Synthetic and Mechanistic Interrogation of Pd/Isocyanide-Catalyzed Cross-Coupling: π-Acidic Ligands Enable Self-Aggregating Monoligated Pd(0) Intermediates
Barnett, Brandon R.; Labios, Liezel A.; Stauber, Julia M.; Moore, Curtis E.; Rheingold, Arnold L.; Figueroa, Joshua S.; Organometallics 36 (2017) 944–; doi:10.1021/acs.organomet.7b00035

data_4087105
_publ_section_title
;
 Synthetic and Mechanistic Interrogation of Pd/Isocyanide-Catalyzed
 Cross-Coupling: \p-Acidic Ligands Enable Self-Aggregating Monoligated
 Pd(0) Intermediates
;
_journal_issue                   4
_journal_name_full               Organometallics
_journal_page_first              944
_journal_paper_doi               10.1021/acs.organomet.7b00035
_journal_volume                  36
_journal_year                    2017
_chemical_formula_moiety         'C96 H111 N3 O3 Pd3, C4 H10 O'
_chemical_formula_sum            'C100 H121 N3 O4 Pd3'
_chemical_formula_weight         1748.19
_chemical_name_common            Pd3(u-CO)3(CNArDipp2)3
_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     direct
_audit_creation_date             2016-08-19
_audit_creation_method
;
Olex2 1.2
(compiled Jan 19 2015 12:28:14 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                80.016(7)
_cell_angle_beta                 84.921(7)
_cell_angle_gamma                65.649(6)
_cell_formula_units_Z            2
_cell_length_a                   15.618(8)
_cell_length_b                   16.161(8)
_cell_length_c                   20.549(10)
_cell_measurement_reflns_used    4102
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.44
_cell_measurement_theta_min      2.30
_cell_volume                     4653(4)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1542
_diffrn_reflns_av_unetI/netI     0.1883
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            60240
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        24.407
_diffrn_reflns_theta_max         24.407
_diffrn_reflns_theta_min         1.399
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.623
_exptl_absorpt_correction_T_max  0.957
_exptl_absorpt_correction_T_min  0.887
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.248
_exptl_crystal_density_meas      ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1824
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.774
_refine_diff_density_min         -0.729
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.754
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     993
_refine_ls_number_reflns         15041
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.754
_refine_ls_R_factor_all          0.1227
_refine_ls_R_factor_gt           0.0496
_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^)] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0700
_refine_ls_wR_factor_ref         0.0881
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7599
_reflns_number_total             15041
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om7b00035_si_003.cif
_cod_data_source_block           jfig189
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_crystal_density_meas' value 'not measured' was changed to '?'
- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 
;
_cod_database_code               4087105
_shelx_estimated_absorpt_t_max   0.970
_shelx_estimated_absorpt_t_min   0.952
_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. Uiso/Uaniso restraints and constraints
Uanis(C2) = Uanis(C1) = Uanis(C3)
Uanis(C6) = Uanis(C4) = Uanis(C5)
3.a Ternary CH refined with riding coordinates:
 C82(H82), C79(H79), C94(H94), C91(H91), C64(H64), C61(H61), C52(H52),
 C49(H49), C31(H31), C34(H34), C22(H22), C19(H19)
3.b Secondary CH2 refined with riding coordinates:
 C2S(H2Sa,H2Sb), C3S(H3Sa,H3Sb)
3.c Aromatic/amide H refined with riding coordinates:
 C77(H77), C76(H76), C75(H75), C71(H71), C70(H70), C69(H69), C89(H89),
 C88(H88), C87(H87), C59(H59), C58(H58), C57(H57), C39(H39), C40(H40), C41(H41),
  C45(H45), C46(H46), C47(H47), C29(H29), C28(H28), C27(H27), C9(H9), C10(H10),
 C11(H11), C17(H17), C16(H16), C15(H15)
3.d Idealised Me refined as rotating group:
 C1S(H1Sa,H1Sb,H1Sc), C4S(H4Sa,H4Sb,H4Sc), C83(H83a,H83b,H83c), C84(H84a,H84b,
 H84c), C81(H81a,H81b,H81c), C80(H80a,H80b,H80c), C96(H96a,H96b,H96c), C95(H95a,
 H95b,H95c), C93(H93a,H93b,H93c), C65(H65a,H65b,H65c), C62(H62a,H62b,H62c),
 C63(H63a,H63b,H63c), C53(H53a,H53b,H53c), C54(H54a,H54b,H54c), C50(H50a,H50b,
 H50c), C32(H32a,H32b,H32c), C33(H33a,H33b,H33c), C35(H35a,H35b,H35c), C36(H36a,
 H36b,H36c), C23(H23a,H23b,H23c), C20(H20a,H20b,H20c), C21(H21a,H21b,H21c),
 C92(H92a,H92b,H92c), C51(H51a,H51b,H51c), C66(H66a,H66b,H66c), C24(H24a,H24b,
 H24c)
;
_shelx_res_checksum              63772
_shelx_hkl_checksum              81094
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'