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_4087100
_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         'C34 H42 Cl N Pd, 1/2(C4 H8 O)'
_chemical_formula_sum            'C36 H46 Cl N O0.5 Pd'
_chemical_formula_weight         642.59
_chemical_name_common            PdCl(allyl)(CNArDipp2)
_chemical_name_systematic
;
 ? 
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-08-23
_audit_creation_method
;
Olex2 1.2
(compiled Jan 19 2015 12:28:14 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 105.030(3)
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   22.184(6)
_cell_length_b                   18.952(5)
_cell_length_c                   16.253(5)
_cell_measurement_reflns_used    9964
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.41
_cell_measurement_theta_min      2.51
_cell_volume                     6600(3)
_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  'XLMP (Sheldrick, 2008)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX 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  0.0400
_diffrn_reflns_av_unetI/netI     0.0461
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            36510
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         25.45
_diffrn_reflns_theta_min         0.95
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.669
_exptl_absorpt_correction_T_max  0.8723
_exptl_absorpt_correction_T_min  0.7900
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.294
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Block
_exptl_crystal_F_000             2688
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.588
_refine_diff_density_min         -0.688
_refine_diff_density_rms         0.073
_refine_ls_extinction_coef       'not measured'
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     769
_refine_ls_number_reflns         12145
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0553
_refine_ls_R_factor_gt           0.0378
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0314P)^2^+8.2316P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0834
_refine_ls_wR_factor_ref         0.0972
_reflns_number_gt                9447
_reflns_number_total             12145
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            om7b00035_si_003.cif
_cod_data_source_block           jfig198
_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_cell_volume        6599(3)
_cod_original_formula_sum        'C36 H46 Cl N O0.50 Pd'
_cod_database_code               4087100
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C37-C36B
 1.4 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C36B) = Uanis(C36)
4. Others
 Fixed Sof: C2(0.6) H2(0.6) C2B(0.4) H2B(0.4) H3aa(0.6) H3ab(0.6) H3bc(0.4)
 H3bd(0.4) C4(0.6) H4a(0.6) H4b(0.6) C4B(0.4) H4Ba(0.4) H4Bb(0.4) C36(0.7)
 H36(0.7) C36B(0.3) H36B(0.3) H37a(0.7) H37b(0.7) H37c(0.3) H37d(0.3) H38a(0.7)
 H38b(0.7) H38c(0.3) H38d(0.3) H63(0.6) H63a(0.4) C64(0.6) H64a(0.6) H64b(0.6)
 H64c(0.6) C65(0.6) H65a(0.6) H65b(0.6) H65c(0.6) C64B(0.4) H64d(0.4) H64e(0.4)
 H64f(0.4) C65B(0.4) H65d(0.4) H65e(0.4) H65f(0.4)
5.a Ternary CH refined with riding coordinates:
 C23(H23), C26(H26), C29(H29), C32(H32), C57(H57), C60(H60), C63(H63),
 C63(H63a), C66(H66)
5.b Secondary CH2 refined with riding coordinates:
 C1S(H1Sa,H1Sb), C2S(H2Sa,H2Sb), C3S(H3Sa,H3Sb), C4S(H4Sa,H4Sb)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C2B(H2B), C7(H7), C8(H8), C9(H9), C13(H13), C14(H14), C15(H15),
 C19(H19), C20(H20), C21(H21), C36(H36), C36B(H36B), C41(H41), C42(H42),
 C43(H43), C47(H47), C48(H48), C49(H49), C53(H53), C54(H54), C55(H55)
5.d X=CH2 refined with riding coordinates:
 C3(H3aa,H3ab), C3(H3bc,H3bd), C4(H4a,H4b), C4B(H4Ba,H4Bb), C37(H37a,H37b),
 C37(H37c,H37d), C38(H38a,H38b), C38(H38c,H38d)
5.e Idealised Me refined as rotating group:
 C24(H24a,H24b,H24c), C25(H25a,H25b,H25c), C27(H27a,H27b,H27c), C28(H28a,H28b,
 H28c), C30(H30a,H30b,H30c), C31(H31a,H31b,H31c), C33(H33a,H33b,H33c), C34(H34a,
 H34b,H34c), C58(H58a,H58b,H58c), C59(H59a,H59b,H59c), C61(H61a,H61b,H61c),
 C62(H62a,H62b,H62c), C64(H64a,H64b,H64c), C65(H65a,H65b,H65c), C64B(H64d,H64e,
 H64f), C65B(H65d,H65e,H65f), C67(H67a,H67b,H67c), C68(H68a,H68b,H68c)
;
_olex2_submission_special_instructions 'No special instructions were received'