Metal–silicon triple bonds: reactivity of the silylidyne complexes [Cp*(CO)2M≡Si–Tbb] (M = Cr – W)
Tomer, Kanishk; Schnakenburg, Gregor; Das, Ujjal; Filippou, Alexander C.; Chemical Science 16 (2025) 7773–7793; doi:10.1039/D5SC01063B

data_1574207
_publ_section_title
;
 Metal--silicon triple bonds: reactivity of the silylidyne complexes
 [Cp*(CO)2M\\tb Si--Tbb] (M = Cr -- W)
;
_journal_issue                   18
_journal_name_full               'Chemical Science'
_journal_page_first              7773
_journal_page_last               7793
_journal_paper_doi               10.1039/D5SC01063B
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C36 H64 Cr O2 Si5'
_chemical_formula_sum            'C36 H64 Cr O2 Si5'
_chemical_formula_weight         721.32
_chemical_name_systematic        KT-75
_space_group_crystal_system      monoclinic
_space_group_IT_number           11
_space_group_name_Hall           '-P 2yb'
_space_group_name_H-M_alt        'P 1 21/m 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-11-11
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-04 deposited with the CCDC.	2025-03-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.363(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.061(3)
_cell_length_b                   15.143(4)
_cell_length_c                   12.602(3)
_cell_measurement_reflns_used    5166
_cell_measurement_temperature    100
_cell_measurement_theta_max      23.805
_cell_measurement_theta_min      2.503
_cell_volume                     2282.6(10)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_detector                 'Bruker Photon100 detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0478
_diffrn_reflns_av_unetI/netI     0.0412
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            22149
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.999
_diffrn_reflns_theta_min         1.702
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.407
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6073
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1298 before and 0.0685 after correction.
The Ratio of minimum to maximum transmission is 0.8144.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.049
_exptl_crystal_description       block
_exptl_crystal_F_000             780
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.6
_exptl_crystal_size_min          0.5
_refine_diff_density_max         0.615
_refine_diff_density_min         -0.533
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     469
_refine_ls_number_reflns         4642
_refine_ls_number_restraints     1063
_refine_ls_restrained_S_all      0.987
_refine_ls_R_factor_all          0.1195
_refine_ls_R_factor_gt           0.0830
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1427P)^2^+3.6918P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2300
_refine_ls_wR_factor_ref         0.2701
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3105
_reflns_number_total             4642
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01063b2.cif
_cod_data_source_block           1-Cr
_cod_depositor_comments
'Adding full bibliography for 1574207--1574214.cif.'
_cod_original_cell_volume        2282.7(9)
_cod_database_code               1574207
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.822
_shelx_estimated_absorpt_t_min   0.792
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C12-C11 = C13-C11 = C14-C11
 1.54 with sigma of 0.001
 C12A-C11A = C13A-C11A = C14A-C11A
 1.54 with sigma of 0.001
 O2-O3
 2 with sigma of 0.001
 C11-C13 \\sim C11-C14
 with sigma of 0.02
 C12-C13 \\sim C13-C14 \\sim C14-C12
 with sigma of 0.001
 O3-C31 \\sim O1-C29 \\sim O4-C32
 with sigma of 0.001
 C12A-C13A \\sim C13A-C14A \\sim C14A-C12A
 with sigma of 0.001
 C32-Cr \\sim C29_$1-Cr \\sim C31_$1-Cr
 with sigma of 0.001
3. Rigid bond restraints
 Si3, C15
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
C19 \\sim C19A \\sim C20 \\sim C20A \\sim C21 \\sim C21A \\sim C22 \\sim C22A
\\sim C23 \\sim C23A \\sim C24 \\sim C24A \\sim C25 \\sim C25A \\sim C26 \\sim
C26A \\sim C27 \\sim C27A \\sim C28 \\sim C28A: within 2A with sigma of 0.001
and sigma for terminal atoms of 0.002 within 2A
C11 \\sim C11A \\sim C12 \\sim C12A \\sim C13 \\sim C13A \\sim C14 \\sim C14A:
within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
O1 \\sim O2 \\sim O3 \\sim O4 \\sim C29 \\sim C30 \\sim C31 \\sim C32: within
2A with sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 1*[Sof(O4)+Sof(C32)]+1*[Sof(O1)+Sof(C29)]+1*[Sof(O3)+Sof(C31)]+1*[Sof(O2)+
 Sof(C30)]=1 with esd of 0.0001
 Sof(C23A)=Sof(C19A)=Sof(C20A)=Sof(C21A)=Sof(C22A)=Sof(C28A)=Sof(H28D)=
 Sof(H28E)=Sof(H28F)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C25A)=
 Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=
 Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=0.5*(1-FVAR(2))
 Sof(C23)=Sof(C19)=Sof(C20)=Sof(C21)=Sof(C22)=Sof(C28)=Sof(H28A)=Sof(H28B)=
 Sof(H28C)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25)=Sof(H25A)=Sof(H25B)=
 Sof(H25C)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C27)=Sof(H27A)=Sof(H27B)=
 Sof(H27C)=0.5*FVAR(2)
 Sof(O4)=Sof(C32)=FVAR(2)
 Sof(O1)=Sof(C29)=FVAR(3)
 Sof(O3)=Sof(C31)=FVAR(4)
 Sof(O2)=Sof(C30)=FVAR(5)
 Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=
 Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=1-FVAR(6)
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(6)
 Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C17A)=Sof(H17D)=Sof(H17E)=
 Sof(H17F)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=1-FVAR(7)
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=FVAR(7)
 Sof(C11A)=Sof(C12A)=Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(C13A)=Sof(H13D)=
 Sof(H13E)=Sof(H13F)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=0.5*(1-FVAR(9))
 Sof(C11)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C13)=Sof(H13A)=Sof(H13B)=
 Sof(H13C)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=0.5*FVAR(9)
 Fixed Sof: Cr(0.5)
 Fixed X: O2(0.163641) C6(0.313921)
 Fixed Y: O2(0.45163) C6(0.25)
 Fixed Z: O2(0.64637) C6(0.903529)
7.a Ternary CH refined with riding coordinates:
 C7(H7), C15(H15)
7.b Me refined with riding coordinates:
 C8(H8A,H8B,H8C), C8A(H8AA,H8AB,H8AC), C9(H9A,H9B,H9C), C9A(H9AA,H9AB,H9AC),
 C10(H10A,H10B,H10C), C10A(H10D,H10E,H10F), C12(H12A,H12B,H12C), C12A(H12D,H12E,
 H12F), C13(H13A,H13B,H13C), C13A(H13D,H13E,H13F), C14(H14A,H14B,H14C),
 C14A(H14D,H14E,H14F), C16(H16A,H16B,H16C), C16A(H16D,H16E,H16F), C17(H17A,H17B,
 H17C), C17A(H17D,H17E,H17F), C18(H18A,H18B,H18C), C18A(H18D,H18E,H18F),
 C28(H28A,H28B,H28C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C27(H27A,H27B,H27C), C28A(H28D,H28E,H28F), C24A(H24D,H24E,H24F),
 C25A(H25D,H25E,H25F), C26A(H26D,H26E,H26F), C27A(H27D,H27E,H27F)
7.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5)
7.d Cp* refined as free rotating group:
 C23(C19,C20,C21,C22,C28,C24,C25,C26,C27), C23A(C19A,C20A,C21A,C22A,C28A,C24A,
 C25A,C26A,C27A)
;
_olex2_submission_special_instructions 'No special instructions were received'