Mechanistic Elucidation of the Arylation of Non-SpectatorN-Heterocyclic Carbenes at Copper Using a Combined Experimental and Computational Approach
Williams, Thomas J.; Bray, Joshua T. W.; Lake, Benjamin R. M.; Willans, Charlotte E.; Rajabi, Nasir A.; Ariafard, Alireza; Manzini, Chiara; Bellina, Fabio; Whitwood, Adrian C.; Fairlamb, Ian J. S.; Organometallics 34 (2015) 3497–; doi:10.1021/acs.organomet.5b00093

data_4086057
_publ_section_title
;
 Mechanistic Elucidation of the Arylation of Non-SpectatorN-Heterocyclic
 Carbenes at Copper Using a Combined Experimental and Computational
 Approach
;
_journal_issue                   14
_journal_name_full               Organometallics
_journal_page_first              3497
_journal_paper_doi               10.1021/acs.organomet.5b00093
_journal_volume                  34
_journal_year                    2015
_chemical_formula_moiety         'C38 H28 Br4 N4 Pd2'
_chemical_formula_sum            'C38 H28 Br4 N4 Pd2'
_chemical_formula_weight         1073.08
_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   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-05-28
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.080(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.5542(6)
_cell_length_b                   9.5610(2)
_cell_length_c                   20.4815(7)
_cell_measurement_reflns_used    7668
_cell_measurement_temperature    110.00(14)
_cell_measurement_theta_max      31.8230
_cell_measurement_theta_min      3.0000
_cell_volume                     3587.82(19)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      110.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.925
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0221147000
_diffrn_orient_matrix_UB_12      0.0578430000
_diffrn_orient_matrix_UB_13      -0.0120642000
_diffrn_orient_matrix_UB_21      -0.0208540000
_diffrn_orient_matrix_UB_22      -0.0439455000
_diffrn_orient_matrix_UB_23      -0.0237501000
_diffrn_orient_matrix_UB_31      -0.0239553000
_diffrn_orient_matrix_UB_32      -0.0151170000
_diffrn_orient_matrix_UB_33      0.0228256000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_unetI/netI     0.0874
_diffrn_reflns_laue_measured_fraction_full 0.998
_diffrn_reflns_laue_measured_fraction_max 0.925
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            15998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.925
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         32.175
_diffrn_reflns_theta_min         2.929
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    5.491
_exptl_absorpt_correction_T_max  0.776
_exptl_absorpt_correction_T_min  0.465
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.987
_exptl_crystal_description       block
_exptl_crystal_F_000             2064.000
_exptl_crystal_recrystallization_method CH2Cl2
_exptl_crystal_size_max          0.2308
_exptl_crystal_size_mid          0.1703
_exptl_crystal_size_min          0.0524
_refine_diff_density_max         1.150
_refine_diff_density_min         -1.592
_refine_diff_density_rms         0.193
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.996
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     434
_refine_ls_number_reflns         15998
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.996
_refine_ls_R_factor_all          0.0765
_refine_ls_R_factor_gt           0.0461
_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^)+(0.0569P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1049
_refine_ls_wR_factor_ref         0.1109
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10983
_reflns_number_total             15998
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00093_si_003.cif
_cod_data_source_block           ijsf1427_twin1_hklf4
_cod_depositor_comments
'Adding full bibliography for 4086051--4086058.cif.'
_cod_original_cell_volume        3587.8(2)
_cod_database_code               4086057
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C38 H28 Br4 N4 Pd2'
_chemical_oxdiff_usercomment     'Chiara's CHN-1-24'
_diffrn_oxdiff_twin_integration_method simultaneous
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C22(H22), C23(H23), C24(H24),
  C25(H25), C26(H26), C28(H28), C29(H29), C30(H30), C31(H31), C34(H34),
 C35(H35), C36(H36), C37(H37), C38(H38)
;
_olex2_exptl_crystal_mounting_method 'oil on loop'