Synthesis and Reactivity of Three-Coordinate (dtbpe)Rh Silylamides: CO2Bond Cleavage by a Rhodium(I) Disilylamide
Whited, Matthew T.; Kosanovich, Alex J.; Janzen, Daron E.; Organometallics 33 (2014) 1416–; doi:10.1021/om401130q

data_4082752
_publ_section_title
;
 Synthesis and Reactivity of Three-Coordinate (dtbpe)Rh Silylamides:
 CO2Bond Cleavage by a Rhodium(I) Disilylamide
;
_journal_issue                   6
_journal_name_full               Organometallics
_journal_page_first              1416
_journal_paper_doi               10.1021/om401130q
_journal_volume                  33
_journal_year                    2014
_chemical_formula_moiety         'C25 H58 N P2 Rh Si'
_chemical_formula_sum            'C25 H58 N P2 Rh Si'
_chemical_formula_weight         565.66
_space_group_IT_number           52
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      52
_symmetry_space_group_name_Hall  '-P 2a 2bc'
_symmetry_space_group_name_H-M   'P n n a'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2013-11-15
_audit_creation_method
;
Olex2 1.2
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.2627(14)
_cell_length_b                   17.1177(12)
_cell_length_c                   8.9210(6)
_cell_measurement_reflns_used    1500
_cell_measurement_temperature    173
_cell_measurement_theta_max      27.49
_cell_measurement_theta_min      2.57
_cell_volume                     3094.3(4)
_computing_cell_refinement       'CrystalClear-SM Expert 3.1 b27'
_computing_data_collection       'CrystalClear-SM Expert 3.1 b27 (Rigaku, 2011)'
_computing_data_reduction        'CrystalClear-SM Expert 3.1 b27'
_computing_structure_refinement
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'SIR92 (Altomare, et al., 1994)'
_diffrn_ambient_temperature      173
_diffrn_detector_area_resol_mean 13.653
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Rigaku XtaLAB mini'
_diffrn_measurement_method       \w
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0489
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            29962
_diffrn_reflns_theta_full        27.48
_diffrn_reflns_theta_max         27.48
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.706
_exptl_absorpt_correction_T_max  0.932
_exptl_absorpt_correction_T_min  0.747
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'REQAB (Rigaku, 1998)'
_exptl_crystal_colour            green
_exptl_crystal_density_diffrn    1.214
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1216
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.326
_refine_diff_density_min         -0.353
_refine_diff_density_rms         0.048
_refine_ls_extinction_coef       0.00040(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.001
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     190
_refine_ls_number_reflns         3550
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.001
_refine_ls_R_factor_all          0.0406
_refine_ls_R_factor_gt           0.0265
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0248P)^2^+0.7094P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0529
_refine_ls_wR_factor_ref         0.0560
_reflns_number_gt                2847
_reflns_number_total             3550
_reflns_threshold_expression     F^2^>2.0\s(F^2^)
_cod_data_source_file            om401130q_si_002.cif
_cod_data_source_block           scu1354_compound2b
_cod_database_code               4082752
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.811
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, {H5A,H5B,H5C} of C5, {H1A,H1B,H1C} of C1, {H2A,H2B,H2C}
  of C2, {H13A,H13B,H13C} of C13, {H6A,H6B,H6C} of C6, {H14A,H14B,H14C} of C14,
  {H15A,H15B,H15C} of C15, {H11A,H11B,H11C} of C11, {H10A,H10B,H10C} of C10,
  {H9A,H9B,H9C} of C9, {H7A,H7B,H7C} of C7
 At 1.5 times of:
  {H3A,H3B,H3C} of C3
2. Restrained distances
 Si1-N1
 1.75 with sigma of 0.02
 N1-C4
 1.48 with sigma of 0.02
3. Others
 Fixed Sof: Si1(0.5) N1(0.5) C1(0.5) H1A(0.5) H1B(0.5) H1C(0.5) C2(0.5)
 H2A(0.5) H2B(0.5) H2C(0.5) C3(0.5) H3A(0.5) H3B(0.5) H3C(0.5) C4(0.5) C5(0.5)
 H5A(0.5) H5B(0.5) H5C(0.5) C6(0.5) H6A(0.5) H6B(0.5) H6C(0.5) C7(0.5) H7A(0.5)
 H7B(0.5) H7C(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B)
4.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C6(H6A,
 H6B,H6C), C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,
 H11C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C)
;
_shelx_res_checksum              75324
_shelx_hkl_checksum              31675