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_4087101
_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         'C71 H93 N3 Pd2'
_chemical_formula_sum            'C71 H93 N3 Pd2'
_chemical_formula_weight         1201.28
_chemical_name_common            '[(CNArDipp2)Pd]2(u-allyl)(u-LDA)'
_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
_audit_creation_date             2016-08-11
_audit_creation_method
;
Olex2 1.2
(compiled Jan 19 2015 12:28:14 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.8850(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.5686(13)
_cell_length_b                   16.9767(11)
_cell_length_c                   19.6154(13)
_cell_measurement_reflns_used    8373
_cell_measurement_temperature    100
_cell_measurement_theta_max      26.36
_cell_measurement_theta_min      2.40
_cell_volume                     6508.2(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)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.971
_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  0.0640
_diffrn_reflns_av_unetI/netI     0.0741
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            55502
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         27.509
_diffrn_reflns_theta_min         1.434
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.593
_exptl_absorpt_correction_T_max  0.866
_exptl_absorpt_correction_T_min  0.701
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.226
_exptl_crystal_density_meas      ?
_exptl_crystal_description       block
_exptl_crystal_F_000             2528
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.825
_refine_diff_density_min         -0.713
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     732
_refine_ls_number_reflns         14530
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.0872
_refine_ls_R_factor_gt           0.0469
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0347P)^2^+5.4064P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0873
_refine_ls_wR_factor_ref         0.1022
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9992
_reflns_number_total             14530
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om7b00035_si_003.cif
_cod_data_source_block           jfig269
_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               4087101
_shelx_estimated_absorpt_t_max   0.954
_shelx_estimated_absorpt_t_min   0.819
_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. Shared sites
{C3, C3A}
{C4, C4A}
3. Uiso/Uaniso restraints and constraints
Uanis(C5A) = Uanis(C5)
Uanis(C3) = Uanis(C3A)
Uanis(C4) = Uanis(C4A)
4. Others
 Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(C5A)=Sof(H5A)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=1-
 FVAR(1)
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(C5)=Sof(H5)=Sof(C4)=Sof(H4A)=Sof(H4B)=FVAR(1)
 Fixed Sof: H27(0.5) H27A(0.5) C28(0.5) H28A(0.5) H28B(0.5) H28C(0.5) C29(0.5)
 H29A(0.5) H29B(0.5) H29C(0.5) C28B(0.5) H28D(0.5) H28E(0.5) H28F(0.5)
 C29B(0.5) H29D(0.5) H29E(0.5) H29F(0.5)
5.a Ternary CH refined with riding coordinates:
 C24(H24), C27(H27), C30(H30), C33(H33), C54(H54), C57(H57), C60(H60),
 C63(H63), C66(H66), C69(H69)
5.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C3A(H3AA,H3AB), C4A(H4AA,H4AB)
5.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C14(H14), C15(H15), C16(H16), C20(H20), C21(H21),
 C22(H22), C38(H38), C39(H39), C40(H40), C44(H44), C45(H45), C46(H46), C50(H50),
  C51(H51), C52(H52), C5(H5), C5A(H5A)
5.d Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C28B(H28D,H28E,H28F), C29B(H29D,H29E,H29F), C31(H31A,H31B,H31C),
 C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C55(H55A,H55B,
 H55C), C56(H56A,H56B,H56C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C61(H61A,
 H61B,H61C), C62(H62A,H62B,H62C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C),
 C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C70(H70A,H70B,H70C), C71(H71A,H71B,
 H71C)
;
_shelx_res_checksum              54350
_shelx_hkl_checksum              93842
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'