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_1552100
_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 Cl P5 Pd3, 5(C H Cl3), Cl'
_chemical_formula_sum            'C83 H70 Cl17 P5 Pd3'
_chemical_formula_weight         2144.09
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-02-09
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-01-31 deposited with the CCDC.    2019-07-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.7594(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.6962(2)
_cell_length_b                   18.85329(16)
_cell_length_c                   29.4453(3)
_cell_measurement_reflns_used    23798
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      70.9170
_cell_measurement_theta_min      3.9130
_cell_volume                     9406.60(17)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      110.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_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    -69.00  21.00   1.00    2.50    --    0.00 -57.00-150.00   90
  2  \w    -69.00  21.00   1.00    2.50    --    0.00 -57.00 120.00   90
  3  \w    -18.00  80.00   1.00   10.00    --   54.00 -37.00 -90.00   98
  4  \w     23.00 111.00   1.00   10.00    --   54.00-125.00 -60.00   88
  5  \w     28.00 126.00   1.00   10.00    --   54.00  37.00  90.00   98
  6  \w      1.00  96.00   1.00   10.00    --   54.00 -99.00 150.00   95
  7  \w     38.00 138.00   1.00   20.00    --  108.00 -77.00 150.00  100
  8  \w     36.00 116.00   1.00   20.00    --  108.00-111.00 150.00   80
  9  \w     38.00 130.00   1.00   20.00    --  108.00 -50.00-120.00   92
 10  \w     86.00 178.00   1.00   20.00    --  108.00  50.00 -30.00   92
 11  \w    100.00 178.00   1.00   20.00    --  108.00 111.00-120.00   78
 12  \w     36.00 116.00   1.00   20.00    --  108.00-111.00-150.00   80
 13  \w     74.00 178.00   1.00   20.00    --  108.00  25.00  60.00  104
 14  \w    100.00 178.00   1.00   20.00    --  108.00 111.00 -90.00   78
 15  \w    -30.00  70.00   1.00    2.50    --    0.00  77.00  60.00  100
 16  \w    -59.00  -4.00   1.00    2.50    --    0.00 128.00-137.00   55
 17  \w     28.00  69.00   1.00   10.00    --   54.00  37.00 -90.00   41
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0070680000
_diffrn_orient_matrix_UB_12      0.0812522000
_diffrn_orient_matrix_UB_13      0.0027549000
_diffrn_orient_matrix_UB_21      0.0862199000
_diffrn_orient_matrix_UB_22      0.0079650000
_diffrn_orient_matrix_UB_23      -0.0008676000
_diffrn_orient_matrix_UB_31      -0.0280286000
_diffrn_orient_matrix_UB_32      0.0039262000
_diffrn_orient_matrix_UB_33      -0.0545453000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0356
_diffrn_reflns_av_unetI/netI     0.0357
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            51053
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.077
_diffrn_reflns_theta_max         67.077
_diffrn_reflns_theta_min         3.507
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.146
_exptl_absorpt_correction_T_max  0.950
_exptl_absorpt_correction_T_min  0.265
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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 orangish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.514
_exptl_crystal_description       plate
_exptl_crystal_F_000             4280
_exptl_crystal_size_max          0.189
_exptl_crystal_size_mid          0.164
_exptl_crystal_size_min          0.033
_refine_diff_density_max         1.032
_refine_diff_density_min         -0.653
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1063
_refine_ls_number_reflns         16773
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0438
_refine_ls_R_factor_gt           0.0358
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0527P)^2^+8.9004P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0917
_refine_ls_wR_factor_ref         0.0978
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14442
_reflns_number_total             16773
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc01847f2.cif
_cod_data_source_block           ijsf1804
_cod_original_cell_volume        9406.62(18)
_cod_database_code               1552100
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C84 H71 Cl20 P5 Pd3'
_chemical_oxdiff_usercomment     'Neil Scott nwjs-3-175'
_shelx_estimated_absorpt_t_max   0.731
_shelx_estimated_absorpt_t_min   0.250
_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
2. Restrained distances
 Cl13-C82 \\sim Cl22-C82A \\sim Cl23-C82A \\sim Cl14-C82 \\sim Cl21-C82A \\sim
Cl12-C82
 with sigma of 0.02
 Cl18-C81A \\sim Cl9-C81 \\sim Cl10-C81 \\sim Cl19-C81A \\sim Cl11-C81 \\sim
Cl20-C81A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C82A) = Uanis(C82)
Uanis(C81) = Uanis(C81A)
4. Others
 Sof(H83A)=Sof(Cl24)=Sof(Cl25)=Sof(Cl26)=1-FVAR(1)
 Sof(H83)=Sof(Cl15)=Sof(Cl16)=Sof(Cl17)=FVAR(1)
 Sof(C82A)=Sof(H82A)=Sof(Cl21)=Sof(Cl22)=Sof(Cl23)=1-FVAR(2)
 Sof(C82)=Sof(H82)=Sof(Cl12)=Sof(Cl13)=Sof(Cl14)=FVAR(2)
 Sof(C81)=Sof(H81)=Sof(Cl9)=Sof(Cl10)=Sof(Cl11)=1-FVAR(3)
 Sof(C81A)=Sof(H81A)=Sof(Cl18)=Sof(Cl19)=Sof(Cl20)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C81(H81), C81A(H81A), C82(H82), C82A(H82A), C83(H83), C83(H83A), C79(H79),
 C80(H80)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C20(H20), C21(H21),
  C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), C28(H28), C29(H29),
 C30(H30), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C38(H38), C39(H39),
  C40(H40), C41(H41), C42(H42), C44(H44), C45(H45), C46(H46), C47(H47),
 C48(H48), C50(H50), C51(H51), C52(H52), C53(H53), C54(H54), C56(H56), C57(H57),
  C58(H58), C59(H59), C60(H60), C62(H62), C63(H63), C64(H64), C65(H65),
 C66(H66), C68(H68), C69(H69), C70(H70), C71(H71), C72(H72), C74(H74), C75(H75),
  C76(H76), C77(H77), C78(H78)
;
_shelx_res_checksum              90959
_shelx_fab_checksum              16595
_olex2_date_sample_data_collection 2018-02-01
_olex2_date_sample_submission    2018-01-30
_olex2_exptl_crystal_mounting_method
'hydrocarbon oil on 200 micrometre micromount'
_olex2_submission_original_sample_id NWJS-3-175
_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 1.460
_oxdiff_exptl_absorpt_empirical_full_min 0.861