Additive-Controlled Selective Hydrosilylation Of Aryl Alkenes Catalyzed By Bis(silylene) Pincer Nickel(II) Chloride
Yang, Ziyan; Fan, Qingqing; Zhang, Xiangxu; Li, Xiaoyan; Sun, Hongjian; New Journal of Chemistry  (2025) –; doi:10.1039/D5NJ03998C

data_7064120
_publ_section_title
;
 Additive-Controlled Selective Hydrosilylation Of Aryl Alkenes Catalyzed
 By Bis(silylene) Pincer Nickel(II) Chloride
;
_journal_name_full               'New Journal of Chemistry'
_journal_paper_doi               10.1039/D5NJ03998C
_journal_year                    2025
_chemical_formula_moiety         '4(C40 H59 Cl N6 Ni Si2), 1[C4H10O], 1[C4H10O]'
_chemical_formula_sum            'C160 H236 Cl4 N24 Ni4 Si8'
_chemical_formula_weight         3097.07
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-10-31
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-11-04 deposited with the CCDC.	2025-11-19 downloaded from the CCDC.
;
_cell_angle_alpha                86.6620(10)
_cell_angle_beta                 83.5230(10)
_cell_angle_gamma                87.2840(10)
_cell_formula_units_Z            2
_cell_length_a                   13.5659(2)
_cell_length_b                   24.4752(3)
_cell_length_c                   27.3535(3)
_cell_measurement_reflns_used    51464
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      76.2990
_cell_measurement_theta_min      3.4590
_cell_volume                     9001.2(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.939
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     60.00 117.00   0.50    0.10    --   48.67  42.00 -54.00  114
  2  \w     94.00 174.00   0.50    0.45    --  106.65  42.00 -54.00  160
  3  \w     92.00 172.00   0.50    0.45    --  106.65  57.00   0.00  160
  4  \w    117.00 176.00   0.50    0.45    --  106.65  38.00  30.00  118
  5  \w     96.00 178.00   0.50    0.45    --  106.65  19.00  90.00  164
  6  \w    -23.00  47.00   0.50    0.10    --   48.67 -42.00 153.00  140
  7  \w     40.00 105.00   0.50    0.45    --  106.65 -99.00  60.00  130
  8  \w     38.00 111.00   0.50    0.45    --  106.65-125.00 -90.00  146
  9  \w     34.00 111.00   0.50    0.45    --  106.65-125.00-120.00  154
 10  \w     37.00 106.00   0.50    0.45    --  106.65 -99.00 -90.00  138
 11  \w     34.00 106.00   0.50    0.45    --  106.65 -99.00 -30.00  144
 12  \w     34.00 106.00   0.50    0.45    --  106.65 -99.00  30.00  144
 13  \w     34.00 104.00   0.50    0.45    --  106.65 -99.00 120.00  140
 14  \w     34.00 105.00   0.50    0.45    --  106.65 -99.00 150.00  142
 15  \w    -71.00  20.00   0.50    0.10    --  -48.67  77.00 -30.00  182
 16  \w    -45.00 -19.00   0.50    0.45    --  -91.75  42.00 -54.00   52
 17  \w    -47.00  20.00   0.50    0.10    --  -48.67  42.00 -54.00  134
 18  \w    -27.00  27.00   0.50    0.10    --  -48.67  19.00  90.00  108
 19  \w   -163.00 -86.00   0.50    0.45    --  -91.75 -42.00 153.00  154
 20  \w   -120.00 -36.00   0.50    0.10    --  -48.67 -42.00 153.00  168
 21  \w   -163.00 -73.00   0.50    0.45    --  -91.75 -77.00-150.00  180
 22  \w   -163.00 -87.00   0.50    0.45    --  -91.75 -99.00 -60.00  152
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0958005000
_diffrn_orient_matrix_UB_12      -0.0292129000
_diffrn_orient_matrix_UB_13      0.0195701000
_diffrn_orient_matrix_UB_21      0.0622605000
_diffrn_orient_matrix_UB_22      -0.0470381000
_diffrn_orient_matrix_UB_23      0.0228702000
_diffrn_orient_matrix_UB_31      -0.0055200000
_diffrn_orient_matrix_UB_32      0.0302684000
_diffrn_orient_matrix_UB_33      0.0481248000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0530
_diffrn_reflns_av_unetI/netI     0.0567
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.939
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            98903
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.939
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.538
_diffrn_reflns_theta_min         3.499
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.921
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88707
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.143
_exptl_crystal_description       block
_exptl_crystal_F_000             3312
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.360
_refine_diff_density_min         -0.412
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1895
_refine_ls_number_reflns         35506
_refine_ls_number_restraints     78
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0536
_refine_ls_R_factor_gt           0.0410
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0478P)^2^+1.4284P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1040
_refine_ls_wR_factor_ref         0.1113
_reflns_Friedel_coverage         0.000
_reflns_number_gt                27983
_reflns_number_total             35506
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj03998c2.cif
_cod_data_source_block           241113g_auto
_cod_database_code               7064120
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         NiSiClNC
_shelx_estimated_absorpt_t_max   0.910
_shelx_estimated_absorpt_t_min   0.861
_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. Uiso/Uaniso restraints and constraints
C16 \\sim C18 \\sim C18A \\sim C17A \\sim C17 \\sim C19A \\sim C19: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
3. Same fragment restrains
{C16, C17A, C18A, C19A} sigma for 1-2: 0.01, 1-3: 0.02
as in
{C16, C19, C17, C18}
4. Others
 Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(C18A)=Sof(H18D)=Sof(H18E)=
 Sof(H18F)=Sof(C19A)=Sof(H19D)=Sof(H19E)=Sof(H19F)=1-FVAR(1)
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C87(H87A,H87B), C127(H12A,H12B), C7(H7A,H7B), C47(H47A,H47B), C9(H9A,H9B),
 C49(H49A,H49B), C129(H12F,H12G)
5.b Aromatic/amide H refined with riding coordinates:
 C25(H25), C125(H125), C4(H4), C5(H5), C123(H123), C84(H84), C124(H124),
 C6(H6), C45(H45), C86(H86), C120(H120), C85(H85), C44(H44), C134(H134),
 C24(H24), C46(H46), C148(H148), C116(H116), C36(H36), C61(H61), C149(H149),
 C105(H105), C119(H119), C117(H117), C40(H40), C118(H118), C64(H64), C62(H62),
 C65(H65), C136(H136), C21(H21), C133(H133), C77(H77), C23(H23), C37(H37),
 C150(H150), C22(H22), C38(H38), C63(H63), C101(H101), C104(H104), C151(H151),
 C137(H137), C39(H39), C76(H76), C135(H135), C103(H103), C152(H152), C102(H102),
  C80(H80), C79(H79), C78(H78)
5.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C128(H12C,H12D,
 H12E), C88(H88A,H88B,H88C), C59(H59A,H59B,H59C), C109(H10D,H10E,H10F),
 C68(H68A,H68B,H68C), C32(H32A,H32B,H32C), C70(H70A,H70B,H70C), C8(H8A,H8B,H8C),
  C144(H14D,H14E,H14F), C89(H89A,H89B,H89C), C33(H33A,H33B,H33C), C69(H69A,H69B,
 H69C), C98(H98A,H98B,H98C), C145(H14G,H14H,H14I), C34(H34A,H34B,H34C),
 C48(H48A,H48B,H48C), C13(H13A,H13B,H13C), C110(H11A,H11B,H11C), C156(H15D,H15E,
 H15F), C50(H50A,H50B,H50C), C108(H10G,H10H,H10I), C143(H14J,H14K,H14L),
 C30(H30A,H30B,H30C), C141(H14M,H14N,H14O), C113(H11D,H11E,H11F), C97(H97A,H97B,
 H97C), C155(H15G,H15H,H15I), C92(H92A,H92B,H92C), C58(H58A,H58B,H58C),
 C10(H10A,H10B,H10C), C55(H55A,H55B,H55C), C57(H57A,H57B,H57C), C73(H73A,H73B,
 H73C), C160(H16A,H16B,H16C), C93(H93A,H93B,H93C), C140(H14P,H14Q,H14R),
 C159(H15J,H15K,H15L), C112(H11G,H11H,H11I), C130(H13D,H13E,H13F), C99(H99A,
 H99B,H99C), C15(H15A,H15B,H15C), C94(H94A,H94B,H94C), C14(H14A,H14B,H14C),
 C72(H72A,H72B,H72C), C139(H13G,H13H,H13I), C74(H74A,H74B,H74C), C154(H15M,H15N,
 H15O), C158(H15P,H15Q,H15R), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C),
 C29(H29A,H29B,H29C), C114(H11J,H11K,H11L), C28(H28A,H28B,H28C), C17A(H17D,H17E,
 H17F), C18A(H18D,H18E,H18F), C19A(H19D,H19E,H19F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              41165
_shelx_fab_checksum              27843
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.292
_oxdiff_exptl_absorpt_empirical_full_min 0.678