Reactive Coordinatively Saturated Mo(III) Complex: Exploiting the Adaptive Hapticity of Tris(tert-butoxy)silanolate Ligands
Pucino, Margherita; Allouche, Florian; Gordon, Christopher P.; Wörle, Michael; Mougel, Victor; Coperet, Christophe; Chemical Science  (2019) –; doi:10.1039/C9SC01955C

data_1551048
_publ_section_title
;
 Reactive Coordinatively Saturated Mo(III) Complex: Exploiting the
 Adaptive Hapticity of Tris(tert-butoxy)silanolate Ligands
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC01955C
_journal_year                    2019
_chemical_formula_moiety         '1(C37 H81 Mo O13 Si3)'
_chemical_formula_sum            'C37 H81 Mo O13 Si3'
_chemical_formula_weight         914.22
_chemical_name_systematic        '[Mo(CO)(TBOS)3] '
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-09-19
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-03-01 deposited with the CCDC.    2019-05-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 117.032(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   26.8309(13)
_cell_length_b                   15.5455(7)
_cell_length_c                   27.4545(13)
_cell_measurement_reflns_used    9969
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.11
_cell_measurement_theta_min      2.65
_cell_volume                     10200.2(8)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0769
_diffrn_reflns_av_unetI/netI     0.0392
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            201998
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.332
_exptl_absorpt_coefficient_mu    0.379
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6790
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0691 before and 0.0649 after correction.
The Ratio of minimum to maximum transmission is 0.9106.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.191
_exptl_crystal_description       block
_exptl_crystal_F_000             3928
_exptl_crystal_preparation       'reaction of Mo(silox)3(CO) with CO2'
_exptl_crystal_recrystallization_method
'slow evaporation of a pentane solution at -40 degrees Celsius'
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.887
_refine_diff_density_min         -0.881
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1212
_refine_ls_number_reflns         20874
_refine_ls_number_restraints     1095
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0686
_refine_ls_R_factor_gt           0.0413
_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^)+(0.0289P)^2^+16.9600P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0851
_refine_ls_wR_factor_ref         0.0984
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15639
_reflns_number_total             20874
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc01955c2.cif
_cod_data_source_block           mo_CCDC1
_cod_database_code               1551048
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C51B) \\sim Ueq, Uanis(C51A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.01
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C52A)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C54A)=Sof(H54A)=Sof(H54B)=
 Sof(H54C)=Sof(C53A)=Sof(H53A)=Sof(H53B)=Sof(H53C)=Sof(O22A)=Sof(C51A)=
 Sof(O23A)=Sof(C55A)=Sof(C1AA)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C59A)=
 Sof(C57A)=Sof(H57D)=Sof(H57E)=Sof(H57F)=Sof(O24A)=Sof(C60A)=Sof(H60D)=
 Sof(H60E)=Sof(H60F)=Sof(C56A)=Sof(H56D)=Sof(H56E)=Sof(H56F)=Sof(C61B)=
 Sof(H61D)=Sof(H61E)=Sof(H61F)=Sof(C58A)=Sof(H58D)=Sof(H58E)=Sof(H58F)=1-FVAR(1)
 Sof(O22B)=Sof(C51B)=Sof(O23B)=Sof(C55B)=Sof(C62B)=Sof(H62A)=Sof(H62B)=
 Sof(H62C)=Sof(C59B)=Sof(C57B)=Sof(H57A)=Sof(H57B)=Sof(H57C)=Sof(C56B)=
 Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(O24B)=Sof(C60B)=Sof(H60A)=Sof(H60B)=
 Sof(H60C)=Sof(C58B)=Sof(H58A)=Sof(H58B)=Sof(H58C)=Sof(C61A)=Sof(H61A)=
 Sof(H61B)=Sof(H61C)=Sof(C52B)=Sof(H52D)=Sof(H52E)=Sof(H52F)=Sof(C54B)=
 Sof(H54D)=Sof(H54E)=Sof(H54F)=Sof(C53B)=Sof(H53D)=Sof(H53E)=Sof(H53F)=FVAR(1)
 Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=Sof(C2A)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=
 Sof(H5AC)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=1-FVAR(2)
 Sof(C2B)=Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(H4BC)=Sof(C5B)=Sof(H5BA)=Sof(H5BB)=
 Sof(H5BC)=Sof(C3B)=Sof(H3BA)=Sof(H3BB)=Sof(H3BC)=FVAR(2)
5.a Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C27(H27A,H27B,H27C), C65(H65A,H65B,H65C), C28(H28A,H28B,
 H28C), C64(H64A,H64B,H64C), C66(H66A,H66B,H66C), C62B(H62A,H62B,H62C),
 C35(H35A,H35B,H35C), C70(H70A,H70B,H70C), C69(H69A,H69B,H69C), C23(H23A,H23B,
 H23C), C13(H13A,H13B,H13C), C25(H25A,H25B,H25C), C33(H33A,H33B,H33C),
 C57B(H57A,H57B,H57C), C40(H40A,H40B,H40C), C56B(H56A,H56B,H56C), C42(H42A,H42B,
 H42C), C41(H41A,H41B,H41C), C31(H31A,H31B,H31C), C11(H11A,H11B,H11C), C73(H73A,
 H73B,H73C), C68(H68A,H68B,H68C), C60B(H60A,H60B,H60C), C8(H8A,H8B,H8C),
 C44(H44A,H44B,H44C), C32(H32A,H32B,H32C), C20(H20A,H20B,H20C), C16(H16A,H16B,
 H16C), C45(H45A,H45B,H45C), C17(H17A,H17B,H17C), C21(H21A,H21B,H21C), C74(H74A,
 H74B,H74C), C36(H36A,H36B,H36C), C19(H19A,H19B,H19C), C72(H72A,H72B,H72C),
 C15(H15A,H15B,H15C), C24(H24A,H24B,H24C), C37(H37A,H37B,H37C), C46(H46A,H46B,
 H46C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C12(H12A,H12B,H12C), C9(H9A,
 H9B,H9C), C7(H7A,H7B,H7C), C50(H50A,H50B,H50C), C58B(H58A,H58B,H58C),
 C61A(H61A,H61B,H61C), C4B(H4BA,H4BB,H4BC), C5B(H5BA,H5BB,H5BC), C3B(H3BA,H3BB,
 H3BC), C52A(H52A,H52B,H52C), C54A(H54A,H54B,H54C), C53A(H53A,H53B,H53C),
 C1AA(H1AA,H1AB,H1AC), C57A(H57D,H57E,H57F), C60A(H60D,H60E,H60F), C56A(H56D,
 H56E,H56F), C61B(H61D,H61E,H61F), C52B(H52D,H52E,H52F), C54B(H54D,H54E,H54F),
 C58A(H58D,H58E,H58F), C53B(H53D,H53E,H53F), C4A(H4AA,H4AB,H4AC), C5A(H5AA,H5AB,
 H5AC), C3A(H3AA,H3AB,H3AC)
;
_olex2_exptl_crystal_mounting_method 'mounted in paratone oil'
_olex2_submission_special_instructions 'No special instructions were received'