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_4086054
_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         'C21 H18.91 Br3 Cu2.09 N2'
_chemical_formula_sum            'C21 H18.91 Br3 Cu2.09 N2'
_chemical_formula_weight         672.10
_chemical_name_systematic
;
 ? 
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_symmetry_space_group_name_Hall  '-P 2n 2ab'
_symmetry_space_group_name_H-M   'P b c n'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-03-22
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:17:34, GUI svn.r4385)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   20.7826(7)
_cell_length_b                   14.9253(4)
_cell_length_c                   6.9568(2)
_cell_measurement_reflns_used    2573
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      29.9370
_cell_measurement_theta_min      3.3690
_cell_volume                     2157.91(11)
_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
'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 0.9981
_diffrn_measured_fraction_theta_max 0.9981
_diffrn_measurement_details
;
  1 omega  -97.00  -56.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -21.4240 -178.0000  -90.0000 41

  2 omega   15.00   90.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       22.8303   57.0000  120.0000 75

  3 omega   51.00   85.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       22.8303    0.0000 -150.0000 34
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0136295000
_diffrn_orient_matrix_UB_12      0.0429146000
_diffrn_orient_matrix_UB_13      0.0162296000
_diffrn_orient_matrix_UB_21      -0.0055187000
_diffrn_orient_matrix_UB_22      -0.0048439000
_diffrn_orient_matrix_UB_23      0.1000642000
_diffrn_orient_matrix_UB_31      0.0308163000
_diffrn_orient_matrix_UB_32      -0.0198066000
_diffrn_orient_matrix_UB_33      0.0107216000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0240
_diffrn_reflns_av_unetI/netI     0.0357
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            6663
_diffrn_reflns_theta_full        30.71
_diffrn_reflns_theta_max         30.71
_diffrn_reflns_theta_min         3.24
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    7.626
_exptl_absorpt_correction_T_max  0.637
_exptl_absorpt_correction_T_min  0.364
_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    2.069
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             1298.4
_exptl_crystal_size_max          0.1626
_exptl_crystal_size_mid          0.1319
_exptl_crystal_size_min          0.0625
_refine_diff_density_max         1.482
_refine_diff_density_min         -1.154
_refine_diff_density_rms         0.117
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     159
_refine_ls_number_reflns         2979
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0624
_refine_ls_R_factor_gt           0.0457
_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^)+(0.0233P)^2^+7.6493P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0854
_refine_ls_wR_factor_ref         0.0927
_reflns_number_gt                2378
_reflns_number_total             2979
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            om5b00093_si_003.cif
_cod_data_source_block           ijsf1221
_cod_depositor_comments
'Adding full bibliography for 4086051--4086058.cif.'
_cod_original_cell_volume        2157.90(12)
_cod_database_code               4086054
_chemical_oxdiff_formula         'C21 H18.9 Br3 Cu2.1 N2'
_chemical_oxdiff_usercomment     'Ian's ijf-N1-71-1'
_reflns_odcompleteness_completeness 99.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H7A of C7A, H8 of C8, H7 of C7, H8A of C8A, H9 of C9, H1 of C1, H3 of C3,
  H4 of C4, {H5AA,H5AB,H5BC,H5BD} of C5, H9A of C9A, H10A of C10A, H10 of C10,
  H11 of C11, H11A of C11A
2. Uiso/Uaniso restraints and constraints
Uanis(C6) ~ Ueq, Uanis(C6A) ~ Ueq, Uanis(C11) ~ Ueq, Uanis(C11A) ~ Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C7) = Uanis(C7A)
Uanis(C8) = Uanis(C8A)
Uanis(C9) = Uanis(C9A)
Uanis(C10) = Uanis(C10A)
Uanis(C11) = Uanis(C11A)
3. Others
 Sof(H5AA)=Sof(H5AB)=1-Sof(H5AB)=1-Sof(H5AB)=Sof(C6)=1-Sof(H5AB)=Sof(C7)=
 Sof(H7)=1-Sof(H5AB)=1-Sof(H5AB)=Sof(C8)=Sof(H8)=1-Sof(H5AB)=1-Sof(H5AB)=
 Sof(C9)=Sof(H9)=1-Sof(H5AB)=1-Sof(H5AB)=Sof(C10)=Sof(H10)=1-Sof(H5AB)=1-
 Sof(H5AB)=Sof(C11)=Sof(H11)=1-Sof(H5AB)=1-Sof(H5AB)
 Sof(H1)=1-Sof(Cu2)
4.a Secondary CH2 refined with riding coordinates:
 C5(H5AA,H5AB), C5(H5BC,H5BD)
4.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C4(H4), C7(H7), C7A(H7A), C8(H8), C8A(H8A), C9(H9), C9A(H9A),
 C10(H10), C10A(H10A), C11(H11), C11A(H11A)
;