Bimetallic Mechanism for Alkyne Cyclotrimerization with a Two-Coordinate Fe Precatalyst
Witzke, Ryan J.; Hait, Diptarka; Chakarawet, Khetpakorn; Head-Gordon, Martin; Tilley, T. Don; ACS Catalysis  (2020) 7800–; doi:10.1021/acscatal.0c01828

data_4517832
_publ_section_title
;
 Bimetallic Mechanism for Alkyne Cyclotrimerization with a Two-Coordinate
 Fe Precatalyst
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              7800
_journal_paper_doi               10.1021/acscatal.0c01828
_journal_year                    2020
_chemical_formula_moiety         'C21 H36 Fe N Si'
_chemical_formula_sum            'C21 H36 Fe N Si'
_chemical_formula_weight         386.45
_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-11-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   22.1414(16)
_cell_length_b                   11.2865(9)
_cell_length_c                   17.5402(14)
_cell_measurement_reflns_used    9975
_cell_measurement_temperature    100
_cell_measurement_theta_max      20.57
_cell_measurement_theta_min      2.32
_cell_volume                     4383.3(6)
_computing_cell_refinement       'SAINT V8.34A Bruker-AXS, Madison WI'
_computing_data_collection       'Bruker APEX2 Bruker-AXS, Madison WI'
_computing_data_reduction        'SAINT V8.34A Bruker-AXS, Madison WI'
_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
_diffrn_detector_area_resol_mean 8.366
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0932
_diffrn_reflns_av_unetI/netI     0.0283
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            71779
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        20.920
_diffrn_reflns_theta_max         20.920
_diffrn_reflns_theta_min         1.839
_diffrn_source                   'microfocus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.745
_exptl_absorpt_correction_T_max  0.7446
_exptl_absorpt_correction_T_min  0.5410
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1359 before and 0.0922 after correction. The Ratio of minimum to maximum transmission is 0.7266. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.171
_exptl_crystal_description       plate
_exptl_crystal_F_000             1672
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.917
_refine_diff_density_min         -0.837
_refine_diff_density_rms         0.163
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.294
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     226
_refine_ls_number_reflns         2328
_refine_ls_number_restraints     72
_refine_ls_restrained_S_all      1.293
_refine_ls_R_factor_all          0.1522
_refine_ls_R_factor_gt           0.1452
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+169.6055P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3275
_refine_ls_wR_factor_ref         0.3304
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2114
_reflns_number_total             2328
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c01828_si_005.cif
_cod_data_source_block           rjw_2_064_0m
_cod_database_code               4517832
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.929
_shelx_estimated_absorpt_t_min   0.830
_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. Uiso/Uaniso restraints and constraints
Uanis(C3) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C19)
\\sim Ueq, Uanis(C20) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C5) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C2) \\sim Ueq, Uanis(C1) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C13) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C9) \\sim Ueq, Uanis(C12) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C8) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3.a Ternary CH refined with riding coordinates:
 C16(H16), C13(H13)
3.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C2(H2A,H2B)
3.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C10(H10), C9(H9)
3.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C14(H14A,H14B,H14C), C6(H6A,H6B,H6C), C19(H19A,H19B,
 H19C), C18(H18A,H18B,H18C), C17(H17A,H17B,H17C), C21(H21A,H21B,H21C), C15(H15A,
 H15B,H15C), C1(H1A,H1B,H1C)
;
_olex2_submission_special_instructions 'No special instructions were received'