trans-Mutation at Gold(III): A Mechanistic Study of a Catalytic Acetylene Functionalization via a Double Insertion Pathway
Holmsen, Marte Sofie Martinsen; Nova, Ainara; Balcells, David; Langseth, Eirin; Øien-Ødegaard, Sigurd; Heyn, Richard H.; Tilset, Mats; Laurenczy, Gábor; ACS Catalysis 7 (2017) 5023–; doi:10.1021/acscatal.7b01364

data_4514184
_publ_section_title
;
 trans-Mutation at Gold(III): A Mechanistic Study of a Catalytic Acetylene
 Functionalization via a Double Insertion Pathway
;
_journal_issue                   8
_journal_name_full               'ACS Catalysis'
_journal_page_first              5023
_journal_paper_doi               10.1021/acscatal.7b01364
_journal_volume                  7
_journal_year                    2017
_chemical_formula_moiety         'C18 H12 Au F6 N O4, 0.25(C2 Cl), 0.25(C2)'
_chemical_formula_sum            'C19 H12 Au Cl0.25 F6 N O4'
_chemical_formula_weight         638.12
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yac'
_space_group_name_H-M_alt        'P 1 2/n 1'
_symmetry_space_group_name_Hall  '-P 2yac'
_symmetry_space_group_name_H-M   'P 1 2/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-02-16
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_audit_update_record
;
2017-02-16 deposited with the CCDC.
2017-04-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.649(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   29.449(3)
_cell_length_b                   4.6494(5)
_cell_length_c                   29.503(3)
_cell_measurement_reflns_used    9430
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.773
_cell_measurement_theta_min      2.862
_cell_volume                     3925.5(7)
_computing_cell_refinement       'APEX3 v2016.9-0 (Bruker-AXS, 2016)'
_computing_data_collection       'APEX3 v2016.9-0 (Bruker-AXS, 2016)'
_computing_data_reduction        'SAINT v8.35A (Bruker-AXS, 2016)'
_computing_molecular_graphics    'Diamond v4.0.1 (Brandenburg, 2014)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2015b)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      99.98
_diffrn_detector                 'Bruker PHOTON100 area detector'
_diffrn_detector_area_resol_mean 10.4167
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0673
_diffrn_reflns_av_unetI/netI     0.0381
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            54424
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.790
_diffrn_reflns_theta_max         25.790
_diffrn_reflns_theta_min         2.081
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    7.613
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.3561
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1355 before and 0.0803 after correction. The Ratio of minimum to maximum transmission is 0.3561. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_density_diffrn    2.160
_exptl_crystal_description       prism
_exptl_crystal_F_000             2418
_exptl_crystal_size_max          0.666
_exptl_crystal_size_mid          0.203
_exptl_crystal_size_min          0.082
_refine_diff_density_max         3.891
_refine_diff_density_min         -4.905
_refine_diff_density_rms         0.242
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.268
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     571
_refine_ls_number_reflns         7528
_refine_ls_number_restraints     126
_refine_ls_restrained_S_all      1.266
_refine_ls_R_factor_all          0.0529
_refine_ls_R_factor_gt           0.0525
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+93.2065P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1170
_refine_ls_wR_factor_ref         0.1172
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7473
_reflns_number_total             7528
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs7b01364_si_003.cif
_cod_data_source_block           msh-296-rota_sx
_cod_original_cell_volume        3925.4(8)
_cod_database_code               4514184
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.574
_shelx_estimated_absorpt_t_min   0.081
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5694(14) 0.4306(14)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C115) \\sim Ueq, Uanis(C116) \\sim Ueq, Uanis(O101) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C108) \\sim Ueq, Uanis(C104) \\sim Ueq, Uanis(C106) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C113) \\sim Ueq, Uanis(C204) \\sim Ueq, Uanis(C202) \\sim Ueq,
Uanis(C105) \\sim Ueq, Uanis(O201) \\sim Ueq, Uanis(N201) \\sim Ueq,
Uanis(C210) \\sim Ueq, Uanis(C107) \\sim Ueq, Uanis(C201) \\sim Ueq,
Uanis(C101) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C213) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C212) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C901) \\sim Ueq, Uanis(C902) \\sim Ueq, Uanis(Cl90) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: Cl90(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C212(H212), C207(H207), C213(H213), C210(H210), C205(H205), C209(H209),
 C52(H52), C203(H203), C108(H108), C109(H109), C103(H103), C111(H111),
 C104(H104), C110(H110), C208(H208), C106(H106), C114(H114), C113(H113)
5.b Idealised Me refined as rotating group:
 C112(H11A,H11B,H11C), C211(H21A,H21B,H21C)
;
_olex2_submission_special_instructions 'No special instructions were received'