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_1552518
_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         'C27 H55 Mn N2 P4 Si'
_chemical_formula_sum            'C27 H55 Mn N2 P4 Si'
_chemical_formula_weight         614.64
_space_group_crystal_system      orthorhombic
_space_group_IT_number           56
_space_group_name_Hall           '-P 2ab 2ac'
_space_group_name_H-M_alt        'P c c n'
_symmetry_space_group_name_Hall  '-P 2ab 2ac'
_symmetry_space_group_name_H-M   'P c c n'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-2-8
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-08-09 deposited with the CCDC.    2019-10-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   30.089(3)
_cell_length_b                   12.8432(11)
_cell_length_c                   17.3407(15)
_cell_measurement_reflns_used    6258
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.842
_cell_measurement_theta_min      2.349
_cell_volume                     6701.1(11)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.994
_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  0.0902
_diffrn_reflns_av_unetI/netI     0.0614
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            43355
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.454
_diffrn_reflns_theta_min         1.354
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.639
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5845
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;   
 'SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0664 before and 0.0555 after correction.
The Ratio of minimum to maximum transmission is 0.7841.
The \l/2 correction factor is 0.00150.'
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.218
_exptl_crystal_description       block
_exptl_crystal_F_000             2640
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.384
_refine_diff_density_min         -1.026
_refine_diff_density_rms         0.107
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.208
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     454
_refine_ls_number_reflns         6872
_refine_ls_number_restraints     898
_refine_ls_restrained_S_all      1.164
_refine_ls_R_factor_all          0.1543
_refine_ls_R_factor_gt           0.1030
_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^)+(0.0535P)^2^+41.5374P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2048
_refine_ls_wR_factor_ref         0.2289
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4578
_reflns_number_total             6872
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04513a3.cif
_cod_data_source_block           MnHSiPh_NHC_iPr
_cod_original_cell_volume        6701.0(10)
_cod_database_code               1552518
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.883
_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. Shared sites
{P3, P3B}
{P4, P4B}
3. Restrained distances
 P4B-Mn1 \\sim Mn1-P4 \\sim Mn1-P2A
 with sigma of 0.005
 P1A-Mn1 \\sim P1B-Mn1 \\sim P1-Mn1
 with sigma of 0.005
 P2-Mn1 \\sim P2B-Mn1 \\sim P3A-Mn1
 with sigma of 0.005
4. Uiso/Uaniso restraints and constraints
Uanis(P2A) = Uanis(P4)
Uanis(C22A) = Uanis(C21)
Uanis(C16A) = Uanis(C18)
Uanis(C16) = Uanis(C18A)
Uanis(C26) = Uanis(C21A)
Uanis(C20A) = Uanis(C27)
Uanis(C26A) = Uanis(C23)
Uanis(C25A) = Uanis(C22)
Uanis(C23A) = Uanis(C20)
Uanis(C17A) = Uanis(C17)
Uanis(P1) = Uanis(P1A)
Uanis(P3A) = Uanis(P2)
Uanis(C26B) = Uanis(C27)
Uanis(C27B) = Uanis(C21A)
Uanis(P4B) = Uanis(P2A)
Uanis(C25B) = Uanis(C25)
Uanis(C24B) = Uanis(C24)
Uanis(C23B) = Uanis(C22)
Uanis(C22B) = Uanis(C26A)
Uanis(C20) = Uanis(C21B)
Uanis(C20B) = Uanis(C21)
Uanis(P2) = Uanis(P2B)
Uanis(C19B) = Uanis(C19)
Uanis(C18) = Uanis(C18B)
Uanis(C17B) = Uanis(C16)
Uanis(C16B) = Uanis(C17)
Uanis(P1) = Uanis(P1B)
Uanis(P3B) = Uanis(P3) = Uanis(P4A)
Uanis(P3B) = Uanis(P1A)
Uanis(C22) = Uanis(C19)
5. 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
6. Same fragment restrains
{P1A, P2A, C16A, C17A, C18A, C19A, C20A, C21A} sigma for 1-2: 0.002, 1-3: 0.004
as
{P1, P2, C16, C17, C18, C19, C20, C21}
{P1A, P2A, C17A, C16A, C18A, C19A, C20A, C21A} sigma for 1-2: 0.002, 1-3: 0.004
as
{P3, P4, C22, C23, C24, C25, C26, C27}
{P1A, P2A, C17A, C16A, C18A, C19A, C20A, C21A} sigma for 1-2: 0.002, 1-3: 0.004
as
{P3A, P4A, C22A, C23A, C24A, C25A, C26A, C27A}
{P1A, P2A, C16A, C17A, C18A, C19A, C21A, C20A} sigma for 1-2: 0.002, 1-3: 0.004
as
{P1B, P2B, C16B, C17B, C18B, C19B, C20B, C21B}
{P1A, P2A, C17A, C16A, C18A, C19A, C21A, C20A} sigma for 1-2: 0.002, 1-3: 0.004
as
{P3B, P4B, C22B, C23B, C24B, C25B, C26B, C27B}
7. Others
 1*[Sof(P1)+Sof(P2)+Sof(C16)+Sof(H16A)+Sof(H16B)+Sof(H16C)+Sof(C17)+Sof(H17B)+
 Sof(H17C)+Sof(H17A)+Sof(C18)+Sof(H18B)+Sof(H18A)+Sof(C19)+Sof(H19A)+Sof(H19B)+
 Sof(C20)+Sof(H20A)+Sof(H20B)+Sof(H20C)+Sof(C21)+Sof(H21C)+Sof(H21A)+Sof(H21B)+
 Sof(P3)+Sof(P4)+Sof(C22)+Sof(H22A)+Sof(H22B)+Sof(H22C)+Sof(C23)+Sof(H23A)+
 Sof(H23B)+Sof(H23C)+Sof(C24)+Sof(H24B)+Sof(H24A)+Sof(C25)+Sof(H25A)+Sof(H25B)+
 Sof(C26)+Sof(H26A)+Sof(H26B)+Sof(H26C)+Sof(C27)+Sof(H27A)+Sof(H27B)+Sof(H27C)]+
 1*[Sof(P1A)+Sof(P2A)+Sof(P3A)+Sof(P4A)+Sof(C22A)+Sof(H22F)+Sof(H22E)+Sof(H22D)+
 Sof(C23A)+Sof(H23D)+Sof(H23E)+Sof(H23F)+Sof(C24A)+Sof(H24C)+Sof(H24D)+
 Sof(C25A)+Sof(H25D)+Sof(H25C)+Sof(C26A)+Sof(H26D)+Sof(H26E)+Sof(H26F)+
 Sof(C27A)+Sof(H27F)+Sof(H27D)+Sof(H27E)+Sof(C16A)+Sof(H16D)+Sof(H16E)+
 Sof(H16F)+Sof(C17A)+Sof(H17E)+Sof(H17D)+Sof(H17F)+Sof(C18A)+Sof(H18C)+
 Sof(H18D)+Sof(C19A)+Sof(H19C)+Sof(H19D)+Sof(C20A)+Sof(H20D)+Sof(H20E)+
 Sof(H20F)+Sof(C21A)+Sof(H21F)+Sof(H21D)+Sof(H21E)]+1*[Sof(P1B)+Sof(P2B)+
 Sof(C16B)+Sof(H16H)+Sof(H16G)+Sof(H16I)+Sof(C17B)+Sof(H17G)+Sof(H17H)+
 Sof(H17I)+Sof(C18B)+Sof(H18E)+Sof(H18F)+Sof(C19B)+Sof(H19E)+Sof(H19F)+
 Sof(C20B)+Sof(H20G)+Sof(H20H)+Sof(H20I)+Sof(C21B)+Sof(H21G)+Sof(H21H)+
 Sof(H21I)+Sof(P3B)+Sof(P4B)+Sof(C22B)+Sof(H22G)+Sof(H22H)+Sof(H22I)+Sof(C23B)+
 Sof(H23G)+Sof(H23H)+Sof(H23I)+Sof(C24B)+Sof(H24E)+Sof(H24F)+Sof(C25B)+
 Sof(H25E)+Sof(H25F)+Sof(C26B)+Sof(H26G)+Sof(H26H)+Sof(H26I)+Sof(C27B)+
 Sof(H27I)+Sof(H27G)+Sof(H27H)]=1 with esd of 0
 Sof(P1)=Sof(P2)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C17)=Sof(H17B)=
 Sof(H17C)=Sof(H17A)=Sof(C18)=Sof(H18B)=Sof(H18A)=Sof(C19)=Sof(H19A)=Sof(H19B)=
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C21)=Sof(H21C)=Sof(H21A)=Sof(H21B)=
 Sof(P3)=Sof(P4)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C23)=Sof(H23A)=
 Sof(H23B)=Sof(H23C)=Sof(C24)=Sof(H24B)=Sof(H24A)=Sof(C25)=Sof(H25A)=Sof(H25B)=
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=
 FVAR(1)
 Sof(P1A)=Sof(P2A)=Sof(P3A)=Sof(P4A)=Sof(C22A)=Sof(H22F)=Sof(H22E)=Sof(H22D)=
 Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C24A)=Sof(H24C)=Sof(H24D)=
 Sof(C25A)=Sof(H25D)=Sof(H25C)=Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=
 Sof(C27A)=Sof(H27F)=Sof(H27D)=Sof(H27E)=Sof(C16A)=Sof(H16D)=Sof(H16E)=
 Sof(H16F)=Sof(C17A)=Sof(H17E)=Sof(H17D)=Sof(H17F)=Sof(C18A)=Sof(H18C)=
 Sof(H18D)=Sof(C19A)=Sof(H19C)=Sof(H19D)=Sof(C20A)=Sof(H20D)=Sof(H20E)=
 Sof(H20F)=Sof(C21A)=Sof(H21F)=Sof(H21D)=Sof(H21E)=FVAR(2)
 Sof(P1B)=Sof(P2B)=Sof(C16B)=Sof(H16H)=Sof(H16G)=Sof(H16I)=Sof(C17B)=Sof(H17G)=
 Sof(H17H)=Sof(H17I)=Sof(C18B)=Sof(H18E)=Sof(H18F)=Sof(C19B)=Sof(H19E)=
 Sof(H19F)=Sof(C20B)=Sof(H20G)=Sof(H20H)=Sof(H20I)=Sof(C21B)=Sof(H21G)=
 Sof(H21H)=Sof(H21I)=Sof(P3B)=Sof(P4B)=Sof(C22B)=Sof(H22G)=Sof(H22H)=Sof(H22I)=
 Sof(C23B)=Sof(H23G)=Sof(H23H)=Sof(H23I)=Sof(C24B)=Sof(H24E)=Sof(H24F)=
 Sof(C25B)=Sof(H25E)=Sof(H25F)=Sof(C26B)=Sof(H26G)=Sof(H26H)=Sof(H26I)=
 Sof(C27B)=Sof(H27I)=Sof(H27G)=Sof(H27H)=FVAR(3)
8.a Ternary CH refined with riding coordinates:
 C7(H7)
8.b Secondary CH2 refined with riding coordinates:
 C18(H18B,H18A), C19(H19A,H19B), C24(H24B,H24A), C25(H25A,H25B), C24A(H24C,
 H24D), C25A(H25D,H25C), C18A(H18C,H18D), C19A(H19C,H19D), C18B(H18E,H18F),
 C19B(H19E,H19F), C24B(H24E,H24F), C25B(H25E,H25F)
8.c Me refined with riding coordinates:
 C27B(H27I,H27G,H27H)
8.d Aromatic/amide H refined with riding coordinates:
 C2(H1A), C3(H3), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15)
8.e Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C16(H16A,
 H16B,H16C), C17(H17B,H17C,H17A), C20(H20A,H20B,H20C), C21(H21C,H21A,H21B),
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C), C22A(H22F,H22E,H22D), C23A(H23D,H23E,H23F), C26A(H26D,H26E,H26F),
 C27A(H27F,H27D,H27E), C16A(H16D,H16E,H16F), C17A(H17E,H17D,H17F), C20A(H20D,
 H20E,H20F), C21A(H21F,H21D,H21E), C16B(H16H,H16G,H16I), C17B(H17G,H17H,H17I),
 C20B(H20G,H20H,H20I), C21B(H21G,H21H,H21I), C22B(H22G,H22H,H22I), C23B(H23G,
 H23H,H23I), C26B(H26G,H26H,H26I)
;
_shelx_res_checksum              61858
_olex2_submission_special_instructions 'No special instructions were received'