Formation of Chlorosilyl Pincer-Type Rhodium Complexes by Multiple Si–H Activations of Bis(phosphine)/Dihydrosilyl Ligands
Whited, Matthew T.; Deetz, Alexander M.; Boerma, Joseph W.; DeRosha, Daniel E.; Janzen, Daron E.; Organometallics 33 (2014) 5070–; doi:10.1021/om5006319

data_4084704
_publ_section_title
;
 Formation of Chlorosilyl Pincer-Type Rhodium Complexes by Multiple Si--H
 Activations of Bis(phosphine)/Dihydrosilyl Ligands
;
_journal_issue                   19
_journal_name_full               Organometallics
_journal_page_first              5070
_journal_paper_doi               10.1021/om5006319
_journal_volume                  33
_journal_year                    2014
_chemical_formula_moiety         'C24 H46 N2 P2 Si'
_chemical_formula_sum            'C24 H46 N2 P2 Si'
_chemical_formula_weight         452.66
_space_group_IT_number           61
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      61
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-06-12
_audit_creation_method
;
Olex2 1.2
(compiled 2014.05.21 svn.r2940 for OlexSys, GUI svn.r4846)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   11.8909(18)
_cell_length_b                   23.798(4)
_cell_length_c                   39.233(6)
_cell_measurement_reflns_used    30854
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      26.40
_cell_measurement_theta_min      3.00
_cell_volume                     11102(3)
_computing_cell_refinement       'CrystalClear-SM Expert 2.0 r13'
_computing_data_collection       'CrystalClear-SM Expert 2.0 r13 (Rigaku, 2011)'
_computing_data_reduction        'CrystalClear-SM Expert 2.0 r13'
_computing_structure_refinement
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'SHELXS97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      173.15
_diffrn_detector_area_resol_mean 6.827
_diffrn_measured_fraction_theta_full 0.980
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_device_type  'Rigaku XtaLAB mini'
_diffrn_measurement_method       \w
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0755
_diffrn_reflns_av_unetI/netI     0.0788
_diffrn_reflns_Laue_measured_fraction_full 0.980
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       49
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            39481
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.362
_diffrn_reflns_theta_min         3.110
_exptl_absorpt_coefficient_mu    0.212
_exptl_absorpt_correction_T_max  0.958
_exptl_absorpt_correction_T_min  0.636
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'REQAB (Rigaku, 1998)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.081
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             3968
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.381
_refine_diff_density_min         -0.285
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     579
_refine_ls_number_reflns         11066
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.1053
_refine_ls_R_factor_gt           0.0661
_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^)+(0.0490P)^2^+5.9450P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1316
_refine_ls_wR_factor_ref         0.1440
_reflns_number_gt                7575
_reflns_number_total             11066
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5006319_si_002.cif
_cod_data_source_block           scu1448_compound4
_cod_database_code               4084704
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.959
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H27D,H27E,H27F} of C27B, {H26D,H26E,H26F} of C26B, {H28A,
  H28B,H28C} of C28A, {H2C,H2D,H2E} of C2, {H3A,H3B,H3C} of C3, {H4A,H4B,H4C}
  of C4, {H6A,H6B,H6C} of C6, {H7A,H7B,H7C} of C7, {H8A,H8B,H8C} of C8, {H18A,
  H18B,H18C} of C18, {H19A,H19B,H19C} of C19, {H20A,H20B,H20C} of C20, {H22A,
  H22B,H22C} of C22, {H23A,H23B,H23C} of C23, {H24A,H24B,H24C} of C24, {H26A,
  H26B,H26C} of C26A, {H27A,H27B,H27C} of C27A, {H42A,H42B,H42C} of C42, {H43A,
  H43B,H43C} of C43, {H44A,H44B,H44C} of C44, {H46A,H46B,H46C} of C46, {H47A,
  H47B,H47C} of C47, {H48A,H48B,H48C} of C48, {H28D,H28E,H28F} of C28B, All C(H,
  H) groups
 At 1.5 times of:
  {H32A,H32B,H32C} of C32, {H31A,H31B,H31C} of C31, {H30A,H30B,H30C} of C30
2. Uiso/Uaniso restraints and constraints
Uanis(C25A) = Uanis(C25B)
Uanis(C26A) = Uanis(C26B)
Uanis(C27A) = Uanis(C27B)
Uanis(C28A) = Uanis(C28B)
3. Others
 Sof(C25B)=Sof(C26B)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C27B)=Sof(H27D)=
 Sof(H27E)=Sof(H27F)=Sof(C28B)=Sof(H28D)=Sof(H28E)=Sof(H28F)=1-FVAR(1)
 Sof(C25A)=Sof(C26A)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C27A)=Sof(H27A)=
 Sof(H27B)=Sof(H27C)=Sof(C28A)=Sof(H28A)=Sof(H28B)=Sof(H28C)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C16(H16A,H16B), C33(H33A,H33B), C40(H40A,H40B)
4.b Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C14(H14), C35(H35), C36(H36), C37(H37), C38(H38)
4.c Idealised Me refined as rotating group:
 C2(H2C,H2D,H2E), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C7(H7A,
 H7B,H7C), C8(H8A,H8B,H8C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,
 H20B,H20C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C),
 C26A(H26A,H26B,H26C), C27A(H27A,H27B,H27C), C28A(H28A,H28B,H28C), C26B(H26D,
 H26E,H26F), C27B(H27D,H27E,H27F), C28B(H28D,H28E,H28F), C30(H30A,H30B,H30C),
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C42(H42A,H42B,H42C), C43(H43A,H43B,
 H43C), C44(H44A,H44B,H44C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,
 H48B,H48C)
;
_shelx_res_checksum              6119
_shelx_hkl_checksum              60815