Insight into the efficiency of cinnamyl-supported precatalysts for the suzuki-miyaura reaction: observation of pd(i) dimers with bridging allyl ligands during catalysis.
Hruszkewycz, Damian P.; Balcells, David; Guard, Louise M.; Hazari, Nilay; Tilset, Mats; Journal of the American Chemical Society 136 (2014) 7300–7316; doi:10.1021/ja412565c

data_4121810
_publ_section_title
;
 Insight into the efficiency of cinnamyl-supported precatalysts for the
 suzuki-miyaura reaction: observation of pd(i) dimers with bridging allyl
 ligands during catalysis.
;
_journal_issue                   20
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7300
_journal_page_last               7316
_journal_paper_doi               10.1021/ja412565c
_journal_volume                  136
_journal_year                    2014
_chemical_formula_moiety         'C58 H79 Cl N4 Pd2'
_chemical_formula_sum            'C58 H79 Cl N4 Pd2'
_chemical_formula_weight         1080.50
_chemical_name_systematic
;
 ? 
;
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-06-04
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 113.824(8)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   20.562(4)
_cell_length_b                   12.0606(2)
_cell_length_c                   24.4409(17)
_cell_measurement_reflns_used    159107
_cell_measurement_temperature    93
_cell_measurement_theta_max      65.2
_cell_measurement_theta_min      2.0
_cell_volume                     5544.6(12)
_computing_cell_refinement
'CrystalClear-SM Expert 2.0 r12 (Rigaku, 2011)'
_computing_data_collection
'CrystalClear-SM Expert 2.0 r12 (Rigaku, 2011)'
_computing_data_reduction
'CrystalClear-SM Expert 2.0 r12 (Rigaku, 2011)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      93
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 22.2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
scan:
    Number of images: 90
               Slice: -48.0000 - 132.0000
         Image width: 2.0000
            Exp time: 2.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 0.0000
                 Phi: 0.0000
                 XTD: 42.2538
              2theta: 41.5800
scan:
    Number of images: 90
               Slice: 0.0000 - 180.0000
         Image width: 2.0000
            Exp time: 5.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 0.0000
                 Phi: 0.0000
                 XTD: 42.2538
              2theta: 89.5800
scan:
    Number of images: 90
               Slice: -48.0000 - 132.0000
         Image width: 2.0000
            Exp time: 2.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 0.0000
                 Phi: 180.0000
                 XTD: 42.2538
              2theta: 41.5800
scan:
    Number of images: 90
               Slice: 0.0000 - 180.0000
         Image width: 2.0000
            Exp time: 5.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 0.0000
                 Phi: 180.0000
                 XTD: 42.2538
              2theta: 89.5800
scan:
    Number of images: 90
               Slice: -48.0000 - 132.0000
         Image width: 2.0000
            Exp time: 2.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 220.0000
                 XTD: 42.2538
              2theta: 41.5800
scan:
    Number of images: 90
               Slice: 0.0000 - 180.0000
         Image width: 2.0000
            Exp time: 5.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 50.0000
                 XTD: 42.2538
              2theta: 89.5800
scan:
    Number of images: 90
               Slice: 0.0000 - 180.0000
         Image width: 2.0000
            Exp time: 5.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 125.0000
                 XTD: 42.2538
              2theta: 89.5800
scan:
    Number of images: 90
               Slice: -48.0000 - 132.0000
         Image width: 2.0000
            Exp time: 2.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 55.0000
                 XTD: 42.2538
              2theta: 41.5800
scan:
    Number of images: 90
               Slice: 0.0000 - 180.0000
         Image width: 2.0000
            Exp time: 5.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 225.0000
                 XTD: 42.2538
              2theta: 89.5800
scan:
    Number of images: 90
               Slice: 0.0000 - 180.0000
         Image width: 2.0000
            Exp time: 5.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 300.0000
                 XTD: 42.2538
              2theta: 89.5800
scan:
    Number of images: 90
               Slice: 0.0000 - 180.0000
         Image width: 2.0000
            Exp time: 5.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 250.0000
                 XTD: 42.2538
              2theta: 89.5800
scan:
    Number of images: 90
               Slice: -48.0000 - 132.0000
         Image width: 2.0000
            Exp time: 2.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 320.0000
                 XTD: 42.2538
              2theta: 41.5800
scan:
    Number of images: 90
               Slice: -48.0000 - 132.0000
         Image width: 2.0000
            Exp time: 2.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 110.0000
                 XTD: 42.2538
              2theta: 41.5800
scan:
    Number of images: 90
               Slice: 0.0000 - 180.0000
         Image width: 2.0000
            Exp time: 5.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 150.0000
                 XTD: 42.2538
              2theta: 89.5800
scan:
    Number of images: 90
               Slice: 0.0000 - 180.0000
         Image width: 2.0000
            Exp time: 5.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 75.0000
                 XTD: 42.2538
              2theta: 89.5800
scan:
    Number of images: 90
               Slice: 0.0000 - 180.0000
         Image width: 2.0000
            Exp time: 5.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 350.0000
                 XTD: 42.2538
              2theta: 89.5800
scan:
    Number of images: 90
               Slice: -48.0000 - 132.0000
         Image width: 2.0000
            Exp time: 2.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 0.0000
                 XTD: 42.2538
              2theta: 41.5800
scan:
    Number of images: 90
               Slice: -48.0000 - 132.0000
         Image width: 2.0000
            Exp time: 2.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 275.0000
                 XTD: 42.2538
              2theta: 41.5800
scan:
    Number of images: 90
               Slice: 0.0000 - 180.0000
         Image width: 2.0000
            Exp time: 5.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 25.0000
                 XTD: 42.2538
              2theta: 89.5800
scan:
    Number of images: 90
               Slice: 0.0000 - 180.0000
         Image width: 2.0000
            Exp time: 5.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 175.0000
                 XTD: 42.2538
              2theta: 89.5800
scan:
    Number of images: 90
               Slice: 0.0000 - 180.0000
         Image width: 2.0000
            Exp time: 5.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 0.0000
                 XTD: 42.2538
              2theta: 89.5800
scan:
    Number of images: 90
               Slice: 0.0000 - 180.0000
         Image width: 2.0000
            Exp time: 5.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 325.0000
                 XTD: 42.2538
              2theta: 89.5800
scan:
    Number of images: 90
               Slice: -48.0000 - 132.0000
         Image width: 2.0000
            Exp time: 2.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 165.0000
                 XTD: 42.2538
              2theta: 41.5800
scan:
    Number of images: 90
               Slice: 0.0000 - 180.0000
         Image width: 2.0000
            Exp time: 5.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 275.0000
                 XTD: 42.2538
              2theta: 89.5800
scan:
    Number of images: 90
               Slice: 0.0000 - 180.0000
         Image width: 2.0000
            Exp time: 5.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 100.0000
                 XTD: 42.2538
              2theta: 89.5800
scan:
    Number of images: 90
               Slice: 0.0000 - 180.0000
         Image width: 2.0000
            Exp time: 5.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 200.0000
                 XTD: 42.2538
              2theta: 89.5800
;
_diffrn_measurement_device
;
AFC11 (Left): Eulerian 3 circle
;
_diffrn_measurement_device_type  'Rigaku Saturn 944+ CCD'
_diffrn_measurement_method       \w
_diffrn_measurement_specimen_support Unknown
_diffrn_orient_matrix_type       FS_PROCESS
_diffrn_orient_matrix_UB_11      -0.039552
_diffrn_orient_matrix_UB_12      -0.053717
_diffrn_orient_matrix_UB_13      -0.017134
_diffrn_orient_matrix_UB_21      0.022306
_diffrn_orient_matrix_UB_22      -0.015505
_diffrn_orient_matrix_UB_23      0.050274
_diffrn_orient_matrix_UB_31      -0.029051
_diffrn_orient_matrix_UB_32      0.061228
_diffrn_orient_matrix_UB_33      -0.002301
_diffrn_radiation_monochromator  confocal
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0488
_diffrn_reflns_av_unetI/netI     0.0163
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            185304
_diffrn_reflns_theta_full        65.09
_diffrn_reflns_theta_max         65.09
_diffrn_reflns_theta_min         2.38
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           30.0
_diffrn_source_power             1.2
_diffrn_source_voltage           40.0
_diffrn_standards_decay_%        0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.959
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.655
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Jacobson, R (1998) Private Communication'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.294
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2256
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.048
_refine_diff_density_min         -0.907
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.207
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     641
_refine_ls_number_reflns         9457
_refine_ls_number_restraints     94
_refine_ls_restrained_S_all      1.203
_refine_ls_R_factor_all          0.0349
_refine_ls_R_factor_gt           0.0349
_refine_ls_shift/su_max          0.029
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0208P)^2^+12.7900P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0821
_refine_ls_wR_factor_ref         0.0821
_reflns_number_gt                9442
_reflns_number_total             9457
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja412565c_si_002.cif
_cod_data_source_block           '_Compound5'
_cod_depositor_comments
'Adding full bibliography for 4121810--4121811.cif.'
_cod_original_cell_volume        5544.6(11)
_cod_database_code               4121810
_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. Rigid bond restraints
 C4, C3, C1A, C2, C2A, C3A, C1, C4A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C4 \\sim C3 \\sim C1A \\sim C2 \\sim C2A \\sim C3A \\sim C1 \\sim C4A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
4. Others
 Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(C2A)=
 Sof(H2A)=Sof(C3A)=Sof(H3A)=1-FVAR(1)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4A)=
 Sof(H4B)=Sof(H4C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C53(H53), C35(H35), C39(H39), C27(H27), C49(H49), C13(H13), C23(H23), C9(H9),
 C3(H3), C3A(H3A)
5.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C1A(H1AA,H1AB)
5.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C19(H19), C45(H45), C46(H46), C42(H42), C57(H57), C58(H58),
 C43(H43), C56(H56), C44(H44), C30(H30), C32(H32), C2(H2), C31(H31), C16(H16),
 C18(H18), C17(H17), C2A(H2A)
5.d Idealised Me refined as rotating group:
 C54(H54A,H54B,H54C), C33(H33A,H33B,H33C), C55(H55A,H55B,H55C), C47(H47A,H47B,
 H47C), C21(H21A,H21B,H21C), C15(H15A,H15B,H15C), C22(H22A,H22B,H22C), C48(H48A,
 H48B,H48C), C34(H34A,H34B,H34C), C8(H8A,H8B,H8C), C28(H28A,H28B,H28C), C7(H7A,
 H7B,H7C), C41(H41A,H41B,H41C), C40(H40A,H40B,H40C), C14(H14A,H14B,H14C),
 C29(H29A,H29B,H29C), C4(H4A,H4B,H4C), C4A(H4AA,H4AB,H4AC)
;