Seeking Heteroatom-Rich Compounds: Synthetic and Mechanistic Studies into Iron Catalyzed Dehydrocoupling of Silanes
Gasperini, Danila; King, Andrew K.; Coles, Nathan T.; Mahon, Mary F.; Webster, Ruth L.; ACS Catalysis  (2020) 6102–6112; doi:10.1021/acscatal.0c01440

data_4517672
_publ_section_title
;
 Seeking Heteroatom-Rich Compounds: Synthetic and Mechanistic Studies into
 Iron Catalyzed Dehydrocoupling of Silanes
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              6102
_journal_page_last               6112
_journal_paper_doi               10.1021/acscatal.0c01440
_journal_year                    2020
_chemical_formula_moiety         'C62 H93 Fe2 N5, C5 H12'
_chemical_formula_sum            'C67 H105 Fe2 N5'
_chemical_formula_weight         1092.25
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-03-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.3820(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.7862(2)
_cell_length_b                   21.4855(3)
_cell_length_c                   21.9569(3)
_cell_measurement_reflns_used    12310
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      72.6670
_cell_measurement_theta_min      3.8110
_cell_volume                     6484.70(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_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_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1150
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0602
_diffrn_reflns_av_unetI/netI     0.0494
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            65093
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.993
_diffrn_reflns_theta_min         3.215
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.883
_exptl_absorpt_correction_T_max  0.74094
_exptl_absorpt_correction_T_min  0.72613
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark orange'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.119
_exptl_crystal_description       block
_exptl_crystal_F_000             2376
_exptl_crystal_size_max          0.093
_exptl_crystal_size_mid          0.093
_exptl_crystal_size_min          0.058
_exptl_crystal_size_rad          0.082
_refine_diff_density_max         0.407
_refine_diff_density_min         -0.298
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     783
_refine_ls_number_reflns         12869
_refine_ls_number_restraints     56
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.0571
_refine_ls_R_factor_gt           0.0416
_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^)+(0.0544P)^2^+0.4273P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0971
_refine_ls_wR_factor_ref         0.1039
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10322
_reflns_number_total             12869
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01440_si_001.cif
_cod_data_source_block           s20rlw39c
_cod_depositor_comments          'Adding full bibliography for 4517672.cif.'
_cod_database_code               4517672
_shelxl_version_number           2014-3
_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
 C61A-C60A \\sim C61-C60
 with sigma of 0.005
 C62-C61 \\sim C62A-C61A
 with sigma of 0.005
 C60A-C59A \\sim C60-C59
 with sigma of 0.005
 N5-C59 \\sim N5A-C59A
 with sigma of 0.005
 C67-C66 \\sim C67A-C66A \\sim C66-C65 \\sim C66A-C65A \\sim C65-C64 \\sim
C65A-C64A \\sim C64-C63 ~
 C64A-C63A
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
C67A \\sim C64A \\sim C65A \\sim C66A \\sim C63A: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.005
Uanis(C61) = Uanis(C61A)
4. Others
 Fixed Sof: N5A(0.4) H5A(0.4) C59A(0.4) H59A(0.4) H59B(0.4) C60A(0.4)
 H60A(0.4) H60B(0.4) C61A(0.4) H61A(0.4) H61B(0.4) C62A(0.4) H62A(0.4)
 H62B(0.4) H62C(0.4) C63A(0.4) H63A(0.4) H63B(0.4) H63C(0.4) C64A(0.4)
 H64A(0.4) H64B(0.4) C65A(0.4) H65A(0.4) H65B(0.4) C66A(0.4) H66A(0.4)
 H66B(0.4) C67A(0.4) H67A(0.4) H67B(0.4) H67C(0.4) N5(0.6) H5(0.6) C59(0.6)
 H59C(0.6) H59D(0.6) C61(0.6) H61C(0.6) H61D(0.6) C60(0.6) H60C(0.6) H60D(0.6)
 C62(0.6) H62D(0.6) H62E(0.6) H62F(0.6) C64(0.6) H64C(0.6) H64D(0.6) C65(0.6)
 H65C(0.6) H65D(0.6) C66(0.6) H66C(0.6) H66D(0.6) C67(0.6) H67D(0.6) H67E(0.6)
 H67F(0.6) C63(0.6) H63D(0.6) H63E(0.6) H63F(0.6)
5.a Ternary CH refined with riding coordinates:
 N5A(H5A), C12(H12), C15(H15), C24(H24), C27(H27), C41(H41), C44(H44),
 C53(H53), C56(H56), N5(H5)
5.b Secondary CH2 refined with riding coordinates:
 C59A(H59A,H59B), C60A(H60A,H60B), C61A(H61A,H61B), C64A(H64A,H64B), C65A(H65A,
 H65B), C66A(H66A,H66B), C59(H59C,H59D), C61(H61C,H61D), C60(H60C,H60D),
 C64(H64C,H64D), C65(H65C,H65D), C66(H66C,H66D)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C8(H8), C9(H9), C10(H10), C20(H20), C21(H21), C22(H22), C32(H32),
 C37(H37), C38(H38), C39(H39), C49(H49), C50(H50), C51(H51)
5.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C5(H5B,H5C,H5D), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C34(H34A,
 H34B,H34C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C45(H45A,H45B,H45C),
 C46(H46A,H46B,H46C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C57(H57A,H57B,
 H57C), C58(H58A,H58B,H58C), C62A(H62A,H62B,H62C), C63A(H63A,H63B,H63C),
 C67A(H67A,H67B,H67C), C62(H62D,H62E,H62F), C67(H67D,H67E,H67F), C63(H63D,H63E,
 H63F)
;