Mechanism of the Ullmann Biaryl Ether Synthesis Catalyzed by Complexes of Anionic Ligands. Evidence for the Reaction of Iodoarenes With Ligated Anionic CuI Intermediates.
Giri, Ramesh; Brusoe, Andrew; Troshin, Konstantin; Wang, Justin Y.; Font, Marc; Hartwig, John F.; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b11853

data_4126978
_publ_contact_author
; 
Danielle L. Gray 
University of Illinois 
School of Chemical Sciences, Box 59-1 
505 South Mathews Avenue 
Urbana, Illinois  61801 
USA 
;
_publ_section_title
;
 Mechanism of the Ullmann Biaryl Ether Synthesis Catalyzed by Complexes of
 Anionic Ligands. Evidence for the Reaction of Iodoarenes With Ligated
 Anionic CuI Intermediates.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b11853
_journal_year                    2017
_chemical_compound_source        synthetic
_chemical_formula_iupac          'C88 H152 Cu4 K4 O16, C5 H12'
_chemical_formula_moiety         'C88 H152 Cu4 K4 O16, C5 H12'
_chemical_formula_sum            'C93 H164 Cu4 K4 O16'
_chemical_formula_weight         1948.80
_chemical_name_common
'potassium bis(2,2,6,6-tetramethyl-5-oxohept-3-en-3-olate)copper(I)'
_chemical_name_systematic
; 
? 
;
_space_group_IT_number           15
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_audit_update_record
; 
? 
;
_cell_angle_alpha                90.00
_cell_angle_beta                 122.2950(10)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   28.2361(8)
_cell_length_b                   17.0454(5)
_cell_length_c                   25.8860(11)
_cell_measurement_reflns_used    9574
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      61.20
_cell_measurement_theta_min      3.19
_cell_volume                     10531.5(6)
_computing_cell_refinement       'SAINT V7.68A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2010.11-3 (Bruker, 2010)'
_computing_data_reduction
; 
SAINT V7.68A, XPREP V2005/2, SADABS V2007/4, TWINABS V2007/5 
(Bruker, 2005 & 2007) 
;
_computing_molecular_graphics
; 
SHELXTL V6.12 (Bruker, 2005), CrystalMaker v2.1.3 (CrystalMaker, 1994) 
;
_computing_publication_material  'XCIF V6.12 (Bruker, 2005)'
_computing_structure_refinement  'SHELXTL V6.12 (Bruker, 2005)'
_computing_structure_solution    'SHELXTL V6.12 (Bruker, 2005)'
_diffrn_ambient_temperature      173(2)
_diffrn_measured_fraction_theta_full 0.930
_diffrn_measured_fraction_theta_max 0.930
_diffrn_measurement_device       'Bruker Kappa/ApexII CCD'
_diffrn_measurement_method       'profile data from \f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_wavelength_id  bc22nasxq
_diffrn_reflns_av_R_equivalents  0.0480
_diffrn_reflns_av_sigmaI/netI    0.0371
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            38620
_diffrn_reflns_theta_full        62.84
_diffrn_reflns_theta_max         62.84
_diffrn_reflns_theta_min         3.19
_exptl_absorpt_coefficient_mu    2.765
_exptl_absorpt_correction_T_max  0.7727
_exptl_absorpt_correction_T_min  0.5556
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details   'SHELXTL/XPREP V2005/2 (Bruker, 2005)'
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.229
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             4168
_exptl_crystal_id                K[Cu(LX3)2]
_exptl_crystal_preparation
; 
The data crystal was mounted using oil (Parantone-N, Exxon) to a 
0.3 mm cryo-loop (Hampton Research) with the (0 1 -2) scattering 
planes roughly normal to the spindle axis. 
;
_exptl_crystal_size_max          0.326
_exptl_crystal_size_mid          0.149
_exptl_crystal_size_min          0.125
_platon_squeeze_details
; 
The electron count from the "squeeze" model converged in good agreement 
with the number of solvate molecules predicted by the complete refinement. 
;
_refine_diff_density_max         0.492
_refine_diff_density_min         -0.499
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    noref
_refine_ls_matrix_type           full
_refine_ls_number_parameters     655
_refine_ls_number_reflns         7877
_refine_ls_number_restraints     518
_refine_ls_restrained_S_all      1.202
_refine_ls_R_factor_all          0.0566
_refine_ls_R_factor_gt           0.0449
_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^)+(0.0697P)^2^+11.7606P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1189
_refine_ls_wR_factor_ref         0.1251
_reflns_number_gt                6417
_reflns_number_total             7877
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja7b11853_si_003.cif
_cod_data_source_block           K[Cu(LX3)2]
_cod_depositor_comments
;
The following automatic conversions were performed:

'_symmetry_cell_setting' value 'Monoclinic' changed to 'monoclinic'
according to
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 
;
_cod_original_sg_symbol_H-M      'C2/c  '
_cod_database_code               4126978