Aryl Methyl Sulfides as Substrates for Rhodium-Catalyzed Alkyne Carbothiolation: Arene Functionalization with Activating Group Recycling
Joel F. Hooper; Adrian B. Chaplin; Carlos González-Rodríguez; Amber L. Thompson; Andrew S. Weller; Michael C. Willis; Journal of the American Chemical Society 134 (2012) 2906–2909; doi:10.1021/ja2108992

data_4117460
_publ_contact_author             'Michael C. Willis & Andrew S. Weller'
_publ_contact_author_email
'michael.willis@chem.ox.ac.uk & andrew.weller@chem.ox.ac.uk'
_publ_section_title
;
 Aryl Methyl Sulfides as Substrates for Rhodium-Catalyzed Alkyne
 Carbothiolation: Arene Functionalization with Activating Group Recycling
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              2906
_journal_page_last               2909
_journal_paper_doi               10.1021/ja2108992
_journal_volume                  134
_journal_year                    2012
_chemical_formula_moiety         'C44 H38 O P2 Rh, C32 H12 B F24'
_chemical_formula_sum            'C76 H50 B F24 O P2 Rh'
_chemical_formula_weight         1610.85
_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   difmap
_atom_sites_solution_primary     direct
_audit_creation_date             11-09-04
_audit_creation_method           CRYSTALS_ver_14.23
_cell_angle_alpha                106.288(2)
_cell_angle_beta                 99.363(2)
_cell_angle_gamma                92.169(2)
_cell_formula_units_Z            2
_cell_length_a                   13.8935(4)
_cell_length_b                   13.9569(4)
_cell_length_c                   18.8869(5)
_cell_measurement_reflns_used    20592
_cell_measurement_temperature    150
_cell_measurement_theta_max      76
_cell_measurement_theta_min      3
_cell_volume                     3455.04(17)
_computing_cell_refinement       'CrysAlis, (Oxford Diffraction, 2002)'
_computing_data_collection       'SuperNova, (Oxford Diffraction, 2010)'
_computing_data_reduction        'CrysAlis, (Oxford Diffraction, 2002)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'SIR92 (Altomare et al., 1994)'
_diffrn_ambient_temperature      150
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Oxford Diffraction SuperNova'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.080
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            57542
_diffrn_reflns_theta_full        74.724
_diffrn_reflns_theta_max         77.036
_diffrn_reflns_theta_min         3.236
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.428
_exptl_absorpt_correction_T_max  0.90
_exptl_absorpt_correction_T_min  0.65
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrysAlis, (Oxford Diffraction, 2002)'
_exptl_crystal_colour            clear_dark_red
_exptl_crystal_density_diffrn    1.548
_exptl_crystal_description       plate
_exptl_crystal_F_000             1620
_exptl_crystal_size_max          0.210
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.030
_refine_diff_density_max         2.81
_refine_diff_density_min         -1.89
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.9882
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1002
_refine_ls_number_reflns         14413
_refine_ls_number_restraints     1424
_refine_ls_R_factor_all          0.0746
_refine_ls_R_factor_gt           0.0642
_refine_ls_shift/su_max          0.0038973
_refine_ls_shift/su_mean         0.0000949
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.14P)^2^ + 3.92P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1827
_refine_ls_wR_factor_gt          0.1697
_refine_ls_wR_factor_ref         0.1827
_reflns_limit_h_max              17
_reflns_limit_h_min              -17
_reflns_limit_k_max              16
_reflns_limit_k_min              -17
_reflns_limit_l_max              23
_reflns_limit_l_min              0
_reflns_number_gt                12163
_reflns_number_total             14422
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   2.41
_oxford_diffrn_Wilson_scale      0.10
_oxford_refine_ls_r_factor_ref   0.0746
_oxford_refine_ls_scale          3.45(4)
_oxford_reflns_number_all        14413
_oxford_reflns_threshold_expression_ref I>-3.0\s(I)
_oxford_structure_analysis_title 212abc11
_cod_data_source_file            ja2108992_si_002_2.cif
_cod_data_source_block           A
_cod_original_cell_volume        3455.03(17)
_cod_original_sg_symbol_H-M      'P -1 '
_cod_original_formula_sum        'C76 H50 B1 F24 O1 P2 Rh1'
_cod_database_code               4117460
_iucr_refine_instruction_details_constraints
;
BLOCK SCALE X'S, U'S 
EQUIV PART(1001,OCC) PART(1002,OCC) 
WEIGHT -1 PART(1002,OCC) 
EQUIV PART(2001,OCC) PART(2002,OCC) 
WEIGHT -1 PART(2002,OCC) 
RIDE C   (   2,X'S) H   (  21,X'S) 
RIDE C   (   3,X'S) H   (  31,X'S) 
RIDE C   (   4,X'S) H   (  41,X'S) 
RIDE C   (   5,X'S) H   (  51,X'S) 
RIDE C   (   7,X'S) H   (  72,X'S) H   (  71,X'S) H   (  73,X'S) 
RIDE C   (   8,X'S) H   (  82,X'S) H   (  81,X'S) H   (  83,X'S) 
RIDE C   (  12,X'S) H   ( 121,X'S) 
RIDE C   (  13,X'S) H   ( 131,X'S) 
RIDE C   (  14,X'S) H   ( 141,X'S) 
RIDE C   (  15,X'S) H   ( 151,X'S) 
RIDE C   (  18,X'S) H   ( 181,X'S) 
RIDE C   (  19,X'S) H   ( 191,X'S) 
RIDE C   (  20,X'S) H   ( 201,X'S) 
RIDE C   (  21,X'S) H   ( 211,X'S) 
RIDE C   (  23,X'S) H   ( 231,X'S) 
RIDE C   (  24,X'S) H   ( 241,X'S) 
RIDE C   (  25,X'S) H   ( 251,X'S) 
RIDE C   (  26,X'S) H   ( 261,X'S) 
RIDE C   (  27,X'S) H   ( 271,X'S) 
RIDE C   (  29,X'S) H   ( 291,X'S) 
RIDE C   (  30,X'S) H   ( 301,X'S) 
RIDE C   (  31,X'S) H   ( 311,X'S) 
RIDE C   (  32,X'S) H   ( 321,X'S) 
RIDE C   (  33,X'S) H   ( 331,X'S) 
RIDE C   (  35,X'S) H   ( 351,X'S) 
RIDE C   (  36,X'S) H   ( 361,X'S) 
RIDE C   (  37,X'S) H   ( 371,X'S) 
RIDE C   (  38,X'S) H   ( 381,X'S) 
RIDE C   (  39,X'S) H   ( 391,X'S) 
RIDE C   (  41,X'S) H   ( 411,X'S) 
RIDE C   (  42,X'S) H   ( 421,X'S) 
RIDE C   (  43,X'S) H   ( 431,X'S) 
RIDE C   (  44,X'S) H   ( 441,X'S) 
RIDE C   (  45,X'S) H   ( 451,X'S) 
RIDE C   ( 202,X'S) H   (2021,X'S) 
RIDE C   ( 204,X'S) H   (2041,X'S) 
RIDE C   ( 206,X'S) H   (2061,X'S) 
RIDE C   ( 212,X'S) H   (2121,X'S) 
RIDE C   ( 214,X'S) H   (2141,X'S) 
RIDE C   ( 216,X'S) H   (2161,X'S) 
RIDE C   ( 222,X'S) H   (2221,X'S) 
RIDE C   ( 224,X'S) H   (2241,X'S) 
RIDE C   ( 226,X'S) H   (2261,X'S) 
RIDE C   ( 232,X'S) H   (2321,X'S) 
RIDE C   ( 234,X'S) H   (2341,X'S) 
RIDE C   ( 236,X'S) H   (2361,X'S) 
END                                                                             
;
_iucr_refine_instruction_details_restraints
;
SAME  C(215)  C(218)  F(210)  F(211)  F(212)  AND 
CONT  C(215)  C(218)  F(310)  F(311)  F(312)  AND 
CONT  C(223)  C(227)  F(213)  F(214)  F(215)  AND 
CONT  C(223)  C(227)  F(313)  F(314)  F(315) 
SIMU  0.01 C(215)  C(218)  F(210)  F(211)  F(212)  AND 
CONT  C(215)  C(218)  F(310)  F(311)  F(312)  AND 
CONT  C(223)  C(227)  F(213)  F(214)  F(215)  AND 
CONT  C(223)  C(227)  F(313)  F(314)  F(315) 
DELU  0.01 C(215)  C(218)  F(210)  F(211)  F(212)  AND 
CONT  C(215)  C(218)  F(310)  F(311)  F(312)  AND 
CONT  C(223)  C(227)  F(213)  F(214)  F(215)  AND 
CONT  C(223)  C(227)  F(313)  F(314)  F(315) 
END                                                                             
;