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_1574210
_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         'C56 H86 N2 O4 Si5 W, C7 H8'
_chemical_formula_sum            'C63 H94 N2 O4 Si5 W'
_chemical_formula_weight         1267.70
_chemical_name_systematic        KT-14
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-03-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2025-02-04 deposited with the CCDC.	2025-03-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.3260(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.4410(2)
_cell_length_b                   14.4060(2)
_cell_length_c                   34.6694(5)
_cell_measurement_reflns_used    45740
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      26.73
_cell_measurement_theta_min      2.52
_cell_volume                     6624.34(17)
_computing_cell_refinement       'STOE X-AREA'
_computing_data_collection       'STOE X-AREA'
_computing_data_reduction        'STOE X-RED'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      123(2)
_diffrn_detector                 'image plate (34 cm diameter)'
_diffrn_detector_area_resol_mean 6.67
_diffrn_detector_type            STOE
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.968
_diffrn_measurement_details
;
 742 frames, detector distance = 200 mm
;
_diffrn_measurement_device       '2-circle goniometer'
_diffrn_measurement_device_type  'STOE IPDS 2T'
_diffrn_measurement_method       'rotation method'
_diffrn_radiation_collimation    '0.5 mm diameter, monocapillary'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_polarisn_norm  0
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0878
_diffrn_reflns_av_unetI/netI     0.0794
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            98885
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.979
_diffrn_reflns_theta_min         2.523
_diffrn_source
'sealed X-ray tube, 12 x 0.4 mm long-fine focus'
_diffrn_source_current           40
_diffrn_source_power             2.00
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.878
_exptl_absorpt_correction_T_max  0.7818
_exptl_absorpt_correction_T_min  0.6871
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details   'STOE XRed 1.53'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.271
_exptl_crystal_description       plate
_exptl_crystal_F_000             2648
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.909
_refine_diff_density_min         -1.488
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.876
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     748
_refine_ls_number_reflns         13967
_refine_ls_number_restraints     138
_refine_ls_restrained_S_all      0.880
_refine_ls_R_factor_all          0.0819
_refine_ls_R_factor_gt           0.0393
_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^)+(0.0444P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0773
_refine_ls_wR_factor_ref         0.0856
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8640
_reflns_number_total             13967
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01063b2.cif
_cod_data_source_block           2-W
_cod_depositor_comments
'Adding full bibliography for 1574207--1574214.cif.'
_cod_database_code               1574210
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.963
_shelx_estimated_absorpt_t_min   0.466
_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. Uiso/Uaniso restraints and constraints
C47S \\sim C48S \\sim C49S \\sim C51S: within 2A with sigma of 0.001 and sigma
for terminal atoms of 0.002
C52S \\sim C53S \\sim C54S \\sim C55S \\sim C56S: within 2A with sigma of 0.001
and sigma for terminal atoms of 0.002
Uanis(C47) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C50)
\\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C53) \\sim Ueq,
Uanis(C54) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C50S)
\\sim Ueq, Uanis(C51S) \\sim Ueq, Uanis(C47S) \\sim Ueq, Uanis(C48S) \\sim Ueq,
Uanis(C49S) \\sim Ueq, Uanis(C55S) \\sim Ueq, Uanis(C56S) \\sim Ueq,
Uanis(C52S) \\sim Ueq, Uanis(C53S) \\sim Ueq, Uanis(C54S) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
Uanis(C50S) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
3. Others
 Sof(C50S)=Sof(C47S)=Sof(C48S)=Sof(C49S)=Sof(C51S)=Sof(C52S)=Sof(H52A)=
 Sof(H52B)=Sof(H52C)=Sof(C53S)=Sof(H53A)=Sof(H53B)=Sof(H53C)=Sof(C54S)=
 Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C55S)=Sof(H55A)=Sof(H55B)=Sof(H55C)=
 Sof(C56S)=Sof(H56A)=Sof(H56B)=Sof(H56C)=1-FVAR(1)
 Sof(C47)=Sof(C48)=Sof(C49)=Sof(C50)=Sof(C51)=Sof(C52)=Sof(H52D)=Sof(H52E)=
 Sof(H52F)=Sof(C53)=Sof(H53D)=Sof(H53E)=Sof(H53F)=Sof(C54)=Sof(H54D)=Sof(H54E)=
 Sof(H54F)=Sof(C55)=Sof(H55D)=Sof(H55E)=Sof(H55F)=Sof(C56)=Sof(H56D)=Sof(H56E)=
 Sof(H56F)=FVAR(1)
4.a :
 C47(C48,C49,C50,C51,C52,C53,C54,C55,C56), C50S(C47S,C48S,C49S,C51S,C52S,C53S,
 C54S,C55S,C56S)
4.b Ternary CH refined with riding coordinates:
 C7(H7), C18(H18)
4.c Me refined with riding coordinates:
 C52S(H52A,H52B,H52C), C53S(H53A,H53B,H53C), C54S(H54A,H54B,H54C), C55S(H55A,
 H55B,H55C), C56S(H56A,H56B,H56C)
4.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C28(H28), C30(H30), C40(H40), C42(H42), C58(H58), C59(H59),
 C60(H60), C61(H61), C62(H62)
4.e Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,
 H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C),
 C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C44(H44A,H44B,
 H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C52(H52D,H52E,H52F), C53(H53D,
 H53E,H53F), C54(H54D,H54E,H54F), C55(H55D,H55E,H55F), C56(H56D,H56E,H56F),
 C63(H63A,H63B,H63C)
;
_shelx_res_checksum              29014
_olex2_submission_special_instructions 'No special instructions were received'