The ubiquitous cross-coupling catalyst system ‘Pd(OAc)2’/2PPh3 forms a unique dinuclear PdI complex: an important entry point into catalytically competent cyclic Pd3 clusters
Scott, Neil W. J.; Ford, Mark J.; Schotes, Christoph; Parker, Rachel R.; Whitwood, Adrian C.; Fairlamb, Ian J. S.; Chemical Science  (2019) –; doi:10.1039/C9SC01847F

data_1552099
_publ_section_title
;
 The ubiquitous cross-coupling catalyst system
 &#x2018;Pd(OAc)2&#x2019;/2PPh3 forms a unique dinuclear PdI complex: an
 important entry point into catalytically competent cyclic Pd3 clusters
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC01847F
_journal_year                    2019
_chemical_formula_moiety         'C78 H65 Br2 P5 Pd3, C4 H8 O'
_chemical_formula_sum            'C82 H73 Br2 O P5 Pd3'
_chemical_formula_weight         1708.27
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-03-05 deposited with the CCDC.    2019-07-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.645(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.3726(5)
_cell_length_b                   23.1564(6)
_cell_length_c                   18.9888(4)
_cell_measurement_reflns_used    7691
_cell_measurement_temperature    110.05(10)
_cell_measurement_theta_max      71.0000
_cell_measurement_theta_min      4.2030
_cell_volume                     7164.3(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      110.05(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_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     19.00  66.00   1.00    8.00    --    0.00  57.00   0.00   47
  2  \w     31.00  59.00   1.00    8.00    --    0.00  57.00 -60.00   28
  3  \w    -21.00  30.00   1.00    8.00    --    0.00  57.00 -60.00   51
  4  \w    -12.00  74.00   1.00   31.50    --   54.00 -57.00 -30.00   86
  5  \w    -14.00  67.00   1.00   31.50    --   54.00 -57.00  60.00   81
  6  \w    -17.00  59.00   1.00   31.50    --   54.00 -37.00 120.00   76
  7  \w     50.00 106.00   1.00   31.50    --   54.00-125.00-180.00   56
  8  \w     96.00 121.00   1.00   31.50    --   54.00  37.00 -60.00   25
  9  \w    136.00 163.00   1.00   31.50    --  108.00  63.00  60.00   27
 10  \w     87.00 169.00   1.00   31.50    --  108.00  50.00 150.00   82
 11  \w     39.00 177.00   1.00   31.50    --  108.00  12.00 120.00  138
 12  \w     67.00 112.00   1.00   31.50    --  108.00-111.00 -30.00   45
 13  \w     62.00 146.00   1.00   31.50    --  108.00 -91.00  30.00   84
 14  \w     47.00 101.00   1.00   31.50    --  108.00-111.00 -90.00   54
 15  \w     40.00 100.00   1.00   31.50    --  108.00 -77.00 -60.00   60
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0847294000
_diffrn_orient_matrix_UB_12      -0.0186032000
_diffrn_orient_matrix_UB_13      0.0206698000
_diffrn_orient_matrix_UB_21      0.0395791000
_diffrn_orient_matrix_UB_22      -0.0192332000
_diffrn_orient_matrix_UB_23      0.0731888000
_diffrn_orient_matrix_UB_31      -0.0133876000
_diffrn_orient_matrix_UB_32      0.0608685000
_diffrn_orient_matrix_UB_33      0.0296648000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0403
_diffrn_reflns_av_unetI/netI     0.0559
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            24240
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         3.902
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.728
_exptl_absorpt_correction_T_max  0.825
_exptl_absorpt_correction_T_min  0.292
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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 red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.584
_exptl_crystal_description       block
_exptl_crystal_F_000             3424
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.277
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.036
_refine_diff_density_max         2.882
_refine_diff_density_min         -1.583
_refine_diff_density_rms         0.171
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.202
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     845
_refine_ls_number_reflns         12724
_refine_ls_number_restraints     23
_refine_ls_restrained_S_all      1.201
_refine_ls_R_factor_all          0.0884
_refine_ls_R_factor_gt           0.0704
_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^)+148.0454P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1630
_refine_ls_wR_factor_ref         0.1714
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10201
_reflns_number_total             12724
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc01847f2.cif
_cod_data_source_block           ijsf1905
_cod_database_code               1552099
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C78 H65 Br2 P5 Pd3'
_chemical_oxdiff_usercomment     'Neil Scott NWJS-4-325-crystals2'
_reflns_odcompleteness_completeness 99.32
_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, All C(H,H,H,H) groups
2. Restrained distances
 C82A-C79
 1.5 with sigma of 0.02
 O1A-C82A
 1.42 with sigma of 0.02
 O1A-C81
 1.42 with sigma of 0.02
 C82B-C81
 1.5 with sigma of 0.02
 C81-C80
 1.5 with sigma of 0.02
 C80-C79
 1.5 with sigma of 0.02
 C82B-O1B
 1.42 with sigma of 0.02
 O1B-C79
 1.42 with sigma of 0.02
 C82A-C80
 2.36 with sigma of 0.04
 C79-O1A
 2.34 with sigma of 0.04
 O1A-C80
 2.34 with sigma of 0.04
 C82A-C81
 2.32 with sigma of 0.04
 C81-C79
 2.36 with sigma of 0.04
 C82B-C80
 2.36 with sigma of 0.04
 C81-O1B
 2.34 with sigma of 0.04
 O1B-C80
 2.34 with sigma of 0.04
 C82B-C79
 2.32 with sigma of 0.04
 O1B-C79 \\sim O1B-C82B \\sim O1A-C82A \\sim O1A-C81
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(O1A) = Uanis(C82B)
Uanis(O1B) = Uanis(C82A)
4. Others
 Sof(H79C)=Sof(H79D)=Sof(H81C)=Sof(H81D)=Sof(O1A)=Sof(C82A)=Sof(H82C)=
 Sof(H82D)=1-FVAR(1)
 Sof(C82B)=Sof(H82A)=Sof(H82B)=Sof(H79A)=Sof(H79B)=Sof(O1B)=Sof(H81A)=
 Sof(H81B)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C82B(H82A,H82B), C79(H79A,H79B), C79(H79C,H79D), C80(H80A,H80B), C81(H81A,
 H81B), C81(H81C,H81D), C82A(H82C,H82D)
5.b Aromatic/amide H refined with riding coordinates:
 C74(H74), C56(H56), C58(H58), C6(H6), C78(H78), C8(H8), C75(H75), C57(H57),
 C24(H24), C26(H26), C12(H12), C60(H60), C76(H76), C59(H59), C68(H68), C42(H42),
  C2(H2), C14(H14), C38(H38), C20(H20), C54(H54), C5(H5), C62(H62), C66(H66),
 C21(H21), C30(H30), C11(H11), C9(H9), C3(H3), C77(H77), C27(H27), C44(H44),
 C4(H4), C23(H23), C71(H71), C40(H40), C36(H36), C22(H22), C33(H33), C17(H17),
 C41(H41), C10(H10), C15(H15), C28(H28), C18(H18), C65(H65), C72(H72), C63(H63),
  C48(H48), C32(H32), C70(H70), C29(H29), C39(H39), C64(H64), C45(H45),
 C53(H53), C46(H46), C51(H51), C69(H69), C34(H34), C50(H50), C16(H16), C35(H35),
  C52(H52), C47(H47)
;
_olex2_date_sample_data_collection 2019-02-15
_olex2_date_sample_submission    2019-02-13
_olex2_exptl_crystal_mounting_method 'oil on micromount 200 micrometre'
_olex2_submission_original_sample_id 'Neil Scott NWJS-4-325-crystals2'
_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 1.349
_oxdiff_exptl_absorpt_empirical_full_min 0.711