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_4119955
_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         'C21 H25 N O Rh, C F3 O3 S'
_chemical_formula_sum            'C22 H25 F3 N O4 Rh S'
_chemical_formula_weight         559.40
_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     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-03-20
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:20:19, GUI svn.r4385)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 107.018(7)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   16.1337(9)
_cell_length_b                   12.6977(7)
_cell_length_c                   11.6815(7)
_cell_measurement_reflns_used    2045
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      23.9100
_cell_measurement_theta_min      3.4610
_cell_volume                     2288.3(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
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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_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
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SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9980
_diffrn_measured_fraction_theta_max 0.8923
_diffrn_measurement_details
;
  1 omega -103.00  -77.50   1.5000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  178.0000  120.0000 17

  2 omega  -48.00   45.00   1.5000   40.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512  -57.0000   60.0000 62

  3 omega  -47.00  -21.50   1.5000   40.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512  -38.0000  -90.0000 17

  4 omega   25.00   53.50   1.5000   40.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512  -38.0000  -90.0000 19

  5 omega   -1.00   92.00   1.5000   40.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512   57.0000 -150.0000 62
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0000942000
_diffrn_orient_matrix_UB_12      -0.0535084000
_diffrn_orient_matrix_UB_13      0.0174011000
_diffrn_orient_matrix_UB_21      -0.0459713000
_diffrn_orient_matrix_UB_22      0.0005809000
_diffrn_orient_matrix_UB_23      -0.0166175000
_diffrn_orient_matrix_UB_31      -0.0015358000
_diffrn_orient_matrix_UB_32      -0.0158806000
_diffrn_orient_matrix_UB_33      -0.0587926000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0522
_diffrn_reflns_av_unetI/netI     0.0819
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            9771
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.37
_diffrn_reflns_theta_min         3.01
_diffrn_source                   'SuperNova (Mo) x-ray Source'
_exptl_absorpt_coefficient_mu    0.891
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63371
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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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)
empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark orange'
_exptl_crystal_density_diffrn    1.624
_exptl_crystal_description       block
_exptl_crystal_F_000             1136
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.807
_refine_diff_density_min         -1.143
_refine_diff_density_rms         0.108
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     295
_refine_ls_number_reflns         4683
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.1040
_refine_ls_R_factor_gt           0.0626
_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^)+(0.0632P)^2^+2.2311P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1394
_refine_ls_wR_factor_ref         0.1702
_reflns_number_gt                2925
_reflns_number_total             4683
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja404414q_si_001.cif
_cod_data_source_block           huaws0316_3
_cod_database_code               4119955
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H4 of C4, H3 of C3, H2 of C2, H1 of C1, H7 of C7, H10 of C10, H9 of C9, H8
  of C8
 At 1.5 times of:
  {H1A,H1B} of O1, {H17A,H17B,H17C} of C17, {H19A,H19B,H19C} of C19, {H21A,
  H21B,H21C} of C21, {H18A,H18B,H18C} of C18, {H20A,H20B,H20C} of C20
2.a Rotating group:
 O1(H1A,H1B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C10(H10)
2.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C21(H21A,H21B,H21C)
;