Dehydrogenation of Saturated CC and BN Bonds at Cationic N-Heterocyclic Carbene Stabilized M(III) Centers (M = Rh, Ir)
Christina Y. Tang; Amber L. Thompson; Simon Aldridge; Journal of the American Chemical Society 132 (2010) 10578–10591; doi:10.1021/ja1043787

data_4102763
_publ_contact_author             'Simon Aldridge'
_publ_contact_author_email       simon.aldridge@chem.ox.ac.uk
_publ_section_title
;
 Dehydrogenation of Saturated CC and BN Bonds at Cationic N-Heterocyclic
 Carbene Stabilized M(III) Centers (M = Rh, Ir)
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10578
_journal_page_last               10591
_journal_paper_doi               10.1021/ja1043787
_journal_volume                  132
_journal_year                    2010
_chemical_formula_moiety
'0.791(C46 H58 N4 O Rh ), 0.209(C42 H50 Cl N4 Rh), C32 H12 B F24'
_chemical_formula_sum            'C77.16 H68.33 B Cl0.21 F24 N4 O0.79 Rh'
_chemical_formula_weight         1641.44
_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
_audit_creation_date             10-05-06
_audit_creation_method           CRYSTALS_ver_14.06
_cell_angle_alpha                88.662(16)
_cell_angle_beta                 71.192(9)
_cell_angle_gamma                87.422(13)
_cell_formula_units_Z            2
_cell_length_a                   12.692(4)
_cell_length_b                   17.585(7)
_cell_length_c                   18.027(6)
_cell_measurement_reflns_used    12309
_cell_measurement_temperature    150
_cell_measurement_theta_max      32
_cell_measurement_theta_min      1
_cell_volume                     3805(2)
_computing_cell_refinement
'CrystalClear-SM Expert 2.0 r4 (Rigaku, 2009)'
_computing_data_collection
'CrystalClear-SM Expert 2.0 r4 (Rigaku, 2009)'
_computing_data_reduction
'CrystalClear-SM Expert 2.0 r4 (Rigaku, 2009)'
_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 0.963
_diffrn_measured_fraction_theta_max 0.840
_diffrn_measurement_details
;
scan:
    Number of images: 175
               Slice: -60.0000 - 115.0000
         Image width: 1.0000
            Exp time: 0.5000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 0.0000
                 Phi: 0.0000
                 XTD: 59.5737
              2theta: 30.1322
scan:
    Number of images: 120
               Slice: -60.0000 - 60.0000
         Image width: 1.0000
            Exp time: 0.5000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: -50.0000
                 Phi: 0.0000
                 XTD: 59.5737
              2theta: 30.1322
scan:
    Number of images: 120
               Slice: -60.0000 - 60.0000
         Image width: 1.0000
            Exp time: 0.5000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: -50.0000
                 Phi: 120.0000
                 XTD: 59.5737
              2theta: 30.1322
scan:
    Number of images: 120
               Slice: -60.0000 - 60.0000
         Image width: 1.0000
            Exp time: 0.5000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: -50.0000
                 Phi: 240.0000
                 XTD: 59.5737
              2theta: 30.1322

;
_diffrn_measurement_device       'CrystalLogic Kappa (3 circle)'
_diffrn_measurement_device_type  'Rigaku Saturn724+ (2x2 bin mode)'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      0.038217
_diffrn_orient_matrix_UB_12      -0.014205
_diffrn_orient_matrix_UB_13      0.072642
_diffrn_orient_matrix_UB_21      -0.032603
_diffrn_orient_matrix_UB_22      0.040852
_diffrn_orient_matrix_UB_23      0.022557
_diffrn_orient_matrix_UB_31      -0.046424
_diffrn_orient_matrix_UB_32      -0.035524
_diffrn_orient_matrix_UB_33      -0.004146
_diffrn_radiation_monochromator  Synchrotron
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_wavelength     0.68890
_diffrn_reflns_av_R_equivalents  0.046
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            23736
_diffrn_reflns_theta_full        25.026
_diffrn_reflns_theta_max         31.678
_diffrn_reflns_theta_min         1.124
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.337
_exptl_absorpt_correction_T_max  1.00
_exptl_absorpt_correction_T_min  0.67
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrystalClear-SM Expert 2.0 r4 (Rigaku, 2009)'
_exptl_crystal_colour            clear_pale_yellow
_exptl_crystal_density_diffrn    1.433
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1670.381
_exptl_crystal_size_max          0.01
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.08
_refine_diff_density_min         -1.18
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   1.0660
_refine_ls_hydrogen_treatment    none
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1103
_refine_ls_number_reflns         18359
_refine_ls_number_restraints     765
_refine_ls_R_factor_all          0.0954
_refine_ls_R_factor_gt           0.0754
_refine_ls_shift/su_max          0.0096013
_refine_ls_shift/su_mean         0.0001364
_refine_ls_structure_factor_coef F
_refine_ls_weighting_details
;
 Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) 
 [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] 
 where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax 
 Method = Robust Weighting (Prince, 1982) 
 W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ 
 A~i~ are: 
 2.50 3.14 2.50 1.04 0.566 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0962
_refine_ls_wR_factor_gt          0.0803
_refine_ls_wR_factor_ref         0.0803
_reflns_limit_h_max              19
_reflns_limit_h_min              -18
_reflns_limit_k_max              26
_reflns_limit_k_min              -26
_reflns_limit_l_max              26
_reflns_limit_l_min              0
_reflns_number_gt                18359
_reflns_number_total             23736
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   2.94
_oxford_diffrn_Wilson_scale      7.40
_oxford_refine_ls_r_factor_ref   0.0754
_oxford_refine_ls_scale          0.447
_oxford_reflns_number_all        23688
_oxford_reflns_threshold_expression_ref I>2.0\s(I)
_oxford_structure_analysis_title DIA0058
_cod_data_source_file            ja1043787_si_002_09.cif
_cod_data_source_block           '[Rh(IMes)2(H)2(thf)]+[BArf4]-'
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_crystal_density_meas' value 'not measured' was changed to '?'
- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 3008 2015-01-20 13:52:24Z robertas 
;
_cod_original_cell_volume        3804(2)
_cod_original_sg_symbol_H-M      'P -1 '
_cod_original_formula_sum        'C77.16 H68.33 B1 Cl0.21 F24 N4 O0.79 Rh1'
_cod_database_code               4102763