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_1574211
_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         'C44 H84 Mo N4 O2 Si7'
_chemical_formula_sum            'C44 H84 Mo N4 O2 Si7'
_chemical_formula_weight         993.72
_chemical_name_systematic        KT-167
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-08-01
_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                 118.635(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1671(3)
_cell_length_b                   42.6785(10)
_cell_length_c                   12.6572(4)
_cell_measurement_reflns_used    20405
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      29.58
_cell_measurement_theta_min      2.70
_cell_volume                     5768.7(3)
_computing_cell_refinement       'X-Area Recipe 2.0.1 (STOE, 2023)'
_computing_data_collection       'X-Area WinXpose 2.0.29.0 (STOE, 2023)'
_computing_data_reduction
;
X-Area Integrate 2.5.15.0 (STOE, 2023)
X-Area LANA 2.7.12 (STOE, 2023)
;
_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)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       '2-circle goniometer'
_diffrn_measurement_device_type  'STOE IPDS 2T'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '0.5 mm diameter, monocapillary'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_polarisn_norm  0
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0264
_diffrn_reflns_av_unetI/netI     0.0213
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       51
_diffrn_reflns_limit_k_min       -51
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            43029
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.249
_diffrn_reflns_theta_min         2.133
_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    0.407
_exptl_absorpt_correction_T_max  0.9062
_exptl_absorpt_correction_T_min  0.7942
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE X-Red32, absorption correction by Gaussian integration, analogous to
P. Coppens in: F. R. Ahmed (Editor), "Crystallographic Computing", Munksgaard,
Copenhagen (1970), 255 - 270. Afterwards scaling of reflection intensities was
performed within STOE LANA. J. Koziskova, F. Hahn, J. Richter, J. Kozisek, Acta
Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
Finally a spherical absorption correction was done within STOE LANA.
;
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.144
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2128
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.13
_refine_diff_density_max         2.633
_refine_diff_density_min         -0.967
_refine_diff_density_rms         0.110
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     578
_refine_ls_number_reflns         10458
_refine_ls_number_restraints     674
_refine_ls_restrained_S_all      1.123
_refine_ls_R_factor_all          0.0863
_refine_ls_R_factor_gt           0.0761
_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^)+(0.0739P)^2^+32.7690P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1797
_refine_ls_wR_factor_ref         0.1874
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9166
_reflns_number_total             10458
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01063b2.cif
_cod_data_source_block           4-Mo
_cod_depositor_comments
'Adding full bibliography for 1574207--1574214.cif.'
_cod_database_code               1574211
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.949
_shelx_estimated_absorpt_t_min   0.898
_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 C(H,H,H,H,H,H) groups
2. Rigid bond restraints
 Si2, C10
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Si6, C28
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N4, C29
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C14, C16
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C36, C41
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Si3, C11
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C3, C12
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Si5, C23
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C35, C36
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Mo, C36
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Mo, C37
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Si3, C12
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Si3, C13
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C37, C42
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C31S) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C15)
\\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C28) \\sim Ueq,
Uanis(C41) \\sim Ueq, Uanis(C42) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C30S) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C10)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C11) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(Si3) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
Uanis(C37) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C23) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.05 and sigma for 1-3 distances of 0.05
5. Others
 Sof(Si7S)=Sof(H29A)=Sof(C30S)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C31S)=
 Sof(H31D)=Sof(H31E)=Sof(H31F)=Sof(H32D)=Sof(H32E)=Sof(H32F)=1-FVAR(1)
 Sof(Si7)=Sof(H29)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C31)=Sof(H31A)=
 Sof(H31B)=Sof(H31C)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C7(H7), C18(H18)
6.b Me refined with riding coordinates:
 C32(H32A,H32B,H32C), C32(H32D,H32E,H32F)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C25(H25), C29(H29), C29(H29A)
6.d 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),
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,
 H30C), C30S(H30D,H30E,H30F), C31(H31A,H31B,H31C), C31S(H31D,H31E,H31F),
 C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,
 H41C), C42(H42A,H42B,H42C)
;
_shelx_res_checksum              69110
_olex2_submission_special_instructions 'No special instructions were received'