sigma of 0.01
 C39B-Cl3A = C39B-Cl4B = C39B-Cl5B
 1.746 with sigma of 0.01
 Cl3A-Cl4A = Cl3A-Cl5A = Cl4A-Cl5A
 2.9 with sigma of 0.02
 Cl3B-Cl4B = Cl3B-Cl5B = Cl4B-Cl5B
 2.9 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C39A) = Uanis(C39B)
Uanis(Cl3A) = Uanis(Cl3B)
Uanis(Cl4A) = Uanis(Cl4B)
Uanis(Cl5A) = Uanis(Cl5B)
4. Others
 Sof(Cl5B)=Sof(Cl4B)=Sof(Cl3B)=Sof(C39B)=Sof(H39B)=1-FVAR(1)
 Sof(Cl3A)=Sof(Cl4A)=Sof(C39A)=Sof(H39A)=Sof(Cl5A)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C31(H31), C7(H7), C1(H1), C25(H25), C28(H28), C39A(H39A), C39B(H39B)
5.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C2(H2A,H2B), C8(H8A,H8B), C12(H12A,H12B), C9(H9A,H9B), C11(H11A,
 H11B), C3(H3A,H3B), C10(H10A,H10B), C5(H5A,H5B), C4(H4A,H4B)
5.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C17(H17), C16(H16), C23(H23), C21(H21), C38(H38),
 C34(H34), C35(H35), C37(H37), C36(H36)
5.d Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C27(H27A,H27B,H27C), C26(H26A,H26B,
 H26C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              9514
_shelx_hkl_checksum              16073
_olex2_date_sample_data_collection 2020-03-16
_olex2_exptl_crystal_mounting_method 'Little loop'
_olex2_submission_original_sample_id VL143
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.676
_oxdiff_exptl_absorpt_empirical_full_min 0.241