A two-coordinate Ni(I) silyl complex: CO2 insertion and oxidatively-induced silyl migrations
Witzke, Ryan J.; Tilley, T. Don; Chemical Communications  (2019) –; doi:10.1039/C9CC03128F

data_7123414
_publ_section_title
;
 A two-coordinate Ni(I) silyl complex: CO2 insertion and
 oxidatively-induced silyl migrations
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC03128F
_journal_year                    2019
_chemical_formula_moiety         'C37 H63 N2 Ni O2 Si4'
_chemical_formula_sum            'C37 H63 N2 Ni O2 Si4'
_chemical_formula_weight         738.96
_chemical_name_common            RJW_3_087
_chemical_name_systematic        IPrNiO2CSi(SiMe3)3
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-10-31
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-11-27 deposited with the CCDC.    2019-05-08 downloaded from the CCDC.
;
_cell_angle_alpha                100.925(2)
_cell_angle_beta                 91.647(2)
_cell_angle_gamma                96.645(2)
_cell_formula_units_Z            2
_cell_length_a                   10.3727(4)
_cell_length_b                   14.3391(6)
_cell_length_c                   15.0287(6)
_cell_measurement_reflns_used    9877
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      39.15
_cell_measurement_theta_min      2.83
_cell_volume                     2177.10(15)
_computing_cell_refinement       'SAINT V8.38A Bruker-AXS, Madison WI'
_computing_data_collection       'Bruker APEX2 Bruker-AXS, Madison WI'
_computing_data_reduction        'SAINT V8.38A Bruker-AXS, Madison WI'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Bruker SHELXTL Bruker-AXS, Madison WI'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 10.42
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measurement_device_type  'Bruker D8 with PHOTON 100 detector'
_diffrn_measurement_method       '\f and \w shutterless scans'
_diffrn_radiation_monochromator  'silicon 111'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.7749
_diffrn_reflns_av_R_equivalents  0.0302
_diffrn_reflns_av_unetI/netI     0.0510
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            38875
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        27.706
_diffrn_reflns_theta_max         39.159
_diffrn_reflns_theta_min         2.831
_diffrn_source
;
Advanced Light Source, station 11.3.1
;
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.737
_exptl_absorpt_correction_T_max  0.7477
_exptl_absorpt_correction_T_min  0.6312
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS-2016/2 - Bruker AXS, Madison WI'
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.127
_exptl_crystal_description       plate
_exptl_crystal_F_000             798
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: pentane'
_refine_diff_density_max         1.142
_refine_diff_density_min         -0.863
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     548
_refine_ls_number_reflns         19211
_refine_ls_number_restraints     306
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0687
_refine_ls_R_factor_gt           0.0502
_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^)+(0.0318P)^2^+1.2188P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1111
_refine_ls_wR_factor_ref         0.1191
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14662
_reflns_number_total             19211
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc03128f2.cif
_cod_data_source_block           rjw_3_087
_cod_original_cell_volume        2177.09(15)
_cod_database_code               7123414
_shelx_shelxl_version_number     2014/7
_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
2. Rigid bond restraints
 Si1, Si2, C32, C33, C34, Si3, C29, C30, C31, Si4, C35, C36, C37, Si2', C32',
 C33', C34', Si3', C29', C30', C31', Si4', C35', C36', C37'
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
3. Uiso/Uaniso restraints and constraints
Si1 \\sim Si2 \\sim C32 \\sim C33 \\sim C34 \\sim Si3 \\sim C29 \\sim C30 \\sim
C31 \\sim Si4 \\sim C35 \\sim C36 \\sim C37 \\sim Si2' \\sim C32' \\sim C33'
\\sim C34' \\sim Si3' \\sim C29' \\sim C30' \\sim C31' \\sim Si4' \\sim C35'
\\sim C36' \\sim C37': within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
4. Others
 Sof(Si2')=Sof(C32')=Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C33')=Sof(H33D)=
 Sof(H33E)=Sof(H33F)=Sof(C34')=Sof(H34D)=Sof(H34E)=Sof(H34F)=Sof(Si3')=
 Sof(C29')=Sof(H29D)=Sof(H29E)=Sof(H29F)=Sof(C30')=Sof(H30D)=Sof(H30E)=
 Sof(H30F)=Sof(C31')=Sof(H31D)=Sof(H31E)=Sof(H31F)=Sof(Si4')=Sof(C35')=
 Sof(H35D)=Sof(H35E)=Sof(H35F)=Sof(C36')=Sof(H36D)=Sof(H36E)=Sof(H36F)=
 Sof(C37')=Sof(H37D)=Sof(H37E)=Sof(H37F)=Sof(H13A)=1-FVAR(1)
 Sof(Si2)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C33)=Sof(H33A)=Sof(H33B)=
 Sof(H33C)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(Si3)=Sof(C29)=Sof(H29A)=
 Sof(H29B)=Sof(H29C)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C31)=Sof(H31A)=
 Sof(H31B)=Sof(H31C)=Sof(Si4)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C36)=
 Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(H13)=
 FVAR(1)
 Fixed Sof: C14(0.5) H14A(0.5) H14B(0.5) H14C(0.5) C15(0.5) H15A(0.5)
 H15B(0.5) H15C(0.5) C14'(0.5) H14D(0.5) H14E(0.5) H14F(0.5) C15'(0.5)
 H15D(0.5) H15E(0.5) H15F(0.5)
5.a Ternary CH refined with riding coordinates:
 C25(H25), C22(H22), C10(H10), C13(H13A), C13(H13)
5.b Me refined with riding coordinates:
 C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C35(H35A,H35B,H35C), C36(H36A,
 H36B,H36C), C37(H37A,H37B,H37C), C32'(H32D,H32E,H32F), C33'(H33D,H33E,H33F),
 C34'(H34D,H34E,H34F), C29'(H29D,H29E,H29F), C30'(H30D,H30E,H30F), C31'(H31D,
 H31E,H31F), C35'(H35D,H35E,H35F), C36'(H36D,H36E,H36F), C37'(H37D,H37E,H37F),
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C14'(H14D,H14E,H14F), C15'(H15D,H15E,
 H15F)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C18(H18), C20(H20), C7(H7), C6(H6), C8(H8), C19(H19)
5.d Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C27(H27A,H27B,H27C), C24(H24A,H24B,H24C), C11(H11A,H11B,
 H11C), C12(H12A,H12B,H12C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              64645
_olex2_submission_special_instructions 'No special instructions were received'