Unusual Reactivity of a Disilyne with 4-Dimethylaminopyridine: Formation of an Intramolecularly N-Coordinated Silylene and Its Isomerization to a Zwitterionic Silyl Anion
Torahiko Yamaguchi; Akira Sekiguchi; Journal of the American Chemical Society 133 (2011) 7352–7354; doi:10.1021/ja202605x

data_4106143
_publ_section_title
;
 Unusual Reactivity of a Disilyne with 4-Dimethylaminopyridine: Formation
 of an Intramolecularly N-Coordinated Silylene and Its Isomerization to a
 Zwitterionic Silyl Anion
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7352
_journal_page_last               7354
_journal_paper_doi               10.1021/ja202605x
_journal_volume                  133
_journal_year                    2011
_chemical_formula_sum            'C46 H112 N2 Si12'
_chemical_formula_weight         1030.46
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_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                 101.1620(10)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   21.1093(17)
_cell_length_b                   11.8779(10)
_cell_length_c                   26.872(2)
_cell_measurement_reflns_used    5327
_cell_measurement_temperature    150
_cell_measurement_theta_max      25.35
_cell_measurement_theta_min      2.25
_cell_volume                     6610.3(9)
_computing_cell_refinement       'APEX2 (Bruker AXS, 2006)'
_computing_data_collection       'APEX2 (Bruker AXS, 2006)'
_computing_data_reduction        'SAINT (Bruker AXS, 2004)'
_computing_molecular_graphics    'XSHEL (Bruker AXS,2002)'
_computing_publication_material  'XCIF (Bruker AXS, 2001)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_diffrn_ambient_temperature      150
_diffrn_detector_area_resol_mean 8.333
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEXII CCD area detector'
_diffrn_measurement_method       'phi and 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  0.0533
_diffrn_reflns_av_sigmaI/netI    0.0741
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            32905
_diffrn_reflns_theta_full        25.89
_diffrn_reflns_theta_max         25.89
_diffrn_reflns_theta_min         1.36
_exptl_absorpt_coefficient_mu    0.264
_exptl_absorpt_correction_T_max  0.9869
_exptl_absorpt_correction_T_min  0.9251
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
;
SADABS Sheldrick 1996
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.035
_exptl_crystal_description       plate
_exptl_crystal_F_000             2280
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.596
_refine_diff_density_min         -0.446
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.005
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     577
_refine_ls_number_reflns         12795
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.006
_refine_ls_R_factor_all          0.0903
_refine_ls_R_factor_gt           0.0481
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0585P)^2^+0.5044P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1082
_refine_ls_wR_factor_ref         0.1245
_reflns_number_gt                8390
_reflns_number_total             12795
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja202605x_si_002.cif
_cod_data_source_block           tora15ap_0m
_cod_original_cell_volume        6610.2(9)
_cod_original_sg_symbol_H-M      'P 1 21/n 1 '
_cod_database_code               4106143