The ubiquitous P(<i>o</i>-tol)<sub>3</sub> ligand promotes formation of catalytically-active higher order palladacyclic clusters.
Husbands, David R.; Tanner, Theo; Whitwood, Adrian C.; Hodnett, Neil S.; Wheelhouse, Katherine M. P.; Fairlamb, Ian J. S.; Chemical science 15 (2024) 18627–18633; doi:10.1039/d4sc05346j

data_1572928
_publ_section_title
;
 The ubiquitous P(<i>o</i>-tol)<sub>3</sub> ligand promotes formation of
 catalytically-active higher order palladacyclic clusters.
;
_journal_issue                   44
_journal_name_full               'Chemical science'
_journal_page_first              18627
_journal_page_last               18633
_journal_paper_doi               10.1039/d4sc05346j
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C63 H60 B2 F O5 P3 Pd4, 1[C4H8O]'
_chemical_formula_sum            'C63 H60 B2 F O5 P3 Pd4'
_chemical_formula_weight         1456.24
_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             2023-11-14
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-11-17 deposited with the CCDC.	2024-10-15 downloaded from the CCDC.
;
_cell_angle_alpha                79.7260(10)
_cell_angle_beta                 74.1320(10)
_cell_angle_gamma                63.091(2)
_cell_formula_units_Z            2
_cell_length_a                   15.0801(3)
_cell_length_b                   15.0825(3)
_cell_length_c                   16.2726(2)
_cell_measurement_reflns_used    15726
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      76.1230
_cell_measurement_theta_min      3.5570
_cell_volume                     3168.19(11)
_computing_cell_refinement       'CrysAlisPro 1.171.43.95a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.95a 64-bit (release 03-11-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.95a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      110.00(10)
_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 1.000
_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    -84.00  -9.00   0.50    4.00    --  -48.64 118.00  57.00  150
  2  \w   -102.00 -76.00   0.50    4.00    --  -48.64 160.00-149.00   52
  3  \w   -106.00 -51.00   0.50    4.00    --  -48.64-160.00 178.00  110
  4  \w     40.00  66.00   0.50    4.00    --   48.64-118.00 -28.00   52
  5  \w     72.00  97.00   0.50    4.00    --   48.64 160.00-149.00   50
  6  \w     55.00 102.00   0.50    4.00    --   48.64-160.00 178.00   94
  7  \w     91.00 116.00   0.50   16.00    --  107.75 160.00-149.00   50
  8  \w    113.00 139.00   0.50   16.00    --  107.75 118.00  57.00   52
  9  \w     56.00  82.00   0.50   16.00    --  107.75-118.00 -28.00   52
 10  \w    107.00 134.00   0.50   16.00    --  107.75-160.00 178.00   54
 11  \w    -56.00  26.00   0.50    4.00    --  -48.64  19.00 -30.00  164
 12  \w   -109.00 -83.00   0.50    4.00    --  -48.64-125.00  60.00   52
 13  \w   -107.00 -74.00   0.50    4.00    --  -48.64-125.00-120.00   66
 14  \w   -108.00 -82.00   0.50    4.00    --  -48.64-125.00   0.00   52
 15  \w   -120.00 -26.00   0.50    4.00    --  -48.64 -77.00   0.00  188
 16  \w   -117.00 -41.00   0.50    4.00    --  -48.64 -37.00-180.00  152
 17  \w    107.00 178.00   0.50   16.00    --  107.75 125.00-150.00  142
 18  \w     38.00 103.00   0.50   16.00    --  107.75 -99.00 -30.00  130
 19  \w     37.00 106.00   0.50   16.00    --  107.75 -99.00 150.00  138
 20  \w     95.00 177.00   0.50   16.00    --  107.75  19.00 -60.00  164
 21  \w     35.00 123.00   0.50   16.00    --  107.75 -77.00 150.00  176
 22  \w     84.00 120.00   0.50   16.00    --  107.75 -37.00 -60.00   72
 23  \w     50.00  93.00   0.50   16.00    --  107.75 -57.00 -30.00   86
 24  \w     32.00 120.00   0.50   16.00    --  107.75 -19.00 120.00  176
 25  \w     49.00 119.00   0.50   16.00    --  107.75 -19.00-180.00  140
 26  \w     35.00  63.00   0.50   16.00    --  107.75 -37.00 -60.00   56
 27  \w     38.00 107.00   0.50   16.00    --  107.75-125.00 120.00  138
 28  \w     65.00  90.00   0.50   16.00    --  107.75 -99.00-120.00   50
 29  \w    118.00 144.00   0.50   16.00    --  107.75 125.00 -90.00   52
 30  \w     41.00 106.00   0.50   16.00    --  107.75 -99.00   0.00  130
 31  \w     78.00 119.00   0.50   16.00    --  107.75 -37.00 120.00   82
 32  \w     49.00 106.00   0.50   16.00    --  107.75 -99.00 -90.00  114
 33  \w     95.00 173.00   0.50   16.00    --  107.75  19.00   0.00  156
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu 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      -0.0477331000
_diffrn_orient_matrix_UB_12      0.0239919000
_diffrn_orient_matrix_UB_13      0.0945465000
_diffrn_orient_matrix_UB_21      0.1008811000
_diffrn_orient_matrix_UB_22      -0.0756687000
_diffrn_orient_matrix_UB_23      0.0244857000
_diffrn_orient_matrix_UB_31      0.0365288000
_diffrn_orient_matrix_UB_32      0.0829007000
_diffrn_orient_matrix_UB_33      -0.0137058000
_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  0.0394
_diffrn_reflns_av_unetI/netI     0.0407
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            36300
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.076
_diffrn_reflns_theta_max         67.076
_diffrn_reflns_theta_min         3.568
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.116
_exptl_absorpt_correction_T_max  0.785
_exptl_absorpt_correction_T_min  0.542
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.95a (Rigaku Oxford Diffraction, 2023)
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 orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.527
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1452
_exptl_crystal_recrystallization_method 'THF/pentane slow vapour diffusion'
_exptl_crystal_size_max          0.104
_exptl_crystal_size_mid          0.067
_exptl_crystal_size_min          0.044
_refine_diff_density_max         1.341
_refine_diff_density_min         -0.537
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     862
_refine_ls_number_reflns         11292
_refine_ls_number_restraints     103
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0469
_refine_ls_R_factor_gt           0.0376
_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^)+(0.0574P)^2^+1.2288P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1006
_refine_ls_wR_factor_ref         0.1056
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9231
_reflns_number_total             11292
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05346j3.cif
_cod_data_source_block           ijsf23078
_cod_depositor_comments
'Adding full bibliography for 1572926--1572929.cif.'
_cod_database_code               1572928
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C67 H66 B2 F1 O6 P3 Pd4'
_chemical_oxdiff_usercomment     'David Husbands DRH-03-32-2'
_shelx_estimated_absorpt_t_max   0.665
_shelx_estimated_absorpt_t_min   0.419
_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
 C14B-C13B \\sim C14A-C13A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C56A) \\sim Ueq, Uanis(C56B) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C12B) \\sim Ueq, Uanis(C9B) \\sim Ueq, Uanis(C10B) \\sim Ueq, Uanis(C9A)
\\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(C11A) \\sim Ueq, Uanis(C11B) \\sim Ueq:
with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C8B) \\sim Ueq, Uanis(C8A) \\sim Ueq, Uanis(C13B) \\sim Ueq, Uanis(C13A)
\\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C57B) \\sim Ueq, Uanis(C57A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F1B) \\sim Ueq, Uanis(F1A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C56B) = Uanis(C56A)
Uanis(C33B) = Uanis(C33A)
Uanis(C14B) = Uanis(C14A)
Uanis(C13A) = Uanis(C13B)
Uanis(C8A) = Uanis(C8B)
Uanis(C49A) = Uanis(C49B)
Uanis(C48A) = Uanis(C48B)
Uanis(C9A) = Uanis(C9B)
Uanis(C10A) = Uanis(C10B)
Uanis(C43A) = Uanis(C43B)
Uanis(C44A) = Uanis(C44B)
Uanis(C11A) = Uanis(C11B)
Uanis(C12A) = Uanis(C12B)
Uanis(C45A) = Uanis(C45B)
Uanis(C46A) = Uanis(C46B)
Uanis(C47A) = Uanis(C47B)
Uanis(C55A) = Uanis(C55B)
Uanis(C54B) = Uanis(C54A)
Uanis(C53A) = Uanis(C53B)
Uanis(C52B) = Uanis(C52A)
Uanis(C51A) = Uanis(C51B)
Uanis(C50A) = Uanis(C50B)
Uanis(C63A) = Uanis(C63B)
Uanis(C62A) = Uanis(C62B)
Uanis(C57A) = Uanis(C57B)
Uanis(C58A) = Uanis(C58B)
Uanis(C59A) = Uanis(C59B)
Uanis(C60A) = Uanis(C60B)
Uanis(C61B) = Uanis(C61A)
Uanis(C28A) = Uanis(C28B)
Uanis(C22B) = Uanis(C22A)
Uanis(C23A) = Uanis(C23B)
Uanis(C24B) = Uanis(C24A)
Uanis(C26A) = Uanis(C26B)
Uanis(C27A) = Uanis(C27B)
Uanis(C25A) = Uanis(C25B)
Uanis(F1B) = Uanis(F1A)
Uanis(C42A) = Uanis(C42B)
Uanis(C41A) = Uanis(C41B)
Uanis(C40A) = Uanis(C40B)
Uanis(C39A) = Uanis(C39B)
Uanis(C38A) = Uanis(C38B)
Uanis(C37A) = Uanis(C37B)
Uanis(C36B) = Uanis(C36A)
Uanis(C35B) = Uanis(C35A)
Uanis(C34B) = Uanis(C34A)
Uanis(C29B) = Uanis(C29A)
Uanis(C30B) = Uanis(C30A)
Uanis(C31B) = Uanis(C31A)
Uanis(C32B) = Uanis(C32A)
Uanis(C33A) = Uanis(C33B)
Uanis(C21B) = Uanis(C21A)
Uanis(C15A) = Uanis(C15B)
Uanis(C16A) = Uanis(C20B)
Uanis(C17A) = Uanis(C19B)
Uanis(C18A) = Uanis(C18B)
Uanis(C19A) = Uanis(C17B)
Uanis(C20A) = Uanis(C16B)
4. Others
 Fixed Sof: C8A(0.5) C9A(0.5) H9A(0.5) C10A(0.5) H10A(0.5) C11A(0.5) H11A(0.5)
 C12A(0.5) H12A(0.5) C13A(0.5) C14A(0.5) H14A(0.5) H14B(0.5) H14C(0.5)
 C15A(0.5) C16A(0.5) H16A(0.5) C17A(0.5) H17A(0.5) C18A(0.5) H18A(0.5)
 C19A(0.5) H19A(0.5) C20A(0.5) C21A(0.5) H21A(0.5) H21B(0.5) H21C(0.5)
 C22A(0.5) C23A(0.5) H23A(0.5) C24A(0.5) H24A(0.5) C25A(0.5) H25A(0.5)
 C26A(0.5) H26A(0.5) C27A(0.5) C28A(0.5) H28A(0.5) H28B(0.5) C29A(0.5)
 C30A(0.5) H30A(0.5) C31A(0.5) H31A(0.5) C32A(0.5) H32A(0.5) C33A(0.5)
 H33A(0.5) C34A(0.5) C35A(0.5) H35A(0.5) H35B(0.5) H35C(0.5) C36A(0.5)
 C37A(0.5) H37A(0.5) C38A(0.5) H38A(0.5) C39A(0.5) H39A(0.5) C40A(0.5)
 H40A(0.5) C41A(0.5) C42A(0.5) H42A(0.5) H42B(0.5) H42C(0.5) C43A(0.5)
 C44A(0.5) H44A(0.5) C45A(0.5) H45A(0.5) C46A(0.5) H46A(0.5) C47A(0.5)
 H47A(0.5) C48A(0.5) C49A(0.5) H49A(0.5) H49B(0.5) C50A(0.5) C51A(0.5)
 H51A(0.5) C52A(0.5) H52A(0.5) C53A(0.5) H53A(0.5) C54A(0.5) H54A(0.5)
 C55A(0.5) C56A(0.5) H56A(0.5) H56B(0.5) H56C(0.5) C57A(0.5) C58A(0.5)
 H58A(0.5) C59A(0.5) H59A(0.5) C60A(0.5) H60A(0.5) C61A(0.5) H61A(0.5)
 C62A(0.5) C63A(0.5) H63A(0.5) H63B(0.5) H63C(0.5) F1A(0.5) P2A(0.5) P3A(0.5)
 Pd2A(0.5) Pd3A(0.5) C8B(0.5) C9B(0.5) H9B(0.5) C10B(0.5) H10B(0.5) C11B(0.5)
 H11B(0.5) C12B(0.5) H12B(0.5) C13B(0.5) C14B(0.5) H14D(0.5) H14E(0.5)
 H14F(0.5) C15B(0.5) C16B(0.5) H16B(0.5) C17B(0.5) H17B(0.5) C18B(0.5)
 H18B(0.5) C19B(0.5) H19B(0.5) C20B(0.5) C21B(0.5) H21D(0.5) H21E(0.5)
 H21F(0.5) C22B(0.5) C23B(0.5) H23B(0.5) C24B(0.5) H24B(0.5) C25B(0.5)
 H25B(0.5) C26B(0.5) H26B(0.5) C27B(0.5) C28B(0.5) H28C(0.5) H28D(0.5)
 C29B(0.5) C30B(0.5) H30B(0.5) C31B(0.5) H31B(0.5) C32B(0.5) H32B(0.5)
 C33B(0.5) H33B(0.5) C34B(0.5) C35B(0.5) H35D(0.5) H35E(0.5) H35F(0.5)
 C36B(0.5) C37B(0.5) H37B(0.5) C38B(0.5) H38B(0.5) C39B(0.5) H39B(0.5)
 C40B(0.5) H40B(0.5) C41B(0.5) C42B(0.5) H42D(0.5) H42E(0.5) H42F(0.5)
 C43B(0.5) C44B(0.5) H44B(0.5) C45B(0.5) H45B(0.5) C46B(0.5) H46B(0.5)
 C47B(0.5) H47B(0.5) C48B(0.5) C49B(0.5) H49C(0.5) H49D(0.5) C50B(0.5)
 C51B(0.5) H51B(0.5) C52B(0.5) H52B(0.5) C53B(0.5) H53B(0.5) C54B(0.5)
 H54B(0.5) C55B(0.5) C56B(0.5) H56D(0.5) H56E(0.5) H56F(0.5) C57B(0.5)
 C58B(0.5) H58B(0.5) C59B(0.5) H59B(0.5) C60B(0.5) H60B(0.5) C61B(0.5)
 H61B(0.5) C62B(0.5) C63B(0.5) H63D(0.5) H63E(0.5) H63F(0.5) F1B(0.5) P2B(0.5)
 P3B(0.5) Pd2B(0.5) Pd3B(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C28A(H28A,H28B), C49A(H49A,H49B), C28B(H28C,H28D), C49B(H49C,H49D)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C9A(H9A), C10A(H10A), C11A(H11A), C12A(H12A),
 C16A(H16A), C17A(H17A), C18A(H18A), C19A(H19A), C23A(H23A), C24A(H24A),
 C25A(H25A), C26A(H26A), C30A(H30A), C31A(H31A), C32A(H32A), C33A(H33A),
 C37A(H37A), C38A(H38A), C39A(H39A), C40A(H40A), C44A(H44A), C45A(H45A),
 C46A(H46A), C47A(H47A), C51A(H51A), C52A(H52A), C53A(H53A), C54A(H54A),
 C58A(H58A), C59A(H59A), C60A(H60A), C61A(H61A), C9B(H9B), C10B(H10B),
 C11B(H11B), C12B(H12B), C16B(H16B), C17B(H17B), C18B(H18B), C19B(H19B),
 C23B(H23B), C24B(H24B), C25B(H25B), C26B(H26B), C30B(H30B), C31B(H31B),
 C32B(H32B), C33B(H33B), C37B(H37B), C38B(H38B), C39B(H39B), C40B(H40B),
 C44B(H44B), C45B(H45B), C46B(H46B), C47B(H47B), C51B(H51B), C52B(H52B),
 C53B(H53B), C54B(H54B), C58B(H58B), C59B(H59B), C60B(H60B), C61B(H61B)
5.c Fitted hexagon refined as free rotating group:
 C8A(C9A,C10A,C11A,C12A,C13A), C29A(C30A,C31A,C32A,C33A,C34A), C8B(C9B,C10B,
 C11B,C12B,C13B), C15B(C16B,C17B,C18B,C19B,C20B), C29B(C30B,C31B,C32B,C33B,C34B)
5.d Idealised Me refined as rotating group:
 C14A(H14A,H14B,H14C), C21A(H21A,H21B,H21C), C35A(H35A,H35B,H35C), C42A(H42A,
 H42B,H42C), C56A(H56A,H56B,H56C), C63A(H63A,H63B,H63C), C14B(H14D,H14E,H14F),
 C21B(H21D,H21E,H21F), C35B(H35D,H35E,H35F), C42B(H42D,H42E,H42F), C56B(H56D,
 H56E,H56F), C63B(H63D,H63E,H63F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              56713
_shelx_fab_checksum              78130
_olex2_date_sample_data_collection 2023-11-10
_olex2_date_sample_submission    2023-11-09
_olex2_exptl_crystal_mounting_method 'oil on 50 micrometre micromount'
_olex2_submission_original_sample_id DRH-03-32-2
_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 1.877
_oxdiff_exptl_absorpt_empirical_full_min 0.721