Cyclotriveratrylene-tethered trinuclear palladium(ii)-NHC complexes; reversal of site selectivity in Suzuki-Miyaura reactions.
Fowler, Jonathan M.; Britton, Edward; Pask, Christopher M.; Willans, Charlotte E.; Hardie, Michaele J.; Dalton transactions (Cambridge, England : 2003) 48 (2019) 14687–14695; doi:10.1039/c9dt03400e

data_7701214
_publ_section_title
;
 Cyclotriveratrylene-tethered trinuclear palladium(ii)-NHC complexes;
 reversal of site selectivity in Suzuki-Miyaura reactions.
;
_journal_issue                   39
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              14687
_journal_page_last               14695
_journal_paper_doi               10.1039/c9dt03400e
_journal_volume                  48
_journal_year                    2019
_chemical_formula_moiety
'C66 H60 Cl3 I6 N9 O6 Pd3, C5 H12, C5 H10, 0.5(C H2 Cl2), 2.5(O)'
_chemical_formula_sum            'C76.5 H90 Cl4 I6 N9 O8.5 Pd3'
_chemical_formula_weight         2493.97
_chemical_name_systematic
;
tris-(3-chloropyridyl)(methyl(cyclotriguaiacylenyl)methylbenzimidazol-2-ylidene)palladium(II) iodide pentane dichloromethane clathrate
;
_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
_audit_creation_date             2018-12-20
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-03-25 deposited with the CCDC.    2019-09-16 downloaded from the CCDC.
;
_cell_angle_alpha                104.839(4)
_cell_angle_beta                 111.072(4)
_cell_angle_gamma                98.298(3)
_cell_formula_units_Z            2
_cell_length_a                   15.6946(6)
_cell_length_b                   15.8484(8)
_cell_length_c                   21.6110(10)
_cell_measurement_reflns_used    7270
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.3880
_cell_measurement_theta_min      3.7440
_cell_volume                     4679.2(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43b (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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3095
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.853
_diffrn_measured_fraction_theta_max 0.853
_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    -75.00 -48.00   1.00   18.50    --  -38.50 -57.00 -90.00   27
  2  \w   -107.00 -81.00   1.00   18.50    --  -38.50 -57.00 -90.00   26
  3  \w    -23.00  30.00   1.00   18.50    --  -38.50  64.00 -47.43   53
  4  \w    -64.00 -33.00   1.00   18.50    --  -38.50  64.00 -85.37   31
  5  \w    -65.00 -25.00   1.00   18.50    --  -38.50  64.00 -47.43   40
  6  \w    -24.00  64.00   1.00   18.50    --   42.71 -57.00  90.00   88
  7  \w     25.00  70.00   1.00   18.50    --   42.71 -65.00   5.24   45
  8  \w     41.00 125.00   1.00   74.00    --  104.98 -30.00-150.00   84
  9  \w     72.00 115.00   1.00   74.00    --  104.98 -65.00 148.97   43
 10  \w     65.00 109.00   1.00   74.00    --  104.98 -65.00 108.39   44
 11  \w     70.00 120.00   1.00   74.00    --  104.98 -65.00 -14.74   50
 12  \w    149.00 175.00   1.00   74.00    --  104.98  45.00-150.00   26
 13  \w     84.00 178.00   1.00   74.00    --  104.98  30.00  30.00   94
 14  \w     36.00  96.00   1.00   74.00    --  104.98 -65.00  72.04   60
 15  \w     66.00  95.00   1.00   74.00    --  104.98 -65.00  36.62   29
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0300912000
_diffrn_orient_matrix_UB_12      -0.0646850000
_diffrn_orient_matrix_UB_13      0.0351978000
_diffrn_orient_matrix_UB_21      0.0965740000
_diffrn_orient_matrix_UB_22      0.0403394000
_diffrn_orient_matrix_UB_23      0.0636998000
_diffrn_orient_matrix_UB_31      -0.0404721000
_diffrn_orient_matrix_UB_32      0.0710030000
_diffrn_orient_matrix_UB_33      0.0355125000
_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     0.0570
_diffrn_reflns_Laue_measured_fraction_full 0.853
_diffrn_reflns_Laue_measured_fraction_max 0.853
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            16060
_diffrn_reflns_point_group_measured_fraction_full 0.853
_diffrn_reflns_point_group_measured_fraction_max 0.853
_diffrn_reflns_theta_full        54.242
_diffrn_reflns_theta_max         54.242
_diffrn_reflns_theta_min         3.115
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    21.621
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80315
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.770
_exptl_crystal_description       block
_exptl_crystal_F_000             2408
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         2.016
_refine_diff_density_min         -1.129
_refine_diff_density_rms         0.144
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     934
_refine_ls_number_reflns         9748
_refine_ls_number_restraints     17
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0707
_refine_ls_R_factor_gt           0.0533
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0802P)^2^+26.2373P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1380
_refine_ls_wR_factor_ref         0.1505
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7663
_reflns_number_total             9748
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt03400e2.cif
_cod_data_source_block           jf2333
_cod_depositor_comments
'Adding full bibliography for 7701214--7701219.cif.'
_cod_original_formula_sum        'C76.50 H90 Cl4 I6 N9 O8.50 Pd3'
_cod_database_code               7701214
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 79.94
_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. Shared sites
{C74, C74A}
3. Restrained distances
 C73-C72 = C76-C75
 1.51 with sigma of 0.01
 C75-C74 = C74-C73
 1.52 with sigma of 0.01
 C77-C78
 1.51 with sigma of 0.01
 C77-C74
 1.52 with sigma of 0.01
 C81-C80 = C81-C82
 1.52 with sigma of 0.01
 C82-C83 = C80-C79
 1.51 with sigma of 0.01
 Cl4-C67
 1.74 with sigma of 0.01
 Cl3-C64
 1.74 with sigma of 0.01
 Cl7-C85
 1.74 with sigma of 0.01
4. Restrained planarity
 Cl4, C67, C68, C69, C70, N10, C66
 with sigma of 0.05
5. Uiso/Uaniso restraints and constraints
Uiso(C66) = Uiso(C68) = Uiso(C69) = Uiso(C70) = Uiso(N10) = Uiso(C67)
Uiso(C74) = Uiso(C74A)
6. Others
 Fixed Sof: Cl3(0.75) N9(0.75) C65(0.75) H65(0.75) C64(0.75) C63(0.75)
 H63(0.75) C61(0.75) H61(0.75) C62(0.75) H62(0.75) C74(0.5) H74A(0.5) H74B(0.5)
 C72(0.4) H72A(0.4) H72B(0.4) H72C(0.4) C73(0.4) H73A(0.4) H73B(0.4) Cl4(0.25)
 C77(0.6) H77A(0.6) H77B(0.6) C78(0.6) H78A(0.6) H78B(0.6) H78C(0.6) C66(0.25)
 H66(0.25) N10(0.25) C70(0.25) H70(0.25) C69(0.25) H69(0.25) C68(0.25)
 H68(0.25) C67(0.25) Cl6(0.5) Cl7(0.5) C85(0.5) H85A(0.5) H85B(0.5) O8(0.5)
 O9(0.5) O10(0.5) C74A(0.5) H74C(0.5) H74D(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C42(H42A,H42B), C34(H34A,H34B), C71(H71A,H71B), C17(H17A,H17B),
 C25(H25A,H25B), C82(H82A,H82B), C81(H81A,H81B), C80(H80A,H80B), C74(H74A,H74B),
  C73(H73A,H73B), C77(H77A,H77B), C85(H85A,H85B), C74A(H74C,H74D)
7.b Me refined with riding coordinates:
 C72(H72A,H72B,H72C), C78(H78A,H78B,H78C)
7.c Aromatic/amide H refined with riding coordinates:
 C37(H37), C40(H40), C11(H11), C19(H19), C22(H22), C14(H14), C29(H29),
 C48(H48), C30(H30), C60(H60), C32(H32), C7(H7), C31(H31), C46(H46), C45(H45),
 C59(H59), C4(H4), C47(H47), C5(H5), C56(H56), C6(H6), C55(H55), C51(H51),
 C53(H53), C58(H58), C54(H54), C65(H65), C63(H63), C61(H61), C62(H62), C66(H66),
  C70(H70), C69(H69), C68(H68)
7.d Fitted hexagon refined as free rotating group:
 C66(N10,C70,C69,C68,C67)
7.e Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C41(H41A,H41B,H41C), C50(H50A,H50B,H50C), C2(H2A,H2B,
 H2C), C24(H24A,H24B,H24C), C16(H16A,H16B,H16C), C83(H83A,H83B,H83C), C79(H79A,
 H79B,H79C), C76(H76A,H76B,H76C)
;
_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 1.924
_oxdiff_exptl_absorpt_empirical_full_min 0.569