Electronic Structure Control of the Nucleophilicity of Transition Metal-Thiolate Complexes: An Experimental and Theoretical Study
Derek C. Fox; Adam T. Fiedler; Heather L. Halfen; Thomas C. Brunold; Jason A. Halfen; Journal of the American Chemical Society 126 (2004) 7627–7638; doi:10.1021/ja039419q

data_4112677
_publ_section_title
;
 Electronic Structure Control of the Nucleophilicity of Transition
 Metal-Thiolate Complexes: An Experimental and Theoretical Study
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7627
_journal_page_last               7638
_journal_paper_doi               10.1021/ja039419q
_journal_volume                  126
_journal_year                    2004
_chemical_formula_sum            'C70 H70 B2 Co N6'
_chemical_formula_weight         1075.87
_chemical_name_common            'complex 5'
_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                   18.620(2)
_cell_length_b                   17.399(2)
_cell_length_c                   36.260(6)
_cell_measurement_reflns_used    25
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      21.25
_cell_measurement_theta_min      10.27
_cell_volume                     11747(3)
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_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    0.0888
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       0
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            10268
_diffrn_reflns_theta_full        24.97
_diffrn_reflns_theta_max         24.97
_diffrn_reflns_theta_min         2.19
_exptl_absorpt_coefficient_mu    0.340
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9168
_exptl_absorpt_correction_type   'psi-scan corrections'
_exptl_crystal_colour            maroon
_exptl_crystal_density_diffrn    1.217
_exptl_crystal_description       block
_exptl_crystal_F_000             4552
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.40
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.326
_refine_diff_density_min         -0.397
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     714
_refine_ls_number_reflns         10268
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.010
_refine_ls_R_factor_all          0.1407
_refine_ls_R_factor_gt           0.0519
_refine_ls_shift/su_max          0.043
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0635P)^2^+1.9633P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1142
_refine_ls_wR_factor_ref         0.1443
_reflns_number_gt                5540
_reflns_number_total             10268
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja039419qsi20031104_024558.cif
_cod_data_source_block           5
_cod_database_code               4112677