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_4121811
_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         'C63 H81 Cl N4 Pd2'
_chemical_formula_sum            'C63 H81 Cl N4 Pd2'
_chemical_formula_weight         1142.56
_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   mixed
_atom_sites_solution_primary     heavy
_audit_creation_date             2013-10-19
_audit_creation_method
;
Olex2 1.2
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_audit_update_record
;
????
;
_cell_angle_alpha                90
_cell_angle_beta                 103.307(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1146(2)
_cell_length_b                   24.5603(4)
_cell_length_c                   20.2741(14)
_cell_measurement_temperature    93
_cell_volume                     5870.4(5)
_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
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      93
_diffrn_measured_fraction_theta_full 0.908
_diffrn_measured_fraction_theta_max 1.000
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54187
_diffrn_reflns_av_R_equivalents  0.1274
_diffrn_reflns_av_unetI/netI     0.0571
_diffrn_reflns_Laue_measured_fraction_full 0.908
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            124466
_diffrn_reflns_point_group_measured_fraction_full 0.908
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.687
_diffrn_reflns_theta_max         63.694
_diffrn_reflns_theta_min         2.873
_exptl_absorpt_coefficient_mu    5.659
_exptl_absorpt_correction_T_max  1.00
_exptl_absorpt_correction_T_min  0.510
_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    1.293
_exptl_crystal_description       plate
_exptl_crystal_F_000             2384
_exptl_crystal_recrystallization_method Methanol/THF
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.510
_refine_diff_density_min         -1.404
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     842
_refine_ls_number_reflns         9649
_refine_ls_number_restraints     682
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0677
_refine_ls_R_factor_gt           0.0591
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0849P)^2^+10.9818P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1542
_refine_ls_wR_factor_ref         0.1603
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8083
_reflns_number_total             9649
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja412565c_si_002.cif
_cod_data_source_block           '_Compound6'
_cod_depositor_comments
'Adding full bibliography for 4121810--4121811.cif.'
_cod_database_code               4121811
_shelxl_version_number           2013-4
_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
 C33-H33B
 0.93 with sigma of 0.02
 C39A-C41A \\sim C41A-C43A \\sim C39-C41 \\sim C41-C43
 with sigma of 0.02
 C40A-C38A \\sim C38A-C42A \\sim C40-C38 \\sim C38-C42
 with sigma of 0.02
 C44-C39 \\sim C44A-C39A \\sim C47A-C43A \\sim C47-C43
 with sigma of 0.02
 C46A-C44A \\sim C47A-C49A
 with sigma of 0.02
 C1A-C2A \\sim C2-C1
 with sigma of 0.02
3. Rigid bond restraints
 C38, C39, C40, C41, C42, C43, H55, C47, C44, C45, C48, C49, C49A, C48A, C38A,
 C39A, C40A, C41A, C42A, C43A, C47A, C45A, C44A, C46A, N4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1, C2, C3, C4, C5, C6, C7, C8, C9, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim H55 \\sim C47 \\sim
C44 \\sim C45 \\sim C48 \\sim C49 \\sim C49A \\sim C48A \\sim C38A \\sim C39A
\\sim C40A \\sim C41A \\sim C42A \\sim C43A \\sim C47A \\sim C45A \\sim C44A
\\sim C46A \\sim N4: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A \\sim C6A \\sim C7A \\sim C8A
\\sim C9A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C1) = Uanis(C3A)
Uanis(C1A) = Uanis(C3)
5. Others
 Sof(C9A)=Sof(H9A)=Sof(C6A)=Sof(H6A)=Sof(C5A)=Sof(H5A)=Sof(C7A)=Sof(H7A)=
 Sof(C4A)=Sof(C8A)=Sof(H8A)=Sof(C2A)=Sof(H2A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=
 Sof(C3A)=Sof(H3A)=1-FVAR(1)
 Sof(C3)=Sof(H3)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=Sof(H2)=Sof(C4)=Sof(C8)=
 Sof(H8)=Sof(C9)=Sof(H9)=Sof(C7)=Sof(H7)=Sof(C6)=Sof(H6)=Sof(C5)=Sof(H5)=FVAR(1)
 Sof(C49A)=Sof(H49D)=Sof(H49E)=Sof(H49F)=Sof(C48A)=Sof(H48D)=Sof(H48E)=
 Sof(H48F)=Sof(C38A)=Sof(C39A)=Sof(C40A)=Sof(H40A)=Sof(C41A)=Sof(H41A)=
 Sof(C42A)=Sof(H42A)=Sof(C43A)=Sof(C47A)=Sof(H47A)=Sof(C45A)=Sof(H45D)=
 Sof(H45E)=Sof(H45F)=Sof(C44A)=Sof(H44A)=Sof(C46A)=Sof(H46D)=Sof(H46E)=
 Sof(H46F)=1-FVAR(2)
 Sof(C38)=Sof(C39)=Sof(C40)=Sof(H40)=Sof(C41)=Sof(H41)=Sof(C42)=Sof(H42)=
 Sof(C43)=Sof(C47)=Sof(H47)=Sof(C44)=Sof(H44)=Sof(C45)=Sof(H45A)=Sof(H45B)=
 Sof(H45C)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(H48C)=Sof(C46)=Sof(H46A)=Sof(H46B)=
 Sof(H46C)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C35(H35), C59(H59), C20(H20), C12(H12), C32(H32), C55(H55), C47(H47),
 C44(H44), C3A(H3A), C47A(H47A), C44A(H44A)
6.b Secondary CH2 refined with riding coordinates:
 C1A(H1AA,H1AB)
6.c Aromatic/amide H refined with riding coordinates:
 C62(H62), C24(H24), C23(H23), C27(H27), C29(H29), C54(H54), C28(H28),
 C53(H53), C52(H52), C40(H40), C41(H41), C42(H42), C16(H16), C17(H17), C15(H15),
  C63(H63), C8(H8), C9(H9), C7(H7), C6(H6), C5(H5), C9A(H9A), C6A(H6A),
 C5A(H5A), C7A(H7A), C8A(H8A), C2A(H2A), C40A(H40A), C41A(H41A), C42A(H42A)
6.d Idealised Me refined as rotating group:
 C60(H60A,H60B,H60C), C61(H61A,H61B,H61C), C36(H36A,H36B,H36C), C11(H11A,H11B,
 H11C), C21(H21A,H21B,H21C), C34(H34A,H34B,H34C), C22(H22A,H22B,H22C), C13(H13A,
 H13B,H13C), C33(H33A,H33B,H33C), C31(H31A,H31B,H31C), C57(H57A,H57B,H57C),
 C45(H45A,H45B,H45C), C48(H48A,H48B,H48C), C46(H46A,H46B,H46C), C49(H49A,H49B,
 H49C), C56(H56A,H56B,H56C), C49A(H49D,H49E,H49F), C48A(H48D,H48E,H48F),
 C45A(H45D,H45E,H45F), C46A(H46D,H46E,H46F)
;
_shelx_res_checksum              1976
_shelx_hkl_checksum              51863