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_4086053
_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
'0.69(C42 H36 Br2 Cu2 N4), 0.62(C21 H18 N2), 0.62(Br)'
_chemical_formula_sum            'C42 H36.62 Br2 Cu1.38 N4'
_chemical_formula_weight         845.11
_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     heavy
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-03-21
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:17:34, GUI svn.r4385)
;
_cell_angle_alpha                69.666(5)
_cell_angle_beta                 82.618(5)
_cell_angle_gamma                69.325(5)
_cell_formula_units_Z            1
_cell_length_a                   9.4035(5)
_cell_length_b                   9.5936(4)
_cell_length_c                   11.2065(7)
_cell_measurement_reflns_used    2584
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      25.0241
_cell_measurement_theta_min      2.8467
_cell_volume                     886.90(9)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
XS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      110.00(10)
_diffrn_detector_area_resol_mean 16.1450
_diffrn_measured_fraction_theta_full 0.9790
_diffrn_measured_fraction_theta_max 0.9790
_diffrn_measurement_details
;
  1 omega    2.00   89.00   1.0000   95.0000
omega____ theta____ kappa____ phi______ frames
    -       19.7386   57.0000    0.0000 87

  2 omega  -10.00   89.00   1.0000   95.0000
omega____ theta____ kappa____ phi______ frames
    -       19.7386   77.0000  120.0000 99

  3 omega   26.00   58.00   1.0000   95.0000
omega____ theta____ kappa____ phi______ frames
    -       19.7386  -99.0000 -120.0000 32

  4 omega  -22.00   90.00   1.0000   95.0000
omega____ theta____ kappa____ phi______ frames
    -       19.7386   19.0000  -60.0000 112
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0462752000
_diffrn_orient_matrix_UB_12      -0.0035103000
_diffrn_orient_matrix_UB_13      0.0554627000
_diffrn_orient_matrix_UB_21      -0.0481445000
_diffrn_orient_matrix_UB_22      0.0779345000
_diffrn_orient_matrix_UB_23      -0.0302312000
_diffrn_orient_matrix_UB_31      -0.0451754000
_diffrn_orient_matrix_UB_32      -0.0299884000
_diffrn_orient_matrix_UB_33      -0.0237991000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0193
_diffrn_reflns_av_unetI/netI     0.0360
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            5054
_diffrn_reflns_theta_full        25.02
_diffrn_reflns_theta_max         25.02
_diffrn_reflns_theta_min         3.01
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.129
_exptl_absorpt_correction_T_max  0.923
_exptl_absorpt_correction_T_min  0.735
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
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)
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.582
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             426.8
_exptl_crystal_size_max          0.126
_exptl_crystal_size_mid          0.0458
_exptl_crystal_size_min          0.0289
_refine_diff_density_max         0.638
_refine_diff_density_min         -0.505
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.325
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     236
_refine_ls_number_reflns         3079
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.325
_refine_ls_R_factor_all          0.0543
_refine_ls_R_factor_gt           0.0493
_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^)+(0.0000P)^2^+2.7516P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0996
_refine_ls_wR_factor_ref         0.1013
_reflns_number_gt                2843
_reflns_number_total             3079
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            om5b00093_si_003.cif
_cod_data_source_block           ijsf1122
_cod_depositor_comments
'Adding full bibliography for 4086051--4086058.cif.'
_cod_original_cell_volume        886.91(8)
_cod_database_code               4086053
_chemical_oxdiff_formula         'C21 H18.3 Br Cu0.7 N2'
_chemical_oxdiff_usercomment     'Ian IJSF-N1-47 schlenk'
_reflns_odcompleteness_completeness 97.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H17 of C17, H18 of C18, H19 of C19, H20 of C20, H21 of C21, H6 of C6, H1 of
  C1, H13 of C13, H12 of C12, H4 of C4, H11 of C11, H10 of C10, {H8A,H8B} of C8,
   H7 of C7, H5 of C5, {H15A,H15B} of C15, H14 of C14
2. Others
 Sof(Br1)=1-Sof(H1)=Sof(Cu1)=1-Sof(H1)
3.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C15(H15A,H15B)
3.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C5(H5), C6(H6), C7(H7), C10(H10), C11(H11), C12(H12),
 C13(H13), C14(H14), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21)
;