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_1552098
_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         'C54 H45 P3 Pd, 1.61(C3 H7), 0.39(C4 H8 O)'
_chemical_formula_sum            'C60.39 H59.39 O0.39 P3 Pd'
_chemical_formula_weight         990.70
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-01-31 deposited with the CCDC.    2019-07-05 downloaded from the CCDC.
;
_cell_angle_alpha                92.507(2)
_cell_angle_beta                 111.038(2)
_cell_angle_gamma                96.346(2)
_cell_formula_units_Z            2
_cell_length_a                   13.5043(4)
_cell_length_b                   13.6723(4)
_cell_length_c                   14.3402(4)
_cell_measurement_reflns_used    9032
_cell_measurement_temperature    110.05(10)
_cell_measurement_theta_max      28.6610
_cell_measurement_theta_min      3.4890
_cell_volume                     2446.12(13)
_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 0.997
_diffrn_measured_fraction_theta_max 0.998
_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      5.00  91.00   1.00   16.00    --   18.24  37.00  60.00   86
  2  \w     -7.00  89.00   1.00   16.00    --   18.24  37.00 150.00   96
  3  \w    -19.00  20.00   1.00   16.00    --   18.24 -99.00 -90.00   39
  4  \w    -17.00  60.00   1.00   16.00    --   18.24 -99.00 -30.00   77
  5  \w    -82.00  11.00   1.00   16.00    --  -18.55 -77.00-180.00   93
  6  \w     -1.00  25.00   1.00   16.00    --  -18.55  57.00  60.00   26
  7  \w    -93.00 -68.00   1.00   16.00    --  -18.55 154.00   6.00   25
;
_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      0.0072445000
_diffrn_orient_matrix_UB_12      -0.0505953000
_diffrn_orient_matrix_UB_13      0.0009490000
_diffrn_orient_matrix_UB_21      0.0492362000
_diffrn_orient_matrix_UB_22      0.0122526000
_diffrn_orient_matrix_UB_23      0.0411197000
_diffrn_orient_matrix_UB_31      -0.0273735000
_diffrn_orient_matrix_UB_32      -0.0060736000
_diffrn_orient_matrix_UB_33      0.0337579000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0266
_diffrn_reflns_av_unetI/netI     0.0457
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            20381
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         3.267
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.518
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.723
_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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.345
_exptl_crystal_description       block
_exptl_crystal_F_000             1031.7
_exptl_crystal_size_max          0.296
_exptl_crystal_size_mid          0.122
_exptl_crystal_size_min          0.078
_refine_diff_density_max         0.470
_refine_diff_density_min         -0.313
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     619
_refine_ls_number_reflns         9977
_refine_ls_number_restraints     14
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0409
_refine_ls_R_factor_gt           0.0326
_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^)+(0.0159P)^2^+1.8801P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0656
_refine_ls_wR_factor_ref         0.0701
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8672
_reflns_number_total             9977
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc01847f2.cif
_cod_data_source_block           ijsf1821
_cod_database_code               1552098
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C76 H66 O4 P4 Pd1'
_chemical_oxdiff_usercomment     'Neil Scott NWJS-4-293-crystals1'
_reflns_odcompleteness_completeness 99.76
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
 C61-O1 = C64-O1
 1.42 with sigma of 0.02
 C61-C62 = C62-C63 = C63-C64
 1.5 with sigma of 0.02
 C60-C59
 1.513 with sigma of 0.02
 C59-C58
 1.524 with sigma of 0.02
 C60-C58
 2.48 with sigma of 0.04
 C59-C58
 2.49 with sigma of 0.04
 C61-C64
 2.32 with sigma of 0.04
 C61-C63 = C62-C64
 2.36 with sigma of 0.04
 C62-O1 = C63-O1
 2.34 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C63) = Uanis(C62)
4. Others
 Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(O1)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(C61)=
 Sof(H61A)=Sof(H61B)=Sof(C62)=Sof(H62A)=Sof(H62B)=1-FVAR(1)
 Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=Sof(C59)=
 Sof(H59A)=Sof(H59B)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C57(H57A,H57B), C56(H56A,H56B), C63(H63A,H63B), C60(H60A,H60B), C64(H64A,
 H64B), C61(H61A,H61B), C59(H59A,H59B), C62(H62A,H62B)
5.b Aromatic/amide H refined with riding coordinates:
 C26(H26), C38(H38), C50(H50), C18(H18), C32(H32), C2(H2), C54(H54), C30(H30),
 C6(H6), C36(H36), C48(H48), C53(H53), C20(H20), C14(H14), C52(H52), C44(H44),
 C5(H5), C12(H12), C9(H9), C3(H3), C51(H51), C35(H35), C29(H29), C27(H27),
 C34(H34), C24(H24), C17(H17), C8(H8), C42(H42), C21(H21), C45(H45), C10(H10),
 C40(H40), C4(H4), C22(H22), C39(H39), C41(H41), C33(H33), C11(H11), C28(H28),
 C47(H47), C15(H15), C23(H23), C46(H46), C16(H16)
5.c Idealised Me refined as rotating group:
 C55(H55A,H55B,H55C), C58(H58A,H58B,H58C)
;
_shelx_res_checksum              2313
_olex2_date_sample_data_collection 2018-10-19
_olex2_date_sample_submission    2018-10-19
_olex2_exptl_crystal_mounting_method 'oil on micrount 200 micrometres'
_olex2_submission_original_sample_id 'Neil Scott NWJS-4-293-crystals1'
_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 1.153
_oxdiff_exptl_absorpt_empirical_full_min 0.904