Interconversion and reactivity of manganese silyl, silylene, and silene complexes
Price, Jeffrey S.; Emslie, David J. H.; Chemical Science  (2019) –; doi:10.1039/C9SC04513A

data_1552515
_publ_section_title
;
 Interconversion and reactivity of manganese silyl, silylene, and silene
 complexes
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC04513A
_journal_year                    2019
_chemical_formula_moiety         'C25 H59 Mn N2 P4 Si'
_chemical_formula_sum            'C25 H59 Mn N2 P4 Si'
_chemical_formula_weight         594.65
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             17-10-17
_audit_creation_method           'STOE X-RED'
_audit_update_record
;
2019-08-09 deposited with the CCDC.    2019-10-23 downloaded from the CCDC.
;
_cell_angle_alpha                70.86(3)
_cell_angle_beta                 84.97(3)
_cell_angle_gamma                87.74(3)
_cell_formula_units_Z            2
_cell_length_a                   10.279(2)
_cell_length_b                   12.666(3)
_cell_length_c                   13.295(3)
_cell_measurement_reflns_used    9943
_cell_measurement_temperature    100
_cell_measurement_theta_max      29.39
_cell_measurement_theta_min      1.70
_cell_volume                     1628.8(7)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 6.67
_diffrn_detector_type            STOE
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_details
;
237 frames, detector distance = 100 mm
;
_diffrn_measurement_device       '2-circle goniometer'
_diffrn_measurement_device_type  'Stoe IPDS 2'
_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  0.0638
_diffrn_reflns_av_unetI/netI     0.1986
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            14976
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.000
_diffrn_reflns_theta_min         1.933
_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
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.655
_exptl_absorpt_correction_T_max  0.9384
_exptl_absorpt_correction_T_min  0.8803
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details
;
'X-SHAPE version 2.05 and X-RED32 version 1.10,
STOE & Cie GmbH: Darmstadt, Germany, 2004'
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.212
_exptl_crystal_description       block
_exptl_crystal_F_000             644
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.409
_refine_diff_density_min         -0.290
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.590
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     371
_refine_ls_number_reflns         7015
_refine_ls_number_restraints     52
_refine_ls_restrained_S_all      0.587
_refine_ls_R_factor_all          0.1071
_refine_ls_R_factor_gt           0.0363
_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^)] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0407
_refine_ls_wR_factor_ref         0.0511
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3543
_reflns_number_total             7015
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04513a3.cif
_cod_data_source_block           MnHSinBu_NHC_iPr
_cod_original_cell_volume        1628.9(6)
_cod_database_code               1552515
_audit_contact_author            'J. Richter'
_shelx_shelxl_version_number     2016/6
_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
2. Restrained distances
 P4A-Mn1 \\sim Mn1-P3
 with sigma of 0.005
 P2A-Mn1 \\sim Mn1-P2
 with sigma of 0.005
 P1A-Mn1 \\sim Mn1-P4
 with sigma of 0.005
 P3A-Mn1 \\sim Mn1-P1
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(P1) = Uanis(P3A)
Uanis(P4) = Uanis(P1A)
Uanis(P2A) = Uanis(P2)
Uanis(C19) = Uanis(C17A)
Uanis(C18) = Uanis(C19A)
Uanis(C18A) = Uanis(C17)
Uanis(C24) = Uanis(C15A)
Uanis(C25) = Uanis(C14A)
Uanis(P1A) = Uanis(P4)
Uanis(P3) = Uanis(P4A)
Uanis(C21) = Uanis(C23A)
Uanis(C20) = Uanis(C24A)
Uanis(C22) = Uanis(C25A)
Uanis(C16A) = Uanis(C23)
Uanis(C15A) = Uanis(C24)
Uanis(C16) = Uanis(C22A)
Uanis(C21A) = Uanis(C15)
Uanis(C14) = Uanis(C20A)
4. Same fragment restrains
{P1, P2, C14, C15, C16, C17, C18, C19} sigma for 1-2: 0.002, 1-3: 0.004
as
{P1A, P2A, C14A, C15A, C16A, C17A, C18A, C19A}
{P1, P2, C14, C15, C16, C17, C18, C19} sigma for 1-2: 0.002, 1-3: 0.004
as
{P3A, P4A, C20A, C21A, C22A, C23A, C24A, C25A}
5. Others
 Sof(P1A)=Sof(P2A)=Sof(C14A)=Sof(H14B)=Sof(H14C)=Sof(H14A)=Sof(C15A)=Sof(H15A)=
 Sof(H15B)=Sof(H15C)=Sof(C16A)=Sof(H16A)=Sof(H16B)=Sof(C17A)=Sof(H17A)=
 Sof(H17B)=Sof(C18A)=Sof(H18C)=Sof(H18A)=Sof(H18B)=Sof(C19A)=Sof(H19A)=
 Sof(H19B)=Sof(H19C)=Sof(P3A)=Sof(P4A)=Sof(C20A)=Sof(H20A)=Sof(H20B)=Sof(H20C)=
 Sof(C21A)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22A)=Sof(H22A)=Sof(H22B)=
 Sof(C23A)=Sof(H23A)=Sof(H23B)=Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(H24C)=
 Sof(C25A)=Sof(H25A)=Sof(H25B)=Sof(H25C)=1-FVAR(1)
 Sof(P1)=Sof(P2)=Sof(P3)=Sof(P4)=Sof(C14)=Sof(H14D)=Sof(H14E)=Sof(H14F)=
 Sof(C15)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16)=Sof(H16C)=Sof(H16D)=Sof(C17)=
 Sof(H17C)=Sof(H17D)=Sof(C18)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C19)=Sof(H19D)=
 Sof(H19E)=Sof(H19F)=Sof(C20)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C21)=Sof(H21D)=
 Sof(H21E)=Sof(H21F)=Sof(C22)=Sof(H22C)=Sof(H22D)=Sof(C23)=Sof(H23C)=Sof(H23D)=
 Sof(C24)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C25)=Sof(H25D)=Sof(H25E)=Sof(H25F)=
 FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C4(H4), C7(H7)
6.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C16(H16C,H16D), C17(H17C,
 H17D), C22(H22C,H22D), C23(H23C,H23D), C16A(H16A,H16B), C17A(H17A,H17B),
 C22A(H22A,H22B), C23A(H23A,H23B)
6.c Me refined with riding coordinates:
 C14A(H14B,H14C,H14A), C15A(H15A,H15B,H15C), C24A(H24A,H24B,H24C), C25A(H25A,
 H25B,H25C)
6.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3)
6.e Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C13(H13A,
 H13B,H13C), C14(H14D,H14E,H14F), C15(H15D,H15E,H15F), C18(H18D,H18E,H18F),
 C19(H19D,H19E,H19F), C20(H20D,H20E,H20F), C21(H21D,H21E,H21F), C24(H24D,H24E,
 H24F), C25(H25D,H25E,H25F), C18A(H18C,H18A,H18B), C19A(H19A,H19B,H19C),
 C20A(H20A,H20B,H20C), C21A(H21A,H21B,H21C)
;
_shelx_res_checksum              76600
_olex2_submission_special_instructions 'No special instructions were received'