An Efficient Rh/O2 Catalytic System for Oxidative C-H Activation/Annulation: Evidence for Rh(I) to Rh(III) Oxidation by Molecular Oxygen
Guoying Zhang; Lei Yang; Yanyu Wang; Yinjun Xie; Hanmin Huang; Journal of the American Chemical Society 135 (2013) 8850–8853; doi:10.1021/ja404414q

data_4119957
_publ_contact_author_name
;
;
_publ_section_title
;
 An Efficient Rh/O2 Catalytic System for Oxidative C-H
 Activation/Annulation: Evidence for Rh(I) to Rh(III) Oxidation by
 Molecular Oxygen
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8850
_journal_page_last               8853
_journal_paper_doi               10.1021/ja404414q
_journal_volume                  135
_journal_year                    2013
_chemical_formula_moiety         'C35 H33 N Rh, C F3 O3 S'
_chemical_formula_sum            'C36 H33 F3 N O3 Rh S'
_chemical_formula_weight         719.60
_chemical_name_systematic
;
 ? 
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-05-31
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.778(3)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   13.6762(7)
_cell_length_b                   13.7277(4)
_cell_length_c                   16.9536(5)
_cell_measurement_reflns_used    5870
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.7670
_cell_measurement_theta_min      3.3270
_cell_volume                     3182.6(2)
_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
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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    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9973
_diffrn_measured_fraction_theta_max 0.8929
_diffrn_measurement_details
;
  1 omega  -16.00   27.20   1.2000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  -99.0000 -180.0000 36

  2 omega    5.00   50.60   1.2000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700   57.0000  -60.0000 38

  3 omega  -47.00   45.40   1.2000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.8075  -77.0000 -180.0000 77

  4 omega  -47.00   57.40   1.2000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.8075  -77.0000  -90.0000 87
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0178108000
_diffrn_orient_matrix_UB_12      -0.0133365000
_diffrn_orient_matrix_UB_13      -0.0376240000
_diffrn_orient_matrix_UB_21      0.0485053000
_diffrn_orient_matrix_UB_22      0.0001581000
_diffrn_orient_matrix_UB_23      0.0153222000
_diffrn_orient_matrix_UB_31      -0.0046395000
_diffrn_orient_matrix_UB_32      -0.0500328000
_diffrn_orient_matrix_UB_33      0.0100119000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0322
_diffrn_reflns_av_unetI/netI     0.0467
_diffrn_reflns_limit_h_max       14
_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       -20
_diffrn_reflns_number            14852
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.37
_diffrn_reflns_theta_min         3.18
_diffrn_source                   'SuperNova (Mo) x-ray Source'
_exptl_absorpt_coefficient_mu    0.657
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91985
_exptl_absorpt_correction_type   multi-scan
_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)
empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark black'
_exptl_crystal_density_diffrn    1.502
_exptl_crystal_description       block
_exptl_crystal_F_000             1472
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.29
_exptl_crystal_size_min          0.27
_refine_diff_density_max         1.031
_refine_diff_density_min         -0.524
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     411
_refine_ls_number_reflns         6487
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0537
_refine_ls_R_factor_gt           0.0377
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0364P)^2^+1.5999P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0840
_refine_ls_wR_factor_ref         0.0943
_reflns_number_gt                5123
_reflns_number_total             6487
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja404414q_si_004.cif
_cod_data_source_block           huaws0321_1
_cod_database_code               4119957
_reflns_odcompleteness_completeness 99.73
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C32) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C35) \\sim Ueq, 
Uanis(C34) \\sim Ueq, Uanis(C33) \\sim Ueq: with sigma of 0.01 and sigma for 
terminal atoms of 0.02
3.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11),
 C16(H16), C17(H17), C18(H18), C19(H19), C21(H21), C22(H22), C23(H23), C24(H24),
  C25(H25)
3.b Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,
 H34C), C35(H35A,H35B,H35C)
;