Ligand-Controlled Regioselectivity in the Hydrothiolation of Alkynes by Rhodium N-Heterocyclic Carbene Catalysts
Andrea Di Giuseppe; Ricardo Castarlenas; Jesús J. Pérez-Torrente; Marcello Crucianelli; Victor Polo; Rodrigo Sancho; Fernando J. Lahoz; Luis A. Oro; Journal of the American Chemical Society 134 (2012) 8171–8183; doi:10.1021/ja300396h

data_4117933
_publ_contact_author_address
;
  Dr. Fernando J. Lahoz
  Departamento de Qu\'imica Inorg\'anica - I.S.Q.C.H.
  Facultad de Ciencias
  Universidad de Zaragoza - C.S.I.C.
  50009 Zaragoza, Spain
;
_publ_contact_author_email       lahoz@unizar.es
_publ_contact_author_fax         '+34 976 761187'
_publ_contact_author_name        'Dr. Fernando J. Lahoz'
_publ_contact_author_phone       '+34 976 761147'
_publ_section_title
;
 Ligand-Controlled Regioselectivity in the Hydrothiolation of Alkynes by
 Rhodium N-Heterocyclic Carbene Catalysts
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8171
_journal_page_last               8183
_journal_paper_doi               10.1021/ja300396h
_journal_volume                  134
_journal_year                    2012
_chemical_formula_moiety         'C40 H55 Cl N3 Rh'
_chemical_formula_sum            'C40 H55 Cl N3 Rh'
_chemical_formula_weight         716.26
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_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_method           SHELXL-97
_cell_angle_alpha                85.301(3)
_cell_angle_beta                 75.467(3)
_cell_angle_gamma                72.538(3)
_cell_formula_units_Z            2
_cell_length_a                   10.374(3)
_cell_length_b                   10.874(3)
_cell_length_c                   17.559(4)
_cell_measurement_reflns_used    3542
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.702
_cell_measurement_theta_min      2.172
_cell_volume                     1829.0(8)
_computing_cell_refinement       'APEX2 v. 2009.7 (Bruker AXS, 2008)'
_computing_data_collection       'APEX2 v. 2009.7 (Bruker AXS, 2008)'
_computing_data_reduction        'APEX2 v. 2009.7 (Bruker AXS, 2008)'
_computing_molecular_graphics    ORTEP
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8.26
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker APEX II CCD system'
_diffrn_measurement_method       '\w rotations with narrow frames'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0667
_diffrn_reflns_av_sigmaI/netI    0.1161
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            18989
_diffrn_reflns_theta_full        26.37
_diffrn_reflns_theta_max         26.37
_diffrn_reflns_theta_min         1.96
_diffrn_standards_decay_%        'no decay'
_exptl_absorpt_coefficient_mu    0.571
_exptl_absorpt_correction_T_max  1.139
_exptl_absorpt_correction_T_min  0.813
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 R.H. Blessing, Acta Cryst. (1995), A51, 33-38
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.301
_exptl_crystal_description       prism
_exptl_crystal_F_000             756
_exptl_crystal_size_max          0.213
_exptl_crystal_size_mid          0.161
_exptl_crystal_size_min          0.057
_refine_diff_density_max         2.557
_refine_diff_density_min         -1.042
_refine_diff_density_rms         0.115
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.003
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     455
_refine_ls_number_reflns         7439
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.006
_refine_ls_R_factor_all          0.0893
_refine_ls_R_factor_gt           0.0571
_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^)+(0.0594P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1263
_refine_ls_wR_factor_ref         0.1372
_reflns_number_gt                5299
_reflns_number_total             7439
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja300396h_si_002_2.cif
_cod_data_source_block           compound_3
_cod_original_cell_volume        1829.1(8)
_cod_database_code               4117933