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_7701218
_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         '2(C66 H59 Cl3 I6 N9 O6 Pd3), 5.5(C4 H8 O2)'
_chemical_formula_sum            'C154 H162 Cl6 I12 N18 O23 Pd6'
_chemical_formula_weight         5006.91
_chemical_name_systematic
;
tris-(3-chloropyridyl)(methyl(cyclotriguaiacylenyl)methylbenzimidazol-2-ylidene)palladium(II) iodide dioxane 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             2018-04-04
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-03-25 deposited with the CCDC.    2019-09-16 downloaded from the CCDC.
;
_cell_angle_alpha                99.360(3)
_cell_angle_beta                 97.234(3)
_cell_angle_gamma                103.156(3)
_cell_formula_units_Z            2
_cell_length_a                   18.4409(5)
_cell_length_b                   21.9443(8)
_cell_length_c                   23.7505(8)
_cell_measurement_reflns_used    14205
_cell_measurement_temperature    120.1(4)
_cell_measurement_theta_max      73.4570
_cell_measurement_theta_min      3.4050
_cell_volume                     9100.6(5)
_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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.1(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3095
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.964
_diffrn_measured_fraction_theta_max 0.926
_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   -102.00 -11.00   1.00   16.50    --  -38.50 -65.00 -94.47   91
  2  \w    -59.00  31.00   1.00   16.50    --  -38.50  37.00-180.00   90
  3  \w   -107.00 -12.00   1.00   16.50    --  -38.50 -64.00  23.41   95
  4  \w     38.00  66.00   1.00   16.50    --   42.71  37.00  30.00   28
  5  \w      9.00  70.00   1.00   16.50    --   42.71 -65.00 110.38   61
  6  \w      0.00  70.00   1.00   16.50    --   42.71 -64.00 -27.67   70
  7  \w     -5.00  70.00   1.00   16.50    --   42.71 -65.00-170.78   75
  8  \w     36.00 108.00   1.00   66.00    --  104.98 -65.00 -28.03   72
  9  \w     63.00  98.00   1.00   66.00    --  104.98 -64.00  29.59   35
 10  \w     61.00  99.00   1.00   66.00    --  104.98 -65.00 -71.35   38
 11  \w     38.00 100.00   1.00   66.00    --  104.98 -65.00 162.78   62
 12  \w     84.00 143.00   1.00   66.00    --  104.98  30.00-120.00   59
 13  \w     62.00 106.00   1.00   66.00    --  104.98 -65.00-166.51   44
 14  \w     65.00 166.00   1.00   66.00    --  104.98  15.00-180.00  101
 15  \w     65.00  96.00   1.00   66.00    --  104.98 -65.00 106.51   31
 16  \w     32.00 126.00   1.00   66.00    --  104.98 -30.00-150.00   94
 17  \w     66.00  96.00   1.00   66.00    --  104.98 -65.00-116.75   30
 18  \w     33.00 107.00   1.00   66.00    --  104.98 -30.00 -30.00   74
 19  \w     44.00  92.00   1.00   66.00    --  104.98 -65.00 134.76   48
 20  \w    140.00 175.00   1.00   66.00    --  104.98  45.00-120.00   35
 21  \w     68.00 117.00   1.00   66.00    --  104.98 -64.00  53.65   49
;
_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      -0.0085115000
_diffrn_orient_matrix_UB_12      -0.0686741000
_diffrn_orient_matrix_UB_13      -0.0324330000
_diffrn_orient_matrix_UB_21      -0.0081208000
_diffrn_orient_matrix_UB_22      0.0222289000
_diffrn_orient_matrix_UB_23      -0.0582265000
_diffrn_orient_matrix_UB_31      0.0862549000
_diffrn_orient_matrix_UB_32      0.0141310000
_diffrn_orient_matrix_UB_33      0.0027352000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0929
_diffrn_reflns_av_unetI/netI     0.1323
_diffrn_reflns_Laue_measured_fraction_full 0.964
_diffrn_reflns_Laue_measured_fraction_max 0.926
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            71312
_diffrn_reflns_point_group_measured_fraction_full 0.964
_diffrn_reflns_point_group_measured_fraction_max 0.926
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.228
_diffrn_reflns_theta_min         3.116
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    22.001
_exptl_absorpt_correction_T_max  0.539
_exptl_absorpt_correction_T_min  0.386
_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_density_diffrn    1.827
_exptl_crystal_description       block
_exptl_crystal_F_000             4820
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.821
_refine_diff_density_min         -1.461
_refine_diff_density_rms         0.193
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1931
_refine_ls_number_reflns         34313
_refine_ls_number_restraints     57
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.1618
_refine_ls_R_factor_gt           0.0805
_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^)+(0.0936P)^2^+39.5615P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1836
_refine_ls_wR_factor_ref         0.2330
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18012
_reflns_number_total             34313
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt03400e2.cif
_cod_data_source_block           jf5-653
_cod_depositor_comments
'Adding full bibliography for 7701214--7701219.cif.'
_cod_database_code               7701218
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C313 H334 Cl12 I24 N36 O48 Pd12 '
_shelx_estimated_absorpt_t_max   0.406
_shelx_estimated_absorpt_t_min   0.308
_reflns_odcompleteness_completeness 96.56
_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. Restrained distances
 Cl2-C55
 1.74 with sigma of 0.01
 Cl3-C58
 1.74 with sigma of 0.01
 C168-O25 = C167-O25
 1.46 with sigma of 0.01
 C159-C158 = O27-C159 = O27-C162 = C162-C161 = N4-C45 = O26-C158 = O26-C161
 1.45 with sigma of 0.02
 C153-C150 = O19-C150 = O19-C151 = C152-C151 = O20-C152 = O20-C153
 1.45 with sigma of 0.02
 C164-O24
 1.45 with sigma of 0.02
 O24-C165
 1.45 with sigma of 0.02
 C165-C166
 1.45 with sigma of 0.02
 C166-O23
 1.45 with sigma of 0.02
 O23-C163
 1.45 with sigma of 0.02
 C164-C163
 1.45 with sigma of 0.02
 O21-C155 = O21-C156 = C157-C156 = O22-C157 = C154-O22 = C154-C155
 1.45 with sigma of 0.02
 C53-Cl2
 2.69 with sigma of 0.02
 C57-Cl2
 2.69 with sigma of 0.02
 Cl3-C56
 2.69 with sigma of 0.02
 C61-Cl3
 2.69 with sigma of 0.02
 C158-O27
 2.37 with sigma of 0.04
 C159-C162
 2.37 with sigma of 0.04
 O27-C161
 2.37 with sigma of 0.04
 C162-O26
 2.37 with sigma of 0.04
 C161-C158
 2.37 with sigma of 0.04
 O26-C159
 2.37 with sigma of 0.04
 C154-C157
 2.37 with sigma of 0.04
 C154-O21
 2.37 with sigma of 0.04
 C155-C156
 2.37 with sigma of 0.04
 O21-C157
 2.37 with sigma of 0.04
 C153-O19
 2.37 with sigma of 0.04
 C150-C151
 2.37 with sigma of 0.04
 O19-C152
 2.37 with sigma of 0.04
 C151-O20
 2.37 with sigma of 0.04
 C152-C153
 2.37 with sigma of 0.04
 O20-C150
 2.37 with sigma of 0.04
 C164-C165
 2.37 with sigma of 0.04
 O24-C166
 2.37 with sigma of 0.04
 C166-C163
 2.37 with sigma of 0.04
 O23-C164
 2.37 with sigma of 0.04
 C163-O24
 2.37 with sigma of 0.04
 C165-O23
 2.37 with sigma of 0.04
 C156-O22
 2.37 with sigma of 0.04
 O22-C155
 2.37 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uiso(C165) = Uiso(C166) = Uiso(O23) = Uiso(C163) = Uiso(C164) = Uiso(O24)
Uiso(C162) = Uiso(O27) = Uiso(C159) = Uiso(C158) = Uiso(O26) = Uiso(C161)
4. Others
 Fixed Sof: Cl3(0.5) Cl2(0.5) C53(0.5) H53(0.5) C55(0.5) C57(0.5) H57(0.5)
 C59(0.5) H59(0.5) C60(0.5) H60(0.5) N7(0.5) C54(0.5) H54(0.5) C56(0.5)
 H56(0.5) C58(0.5) C61(0.5) H61(0.5) N6(0.5) C52(0.5) H52(0.5) O27(0.5)
 O26(0.5) C158(0.5) H15A(0.5) H15B(0.5) C161(0.5) H16D(0.5) H16E(0.5) C159(0.5)
 H15C(0.5) H15D(0.5) C162(0.5) H16F(0.5) H16G(0.5) C155(0.5) H15E(0.5)
 H15F(0.5) C156(0.5) H15G(0.5) H15H(0.5) O21(0.5) C157(0.5) H15I(0.5) H15J(0.5)
 O22(0.5) C154(0.5) H15K(0.5) H15L(0.5) O24(0.5) C152(0.5) H15M(0.5) H15N(0.5)
 C153(0.5) H15O(0.5) H15P(0.5) O19(0.5) O23(0.5) C151(0.5) H15Q(0.5) H15R(0.5)
 C164(0.5) H16H(0.5) H16I(0.5) O20(0.5) C163(0.5) H16J(0.5) H16K(0.5) C166(0.5)
 H16L(0.5) H16M(0.5) C150(0.5) H15S(0.5) H15T(0.5) C165(0.5) H16N(0.5) H16O(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C9(H9A,H9B), C17(H17A,H17B), C109(H10A,H10B), C92(H92A,H92B),
 C20(H20A,H20B), C78(H78A,H78B), C28(H28A,H28B), C85(H85A,H85B), C94(H94A,H94B),
  C139(H13A,H13B), C142(H14M,H14N), C70(H70A,H70B), C143(H14O,H14P), C148(H14A,
 H14B), C145(H14Q,H14R), C144(H14S,H14T), C149(H14C,H14D), C140(H14I,H14J),
 C146(H14E,H14F), C141(H14K,H14L), C147(H14G,H14H), C138(H13C,H13D), C168(H16P,
 H16Q), C167(H16R,H16S), C158(H15A,H15B), C161(H16D,H16E), C159(H15C,H15D),
 C162(H16F,H16G), C155(H15E,H15F), C156(H15G,H15H), C157(H15I,H15J), C154(H15K,
 H15L), C152(H15M,H15N), C153(H15O,H15P), C151(H15Q,H15R), C164(H16H,H16I),
 C163(H16J,H16K), C166(H16L,H16M), C150(H15S,H15T), C165(H16N,H16O)
5.b Aromatic/amide H refined with riding coordinates:
 C137(H137), C118(H118), C5(H5), C132(H132), C128(H128), C4(H4), C24(H24),
 C12(H12), C15(H15), C113(H113), C129(H129), C90(H90), C7(H7), C136(H136),
 C38(H38), C87(H87), C122(H122), C6(H6), C80(H80), C41(H41), C48(H48),
 C135(H135), C133(H133), C46(H46), C42(H42), C120(H120), C123(H123), C49(H49),
 C27(H27), C116(H116), C75(H75), C72(H72), C83(H83), C114(H114), C130(H130),
 C68(H68), C119(H119), C125(H125), C67(H67), C126(H126), C47(H47), C98(H98),
 C35(H35), C32(H32), C127(H127), C66(H66), C99(H99), C65(H65), C101(H101),
 C104(H104), C100(H100), C33(H33), C106(H106), C34(H34), C103(H103), C102(H102),
  C53(H53), C57(H57), C59(H59), C60(H60), C54(H54), C56(H56), C61(H61), C52(H52)
5.c Fitted hexagon refined as free rotating group:
 C53(C55,C57,C59,C60,N7), C54(C56,C58,C61,N6,C52)
5.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C111(H11A,H11B,H11C), C93(H93A,H93B,H93C), C2(H2A,H2B,
 H2C), C77(H77A,H77B,H77C), C51(H51A,H51B,H51C), C108(H10C,H10D,H10E), C37(H37A,
 H37B,H37C), C44(H44A,H44B,H44C), C30(H30A,H30B,H30C), C63(H63A,H63B,H63C),
 C96(H96A,H96B,H96C)
;
_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 2.557
_oxdiff_exptl_absorpt_empirical_full_min 0.502