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_4087099
_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         'C70 H83 Br N2 Pd, 0.5(C4H10O)'
_chemical_formula_sum            'C72 H88 Br N2 O0.5 Pd'
_chemical_formula_weight         1175.75
_chemical_name_common            PdBr(m-Xyl)(CNArDipp2)2
_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             2016-08-25
_audit_creation_method
;
Olex2 1.2
(compiled Jan 19 2015 12:28:14 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                72.626(2)
_cell_angle_beta                 78.681(2)
_cell_angle_gamma                85.724(2)
_cell_formula_units_Z            2
_cell_length_a                   10.9266(13)
_cell_length_b                   14.4884(18)
_cell_length_c                   22.065(3)
_cell_measurement_reflns_used    9902
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25.44
_cell_measurement_theta_min      2.78
_cell_volume                     3268.4(7)
_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      293.15
_diffrn_measured_fraction_theta_full 0.961
_diffrn_measured_fraction_theta_max 0.961
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0416
_diffrn_reflns_av_unetI/netI     0.0555
_diffrn_reflns_Laue_measured_fraction_full 0.961
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            30099
_diffrn_reflns_point_group_measured_fraction_full 0.961
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        25.470
_diffrn_reflns_theta_max         25.470
_diffrn_reflns_theta_min         1.473
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.936
_exptl_absorpt_correction_T_max  0.750
_exptl_absorpt_correction_T_min  0.703
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.195
_exptl_crystal_density_meas      ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1238
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_platon_squeeze_details
;
SQUEEZE was used to account for one molecule of highly
disordered diethyl ether (C4H10O) per unit cell.
;
_refine_diff_density_max         0.652
_refine_diff_density_min         -1.141
_refine_diff_density_rms         0.125
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     685
_refine_ls_number_reflns         11667
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0627
_refine_ls_R_factor_gt           0.0423
_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^)+(0.0794P)^2^+3.2678P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1082
_refine_ls_wR_factor_ref         0.1466
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9099
_reflns_number_total             11667
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om7b00035_si_003.cif
_cod_data_source_block           jfig412_sq
_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_original_formula_sum        'C72 H88 Br N2 O0.50 Pd'
_cod_database_code               4087099
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C51(H51), C30(H30), C24(H24), C27(H27), C54(H54), C21(H21), C57(H57), C60(H60)
2.b Aromatic/amide H refined with riding coordinates:
 C66(H66), C68(H68), C36(H36), C18(H18), C64(H64), C35(H35), C41(H41),
 C17(H17), C48(H48), C13(H13), C42(H42), C6(H6), C47(H47), C11(H11), C37(H37),
 C43(H43), C5(H5), C19(H19), C49(H49), C7(H7), C12(H12)
2.c Idealised Me refined as rotating group:
 C56(H56A,H56B,H56C), C59(H59A,H59B,H59C), C26(H26A,H26B,H26C), C23(H23A,H23B,
 H23C), C52(H52A,H52B,H52C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C32(H32A,
 H32B,H32C), C58(H58A,H58B,H58C), C22(H22A,H22B,H22C), C28(H28A,H28B,H28C),
 C53(H53A,H53B,H53C), C61(H61A,H61B,H61C), C25(H25A,H25B,H25C), C55(H55A,H55B,
 H55C), C31(H31A,H31B,H31C), C29(H29A,H29B,H29C), C62(H62A,H62B,H62C)
;
_shelx_res_checksum              14204
_shelx_hkl_checksum              12654
_shelx_fab_checksum              35191
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'