Oxidative Bond Formation and Reductive Bond Cleavage at Main Group Metal Centers: Reactivity of Five-Valence-Electron MX2 Radicals.
Protchenko, Andrey V.; Dange, Deepak; Blake, Matthew P.; Schwarz, Andrew D.; Jones, Cameron; Mountford, Philip; Aldridge, Simon; Journal of the American Chemical Society 136 (2014) 10902–10905; doi:10.1021/ja5062467

data_4122330
_publ_section_title
;
 Oxidative Bond Formation and Reductive Bond Cleavage at Main Group Metal
 Centers: Reactivity of Five-Valence-Electron MX2 Radicals.
;
_journal_issue                   31
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10902
_journal_page_last               10905
_journal_paper_doi               10.1021/ja5062467
_journal_volume                  136
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C84 H118 B3 N6 Tl1, 0.25(C5 H12)'
_chemical_formula_sum            'C85.25 H121 B3 N6 Tl'
_chemical_formula_weight         1466.74
_chemical_name_systematic
;
[{Tl{B(NArCH)2}}2{C6H10}{B(NArCH)2}].0.5(C5H12)
;
_space_group_IT_number           33
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  'P 2c -2n'
_symmetry_space_group_name_H-M   'P n a 21'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   31.1097(2)
_cell_length_b                   12.83300(13)
_cell_length_c                   21.52790(9)
_cell_measurement_reflns_used    47554
_cell_measurement_temperature    150.0(4)
_cell_measurement_theta_max      76.4877
_cell_measurement_theta_min      3.4412
_cell_volume                     8594.60(11)
_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 0.996
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Oxford Diffraction SuperNova'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.031
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -39
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            93593
_diffrn_reflns_theta_full        26.652
_diffrn_reflns_theta_max         26.652
_diffrn_reflns_theta_min         1.615
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.922
_exptl_absorpt_correction_T_max  0.83
_exptl_absorpt_correction_T_min  0.60
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrysAlis, (Oxford Diffraction, 2002)'
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.133
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             3082
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.100
_refine_diff_density_max         0.84
_refine_diff_density_min         -0.51
_refine_ls_abs_structure_details 'Flack (1983), 5984 Friedel-pairs'
_refine_ls_abs_structure_Flack   0.058(3)
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   1.1254
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     882
_refine_ls_number_reflns         13692
_refine_ls_number_restraints     261
_refine_ls_R_factor_all          0.0262
_refine_ls_R_factor_gt           0.0242
_refine_ls_shift/su_max          0.0154477
_refine_ls_shift/su_mean         0.0003029
_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: 
 0.243 0.265 0.171 0.715E-01 0.277E-01 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0292
_refine_ls_wR_factor_gt          0.0260
_refine_ls_wR_factor_ref         0.0253
_reflns_limit_h_max              39
_reflns_limit_h_min              0
_reflns_limit_k_max              16
_reflns_limit_k_min              0
_reflns_limit_l_max              27
_reflns_limit_l_min              -18
_reflns_number_gt                14342
_reflns_number_total             15250
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   1.99
_oxford_diffrn_Wilson_scale      447.60
_oxford_refine_ls_r_factor_ref   0.0231
_oxford_refine_ls_scale          0.06677(3)
_oxford_reflns_number_all        15191
_oxford_reflns_threshold_expression_ref I>3.0\s(I)
_cod_data_source_file            ja5062467_si_006.cif
_cod_data_source_block           MPB162
_cod_depositor_comments
'Adding full bibliography for 4122328--4122335.cif.'
_cod_original_sg_symbol_Hall     'P 2c -2n '
_cod_original_sg_symbol_H-M      'P n a 21 '
_cod_original_formula_sum        'C85.25 H121 B3 N6 Tl1'
_cod_database_code               4122330