A Highly Chemoselective Cobalt Catalyst for the Hydrosilylation of Alkenes using Tertiary Silanes and Hydrosiloxanes
Ibrahim, Abdulrahman D.; Entsminger, Steven W.; Zhu, Lingyang; Fout, Alison R.; ACS Catalysis 6 (2016) 3589–; doi:10.1021/acscatal.6b01091

data_4516696
_publ_section_title
;
 A Highly Chemoselective Cobalt Catalyst for the Hydrosilylation of
 Alkenes using Tertiary Silanes and Hydrosiloxanes
;
_journal_issue                   6
_journal_name_full               'ACS Catalysis'
_journal_page_first              3589
_journal_paper_doi               10.1021/acscatal.6b01091
_journal_volume                  6
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C68 H67 Co N6 Si2, 2(C4 H10 O)'
_chemical_formula_sum            'C76 H87 Co N6 O2 Si2'
_chemical_formula_weight         1231.62
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2016-01-11
_audit_creation_method
; 
Olex2 1.2 
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103) 
;
_cell_angle_alpha                90
_cell_angle_beta                 100.7617(11)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.1686(4)
_cell_length_b                   15.7163(5)
_cell_length_c                   17.6104(6)
_cell_measurement_reflns_used    9507
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      27.21
_cell_measurement_theta_min      2.24
_cell_volume                     3308.67(19)
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2013.10-0 (Bruker, 2013)'
_computing_data_reduction
; 
SAINT V8.34A, XPREP v2013/3, SADABS V2012/1, TWINABS V2012/1 
(Bruker, 2012 & 2013) 
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELX-2014-6 (Sheldrick, 2014)'
_computing_structure_solution    'SHELX-2014-6 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.15
_diffrn_detector                 'Bruker APEXII CCD area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'profile data from \f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_wavelength_id  cm89w
_diffrn_reflns_av_R_equivalents  0.0346
_diffrn_reflns_av_unetI/netI     0.0337
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            73761
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.230
_diffrn_reflns_theta_min         1.177
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Siemens fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.347
_exptl_absorpt_correction_T_max  0.9455
_exptl_absorpt_correction_T_min  0.8841
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details
; 
SADABS-2014/4 (Bruker,2014) was used for absorption correction. 
wR2(int) was 0.0670 before and 0.0594 after correction. 
The Ratio of minimum to maximum transmission is 0.9351. 
The \l/2 correction factor is 0.00150. 
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.236
_exptl_crystal_description       prism
_exptl_crystal_F_000             1312
_exptl_crystal_id                cm89w
_exptl_crystal_preparation
; 
The data crystal was mounted using oil (Parantone-N, Exxon) to a 
0.3 mm cryo-loop (Hampton Research) with the (0, 1, -2) scattering 
planes roughly normal to the spindle axis. 
;
_exptl_crystal_size_max          0.656
_exptl_crystal_size_mid          0.273
_exptl_crystal_size_min          0.229
_refine_diff_density_max         0.340
_refine_diff_density_min         -0.233
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
; 
 Flack x determined using 6447 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   0.008(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     850
_refine_ls_number_reflns         14756
_refine_ls_number_restraints     194
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0295
_refine_ls_R_factor_gt           0.0276
_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^)+(0.0433P)^2^+0.3754P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0708
_refine_ls_wR_factor_ref         0.0737
_reflns_Friedel_coverage         0.927
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                14122
_reflns_number_total             14756
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs6b01091_si_002.cif
_cod_data_source_block           cm89w_0m
_cod_database_code               4516696
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.925
_shelx_estimated_absorpt_t_min   0.804
_olex2_refinement_description
; 
1. Fixed Uiso 
 At 1.2 times of: 
  All C(H) groups, All C(H,H) groups 
 At 1.5 times of: 
  All C(H,H,H) groups, All Si(H) groups 
2. Uiso/Uaniso restraints and constraints 
O1A \\sim C1A \\sim C2A \\sim C3A \\sim C4A \\sim O1B \\sim C1B \\sim C2B \\sim 
C3B \\sim C4B: within 2A with sigma of 0.01 and sigma for terminal atoms of 
0.02 Uanis(O1A) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C2A) \\sim Ueq, 
Uanis(C3A) \\sim Ueq, Uanis(C4A) \\sim Ueq, Uanis(O1B) \\sim Ueq, Uanis(C1B) 
\\sim Ueq, Uanis(C2B) \\sim Ueq, Uanis(C3B) \\sim Ueq, Uanis(C4B) \\sim Ueq: 
with sigma of 0.01 and sigma for terminal atoms of 0.02 
3. Same fragment restrains 
{O1A, C1A, C2A, C3A, C4A} sigma for 1-2: 0.01, 1-3: 0.04 
as 
{O1B, C1B, C2B, C3B, C4B} 
4. Others 
 Sof(O1B)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(C2B)=Sof(H2BA)=Sof(H2BB)=Sof(H2BC)= 
 Sof(C3B)=Sof(H3BA)=Sof(H3BB)=Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(H4BC)=1-FVAR(1) 
 Sof(O1A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)= 
 Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=FVAR(1) 
5.a Ternary CH refined with riding coordinates: 
 C27(H27), C30(H30), C39(H39), C42(H42) 
5.b Secondary CH2 refined with riding coordinates: 
 C1A(H1AA,H1AB), C3A(H3AA,H3AB), C1B(H1BA,H1BB), C3B(H3BA,H3BB), C6A(H6AA, 
 H6AB), C7A(H7AA,H7AB) 
5.c Aromatic/amide H refined with riding coordinates: 
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C15(H15), 
 C16(H16), C17(H17), C18(H18), C23(H23), C24(H24), C25(H25), C35(H35), 
C36(H36),   C37(H37), C46(H46), C47(H47), C48(H48), C49(H49), C50(H50), 
C52(H52),  C53(H53), C54(H54), C55(H55), C56(H56), C58(H58), C59(H59), 
C60(H60), C61(H61),   C62(H62), C64(H64), C65(H65), C66(H66), C67(H67), 
C68(H68) 
5.d Idealised Me refined as rotating group: 
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C31(H31A,H31B,H31C), 
C32(H32A,H32B,  H32C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), 
C43(H43A,H43B,H43C), C44(H44A,  H44B,H44C), C2A(H2AA,H2AB,H2AC),
 C4A(H4AA,H4AB,H4AC), C2B(H2BA,H2BB,H2BC), 
 C4B(H4BA,H4BB,H4BC), C5A(H5AA,H5AB,H5AC), C8A(H8AA,H8AB,H8AC) 
;
_olex2_submission_special_instructions 'No special instructions were received'