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_1551052
_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         'C36 H81 Mo O13 Si3'
_chemical_formula_sum            'C36 H81 Mo O13 Si3'
_chemical_formula_weight         902.21
_chemical_name_systematic        '[Mo(O)(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                 103.0700(10)
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   18.0787(5)
_cell_length_b                   23.6043(8)
_cell_length_c                   36.5549(12)
_cell_measurement_reflns_used    9586
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.47
_cell_measurement_theta_min      2.34
_cell_volume                     15195.2(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 APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0652
_diffrn_reflns_av_unetI/netI     0.0334
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            308685
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         2.223
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.380
_exptl_absorpt_correction_T_max  0.8620
_exptl_absorpt_correction_T_min  0.8203
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0708 before and 0.0659 after correction.
The Ratio of minimum to maximum transmission is 0.9516.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.183
_exptl_crystal_description       needle
_exptl_crystal_F_000             5820
_exptl_crystal_preparation       'reaction of Mo[OSi(OtBu)3]3 with CO2'
_exptl_crystal_recrystallization_method
'slow evaporation of a solution in pentane at -40 degrees Celsius'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.12
_refine_diff_density_max         2.035
_refine_diff_density_min         -1.506
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1509
_refine_ls_number_reflns         26833
_refine_ls_number_restraints     144
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0638
_refine_ls_R_factor_gt           0.0444
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0300P)^2^+37.4893P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0920
_refine_ls_wR_factor_ref         0.1013
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21292
_reflns_number_total             26833
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc01955c2.cif
_cod_data_source_block           fa
_cod_original_cell_volume        15195.1(8)
_cod_database_code               1551052
_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(C49B) \\sim Ueq, Uanis(C51A) \\sim Ueq, Uanis(C0AA) \\sim Ueq,
Uanis(C52A) \\sim Ueq, Uanis(C49A) \\sim Ueq, Uanis(C50B) \\sim Ueq,
Uanis(C51B) \\sim Ueq, Uanis(C52B) \\sim Ueq, Uanis(C53A) \\sim Ueq,
Uanis(C56A) \\sim Ueq, Uanis(C54A) \\sim Ueq, Uanis(C55B) \\sim Ueq,
Uanis(C53B) \\sim Ueq, Uanis(C55A) \\sim Ueq, Uanis(C54B) \\sim Ueq,
Uanis(C56B) \\sim Ueq, Uanis(C45A) \\sim Ueq, Uanis(C48B) \\sim Ueq,
Uanis(C47B) \\sim Ueq, Uanis(C48A) \\sim Ueq, Uanis(C45B) \\sim Ueq,
Uanis(C46B) \\sim Ueq, Uanis(C46A) \\sim Ueq, Uanis(C47A) \\sim Ueq: with sigma
of 0.001 and sigma for terminal atoms of 0.001
Uanis(Si5) = Uanis(O24A) = Uanis(O23A) = Uanis(O22A) = Uanis(C49B) =
Uanis(C53A) = Uanis(C45A) = Uanis(C51A) = Uanis(C48B) = Uanis(C0AA) =
Uanis(C56A) = Uanis(C54A) = Uanis(C55B) = Uanis(C52A) = Uanis(C47B) =
Uanis(C48A) = Uanis(O22B) = Uanis(O23B) = Uanis(O24B) = Uanis(C53B) =
Uanis(C49A) = Uanis(C45B) = Uanis(C50B) = Uanis(C51B) = Uanis(C52B) =
Uanis(C46B) = Uanis(C46A) = Uanis(C47A) = Uanis(C55A) = Uanis(C54B) =
Uanis(C56B)
3. Others
 Sof(C44B)=Sof(H44A)=Sof(H44B)=Sof(H44C)=Sof(C42B)=Sof(H42A)=Sof(H42B)=
 Sof(H42C)=Sof(C43B)=Sof(H43A)=Sof(H43B)=Sof(H43C)=1-FVAR(1)
 Sof(C42A)=Sof(H42D)=Sof(H42E)=Sof(H42F)=Sof(C43A)=Sof(H43D)=Sof(H43E)=
 Sof(H43F)=Sof(C44A)=Sof(H44D)=Sof(H44E)=Sof(H44F)=FVAR(1)
 Sof(O24A)=Sof(O23A)=Sof(O22A)=Sof(C53A)=Sof(C45A)=Sof(C51A)=Sof(H51A)=
 Sof(H51B)=Sof(H51C)=Sof(C0AA)=Sof(H0AA)=Sof(H0AB)=Sof(H0AC)=Sof(C56A)=
 Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(C54A)=Sof(H54A)=Sof(H54B)=Sof(H54C)=
 Sof(C52A)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C48A)=Sof(H48G)=Sof(H48H)=
 Sof(H48I)=Sof(C49A)=Sof(C46A)=Sof(H46G)=Sof(H46H)=Sof(H46I)=Sof(C47A)=
 Sof(H47G)=Sof(H47H)=Sof(H47I)=Sof(C55A)=Sof(H55D)=Sof(H55E)=Sof(H55F)=1-FVAR(2)
 Sof(C49B)=Sof(C48B)=Sof(H48D)=Sof(H48E)=Sof(H48F)=Sof(C55B)=Sof(H55A)=
 Sof(H55B)=Sof(H55C)=Sof(C47B)=Sof(H47D)=Sof(H47E)=Sof(H47F)=Sof(O22B)=
 Sof(O23B)=Sof(O24B)=Sof(C53B)=Sof(C45B)=Sof(C50B)=Sof(H50A)=Sof(H50B)=
 Sof(H50C)=Sof(C51B)=Sof(H51D)=Sof(H51E)=Sof(H51F)=Sof(C52B)=Sof(H52D)=
 Sof(H52E)=Sof(H52F)=Sof(C46B)=Sof(H46D)=Sof(H46E)=Sof(H46F)=Sof(C54B)=
 Sof(H54D)=Sof(H54E)=Sof(H54F)=Sof(C56B)=Sof(H56D)=Sof(H56E)=Sof(H56F)=FVAR(2)
4.a Idealised Me refined as rotating group:
 C94(H94A,H94B,H94C), C60(H60A,H60B,H60C), C95(H95A,H95B,H95C), C18(H18A,H18B,
 H18C), C74(H74A,H74B,H74C), C96(H96A,H96B,H96C), C58(H58A,H58B,H58C),
 C102(H10A,H10B,H10C), C59(H59A,H59B,H59C), C20(H20A,H20B,H20C), C88(H88A,H88B,
 H88C), C22(H22A,H22B,H22C), C16(H16A,H16B,H16C), C7(H7A,H7B,H7C), C24(H24A,
 H24B,H24C), C76(H76A,H76B,H76C), C86(H86A,H86B,H86C), C75(H75A,H75B,H75C),
 C104(H10D,H10E,H10F), C79(H79A,H79B,H79C), C28(H28A,H28B,H28C), C82(H82A,H82B,
 H82C), C87(H87A,H87B,H87C), C6(H6A,H6B,H6C), C84(H84A,H84B,H84C), C100(H10G,
 H10H,H10I), C27(H27A,H27B,H27C), C26(H26A,H26B,H26C), C19(H19A,H19B,H19C),
 C14(H14A,H14B,H14C), C103(H10J,H10K,H10L), C70(H70A,H70B,H70C), C80(H80A,H80B,
 H80C), C23(H23A,H23B,H23C), C90(H90A,H90B,H90C), C99(H99A,H99B,H99C), C71(H71A,
 H71B,H71C), C8(H8A,H8B,H8C), C40(H40A,H40B,H40C), C11(H11A,H11B,H11C),
 C48(H48A,H48B,H48C), C10(H10M,H10N,H10O), C30(H30A,H30B,H30C), C31(H31A,H31B,
 H31C), C92(H92A,H92B,H92C), C72(H72A,H72B,H72C), C15(H15A,H15B,H15C), C39(H39A,
 H39B,H39C), C63(H63A,H63B,H63C), C83(H83A,H83B,H83C), C32(H32A,H32B,H32C),
 C2(H2A,H2B,H2C), C64(H64A,H64B,H64C), C66(H66A,H66B,H66C), C78(H78A,H78B,H78C),
  C98(H98A,H98B,H98C), C38(H38A,H38B,H38C), C47(H47A,H47B,H47C), C51A(H51A,H51B,
 H51C), C48B(H48D,H48E,H48F), C62(H62A,H62B,H62C), C36(H36A,H36B,H36C), C4(H4A,
 H4B,H4C), C46(H46A,H46B,H46C), C12(H12A,H12B,H12C), C0AA(H0AA,H0AB,H0AC),
 C91(H91A,H91B,H91C), C67(H67A,H67B,H67C), C56A(H56A,H56B,H56C), C54A(H54A,H54B,
 H54C), C3(H3A,H3B,H3C), C55B(H55A,H55B,H55C), C52A(H52A,H52B,H52C), C47B(H47D,
 H47E,H47F), C34(H34A,H34B,H34C), C68(H68A,H68B,H68C), C35(H35A,H35B,H35C),
 C44B(H44A,H44B,H44C), C42B(H42A,H42B,H42C), C48A(H48G,H48H,H48I), C43B(H43A,
 H43B,H43C), C42A(H42D,H42E,H42F), C43A(H43D,H43E,H43F), C44A(H44D,H44E,H44F),
 C50B(H50A,H50B,H50C), C51B(H51D,H51E,H51F), C52B(H52D,H52E,H52F), C46B(H46D,
 H46E,H46F), C46A(H46G,H46H,H46I), C47A(H47G,H47H,H47I), C55A(H55D,H55E,H55F),
 C54B(H54D,H54E,H54F), C56B(H56D,H56E,H56F)
;
_olex2_exptl_crystal_mounting_method 'mounted in paratone oil'
_olex2_submission_special_instructions 'No special instructions were received'