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_4086052
_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         'Br, C21 H19 N2, H2 O'
_chemical_formula_sum            'C21 H21 Br N2 O'
_chemical_formula_weight         397.31
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2011-10-06
_audit_creation_method
;
  Olex2 1.1
  (compiled 2011.09.07 svn.r1971, GUI svn.r3853)
;
_cell_angle_alpha                69.308(4)
_cell_angle_beta                 80.860(4)
_cell_angle_gamma                69.207(4)
_cell_formula_units_Z            2
_cell_length_a                   9.3864(4)
_cell_length_b                   9.9323(4)
_cell_length_c                   11.3331(6)
_cell_measurement_reflns_used    4358
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      31.9829
_cell_measurement_theta_min      2.9524
_cell_volume                     923.36(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
;
_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
;
XL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
olex2.solve (L.J. Bourhis, O.V. Dolomanov, R.J. Gildea, J.A.K. Howard,
H. Puschmann, in preparation, 2011)
;
_diffrn_ambient_temperature      110.0
_diffrn_detector_area_resol_mean 16.1450
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.893
_diffrn_measurement_details
;
  1 omega    6.00   95.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -       26.5735   57.0000  -90.0000 89

  2 omega  -44.00   57.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -       26.5735  -77.0000  -60.0000 101

  3 omega  -36.00   54.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -       26.5735  -77.0000   30.0000 90

  4 omega   -3.00   97.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -       26.5735   77.0000  150.0000 100
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0133329000
_diffrn_orient_matrix_UB_12      -0.0737616000
_diffrn_orient_matrix_UB_13      0.0449156000
_diffrn_orient_matrix_UB_21      0.0115947000
_diffrn_orient_matrix_UB_22      0.0270980000
_diffrn_orient_matrix_UB_23      0.0466279000
_diffrn_orient_matrix_UB_31      -0.0789367000
_diffrn_orient_matrix_UB_32      0.0182731000
_diffrn_orient_matrix_UB_33      0.0170567000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0204
_diffrn_reflns_av_unetI/netI     0.0410
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            8860
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         32.06
_diffrn_reflns_theta_min         2.96
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.237
_exptl_absorpt_correction_T_max  0.440
_exptl_absorpt_correction_T_min  0.301
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
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            'pinkish colourless'
_exptl_crystal_colour_modifier   pinkish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.429
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             408
_exptl_crystal_size_max          0.1712
_exptl_crystal_size_mid          0.1642
_exptl_crystal_size_min          0.1105
_refine_diff_density_max         1.301
_refine_diff_density_min         -0.484
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     226
_refine_ls_number_reflns         5751
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0482
_refine_ls_R_factor_gt           0.0392
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0429P)^2^+0.6465P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0929
_refine_ls_wR_factor_ref         0.0978
_reflns_number_gt                4995
_reflns_number_total             5751
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            om5b00093_si_003.cif
_cod_data_source_block           ijsf1118
_cod_depositor_comments
'Adding full bibliography for 4086051--4086058.cif.'
_cod_original_cell_volume        923.36(7)
_cod_database_code               4086052
_chemical_oxdiff_formula         'C21 H19 Br3 N2'
_chemical_oxdiff_usercomment     'Toms pale pink block'
_reflns_odcompleteness_completeness 99.13
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.01