Evaluation of the Rh(II)-Rh(II)Bond Dissociation Enthalpy for [(TMTAA)Rh]2 by 1H NMR T2 Measurements: Application in Determining the Rh-C(O)- BDE in [(TMTAA)Rh]2C=O
Gregory H. Imler; Michael J. Zdilla; Bradford B. Wayland; Inorganic Chemistry 52 (2013) 11509–11513; doi:10.1021/ic401778c

data_4336297
_publ_section_title
;
 Evaluation of the Rh(II)-Rh(II)Bond Dissociation Enthalpy for
 [(TMTAA)Rh]2 by 1H NMR T2 Measurements: Application in Determining the
 Rh-C(O)- BDE in [(TMTAA)Rh]2C=O
;
_journal_name_full               'Inorganic Chemistry'
_journal_page_first              11509
_journal_page_last               11513
_journal_paper_doi               10.1021/ic401778c
_journal_volume                  52
_journal_year                    2013
_chemical_formula_moiety         '[C44 H44 N8 Rh2][C6 H6][C6 H6]'
_chemical_formula_sum            'C56 H56 N8 Rh2'
_chemical_formula_weight         1046.91
_chemical_name_systematic
; 
 rhodium (II) dibenzotetramethylaza[14]annulene
;
_space_group_IT_number           61
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   20.6966(16)
_cell_length_b                   14.2017(11)
_cell_length_c                   34.284(3)
_cell_measurement_reflns_used    9946
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.988
_cell_measurement_theta_min      2.376
_cell_volume                     10077.0(14)
_computing_cell_refinement       'SAINT (Bruker-AXS)'
_computing_data_collection       'COSMO (Bruker-AXS)'
_computing_data_reduction        'SADABS (Bruker-AXS)'
_computing_molecular_graphics    XP
_computing_publication_material  'APEX2 report generator (Bruker-AXS)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8.333
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Kappa APEX II DUO'
_diffrn_measurement_method       'omega scans'
_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  0.0000
_diffrn_reflns_av_sigmaI/netI    0.0305
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            12013
_diffrn_reflns_theta_full        27.88
_diffrn_reflns_theta_max         27.88
_diffrn_reflns_theta_min         1.19
_exptl_absorpt_coefficient_mu    0.698
_exptl_absorpt_correction_T_max  0.9495
_exptl_absorpt_correction_T_min  0.7822
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 67954 Corrected reflections written to file 
 C:\Frames\guest\1318\work\mo_1318_0m.hkl
 Estimated minimum and maximum transmission:  0.6636  0.7456
 The ratio of these values is more reliable than their absolute values!
 Additional spherical absorption correction applied with mu*r =  0.2000
 Lambda/2 correction factor = 0.0015
;
_exptl_crystal_colour            'dark green'
_exptl_crystal_density_diffrn    1.362
_exptl_crystal_description       block
_exptl_crystal_F_000             4248
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.08
_platon_squeeze_details
;
One disorderd benzene molecule was removed using SQUEEZE. The number
of electrons calculated by SQUEEZE was 43.5 compared to the 
theoretical 42 for a benzene molecule. 
;
_refine_diff_density_max         1.146
_refine_diff_density_min         -1.152
_refine_diff_density_rms         0.158
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     603
_refine_ls_number_reflns         12013
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0456
_refine_ls_R_factor_gt           0.0356
_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^)+(0.0370P)^2^+15.5238P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0847
_refine_ls_wR_factor_ref         0.0880
_reflns_number_gt                10014
_reflns_number_total             12013
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic401778c_si_002.cif
_cod_data_source_block           1318
_cod_original_cell_volume        10077.1(14)
_cod_database_code               4336297