Hydrosilylation with Biscarbene Rh(I) Complexes: Experimental Evidence for a Silylene-Based Mechanism
Peter Gigler; Bettina Bechlars; Wolfgang A. Herrmann; Fritz E. Kühn; Journal of the American Chemical Society 133 (2011) 1589–1596; doi:10.1021/ja110017c

data_4105608
_publ_contact_author_address
;
       Department Chemie,
       Lehrstuhl f\"ur Anorganische Chemie,
       Technische Universit\"at M\"unchen,
       Lichtenbergstrasse 4,
       D-85747 Garching bei M\"unchen,
       Germany.
;
_publ_contact_author_email       bettina.bechlars@ch.tum.de
_publ_contact_author_fax         '+49(0)89 289 13473'
_publ_contact_author_name
;
       Dr. Bettina Bechlars
;
_publ_contact_author_phone       '+49(0)89 289 13073'
_publ_section_title
;
 Hydrosilylation with Biscarbene Rh(I) Complexes: Experimental Evidence
 for a Silylene-Based Mechanism
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1589
_journal_page_last               1596
_journal_paper_doi               10.1021/ja110017c
_journal_volume                  133
_journal_year                    2011
_chemical_formula_moiety         'C32 H48 N4 Rh, F6 P, C H2 Cl2'
_chemical_formula_sum            'C33 H50 Cl2 F6 N4 P Rh'
_chemical_formula_weight         821.55
_chemical_name_systematic        ?
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      4
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             26-Mai-10
_audit_creation_method           'PLATON <TABLE ACC> option'
_audit_update_record
;
   26-Mai-10 Updated by the Author B.B.
             Text writing by B.B.
             Checkcif    OK
;
_cell_angle_alpha                90.00
_cell_angle_beta                 97.897(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   11.6445(4)
_cell_length_b                   12.6184(4)
_cell_length_c                   12.7872(4)
_cell_measurement_reflns_used    9130
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      25.33
_cell_measurement_theta_min      2.39
_cell_volume                     1861.07(11)
_computing_cell_refinement       'SAINT (Bruker, 2008b)'
_computing_data_collection       'APEX II Control Software (Bruker, 2008a)'
_computing_data_reduction        'SAINT (Bruker, 2008b)'
_computing_molecular_graphics    'PLATON (Spek, 2008)'
_computing_publication_material  'PLATON (Spek, 2008)'
_computing_structure_refinement  'SHELXL97 (Sheldrick, 1998)'
_computing_structure_solution    'SHELXS (Sheldrick, 1998)'
_diffrn_ambient_temperature      173(2)
_diffrn_detector                 ' CCD plate '
_diffrn_detector_area_resol_mean 16
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device       ' \k-geometry diffractometer '
_diffrn_measurement_device_type  ' Bruker APEX-II CCD '
_diffrn_measurement_method       ' phi- and omega-rotation '
_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  0.0320
_diffrn_reflns_av_sigmaI/netI    0.0198
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            43029
_diffrn_reflns_theta_full        25.33
_diffrn_reflns_theta_max         25.33
_diffrn_reflns_theta_min         1.61
_diffrn_standards_decay_%        0
_exptl_absorpt_coefficient_mu    0.704
_exptl_absorpt_correction_T_max  0.8605
_exptl_absorpt_correction_T_min  0.7241
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS, Bruker, 2008b'
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.466
_exptl_crystal_description       fragment
_exptl_crystal_F_000             848
_exptl_crystal_size_max          0.49
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.654
_refine_diff_density_min         -0.690
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.03(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     441
_refine_ls_number_reflns         6661
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0336
_refine_ls_R_factor_gt           0.0295
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0241P)^2^+2.1158P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0691
_refine_ls_wR_factor_ref         0.0731
_reflns_number_gt                6295
_reflns_number_total             6661
_reflns_threshold_expression     >2\s(I)
_cod_data_source_file            ja110017c_si_002.cif
_cod_data_source_block           global
_cod_original_cell_volume        1861.07(10)
_cod_database_code               4105608