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_4086055
_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         '0.5(Br4 Cu2), C21 H19 N2, C H Cl3'
_chemical_formula_sum            'C22 H20 Br2 Cl3 Cu N2'
_chemical_formula_weight         642.11
_chemical_name_systematic
;
 ? 
;
_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     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2012-12-06
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:17:34, GUI svn.r4385)
;
_cell_angle_alpha                74.193(3)
_cell_angle_beta                 89.234(3)
_cell_angle_gamma                83.652(3)
_cell_formula_units_Z            2
_cell_length_a                   9.5428(3)
_cell_length_b                   11.1470(4)
_cell_length_c                   11.8115(4)
_cell_measurement_reflns_used    10728
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      30.0138
_cell_measurement_theta_min      2.8160
_cell_volume                     1201.32(7)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_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
'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      110.00(10)
_diffrn_detector_area_resol_mean 16.1450
_diffrn_measured_fraction_theta_full 0.9983
_diffrn_measured_fraction_theta_max 0.9983
_diffrn_measurement_details
;
  1 omega   47.00   97.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172 -162.0000  -97.0000 50

  2 omega  -17.00   67.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172  -99.0000  -30.0000 84

  3 omega  -40.00   30.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172  -57.0000 -120.0000 70

  4 omega   -3.00   23.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172   77.0000  150.0000 26

  5 omega   49.00   94.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172   77.0000  150.0000 45

  6 omega  -39.00   52.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172  -77.0000   30.0000 91

  7 omega   38.00   95.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172   57.0000  120.0000 57

  8 omega    1.00   99.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172   37.0000  -60.0000 98

  9 omega   48.00   97.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172  162.0000  -81.0000 49

 10 omega   34.00   47.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172 -178.0000 -180.0000 13

 11 omega   -4.00   21.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172   77.0000  120.0000 25

 12 omega    5.00   95.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172   57.0000   30.0000 90
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0363643000
_diffrn_orient_matrix_UB_12      0.0567695000
_diffrn_orient_matrix_UB_13      0.0063519000
_diffrn_orient_matrix_UB_21      -0.0046043000
_diffrn_orient_matrix_UB_22      -0.0274652000
_diffrn_orient_matrix_UB_23      0.0614218000
_diffrn_orient_matrix_UB_31      0.0652015000
_diffrn_orient_matrix_UB_32      0.0212376000
_diffrn_orient_matrix_UB_33      0.0091348000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0246
_diffrn_reflns_av_unetI/netI     0.0287
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            19512
_diffrn_reflns_theta_full        30.08
_diffrn_reflns_theta_max         30.08
_diffrn_reflns_theta_min         2.82
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.581
_exptl_absorpt_correction_T_max  0.575
_exptl_absorpt_correction_T_min  0.427
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
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    1.775
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             632
_exptl_crystal_size_max          0.2554
_exptl_crystal_size_mid          0.2002
_exptl_crystal_size_min          0.1321
_refine_diff_density_max         0.847
_refine_diff_density_min         -0.671
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     271
_refine_ls_number_reflns         7072
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0314
_refine_ls_R_factor_gt           0.0250
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0187P)^2^+0.8250P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0529
_refine_ls_wR_factor_ref         0.0553
_reflns_number_gt                6218
_reflns_number_total             7072
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            om5b00093_si_003.cif
_cod_data_source_block           ijsf1222
_cod_depositor_comments
'Adding full bibliography for 4086051--4086058.cif.'
_cod_database_code               4086055
_chemical_oxdiff_formula         'C22 H20 Br2 Cl3 Cu1 N2'
_chemical_oxdiff_usercomment     'Ian's ijf-N1-71-2'
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.01
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  {H8A,H8B} of C8, H10 of C10, H5 of C5, H11 of C11, H7 of C7, H6 of C6, H12
  of C12, H4 of C4, H13 of C13, {H15A,H15B} of C15, H14 of C14, H17 of C17, H22
  of C22, H19 of C19, H21 of C21, H20 of C20, H18 of C18, H1 of C1
2.a Ternary CH refined with riding coordinates:
 C22(H22)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C15(H15A,H15B)
2.c 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)
;