Iron-Catalyzed Trimerization of Terminal Alkynes Enabled by Pyrimidinediimine Ligands: A Regioselective Method for the Synthesis of 1,3,5-Substituted Arenes
Doll, Julianna S.; Eichelmann, Robert; Hertwig, Leif E.; Bender, Thilo; Kohler, Vincenz J.; Bill, Eckhard; Wadepohl, Hubert; Roşca, Dragoş-Adrian; ACS Catalysis  (2021) 5593–5600; doi:10.1021/acscatal.1c00978

data_4518617
_publ_section_title
;
 Iron-Catalyzed Trimerization of Terminal Alkynes Enabled by
 Pyrimidinediimine Ligands: A Regioselective Method for the Synthesis of
 1,3,5-Substituted Arenes
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              5593
_journal_page_last               5600
_journal_paper_doi               10.1021/acscatal.1c00978
_journal_year                    2021
_chemical_formula_sum            'C47 H68 Fe N6'
_chemical_formula_weight         772.92
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ro_dr33
_audit_creation_date             2020-12-02
_audit_creation_method
;
encif (version 1.123)

encifer (version_id = 274361.64)

Olex2 1.3
(compiled 2020.12.01 svn.r5f60950 for OlexSys, GUI svn.r6226)
;
_audit_update_record
'02.12.2020 13:48:11 CET UTC+01:00  encif 1.123'
_cell_angle_alpha                76.8308(19)
_cell_angle_beta                 89.000(2)
_cell_angle_gamma                85.8243(19)
_cell_formula_units_Z            2
_cell_length_a                   10.5970(3)
_cell_length_b                   11.7540(2)
_cell_length_c                   18.0639(5)
_cell_measurement_reflns_used    15588
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      31.0730
_cell_measurement_theta_min      2.9360
_cell_volume                     2185.00(10)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_publication_material
'encif (Wadepohl, 2009-20); encifer (Allen et al., 2004)'
_computing_structure_refinement  'SHELXL-20xx (Sheldrick, 2015)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_temperature      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.950
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -92.00  -2.00   0.50   15.00    --  -23.50 -57.00 -90.00  180
  2  \w      5.00 103.00   0.50   15.00    --   30.69  38.00  30.00  196
  3  \w      1.00 101.00   0.50   15.00    --   30.69  77.00-150.00  200
  4  \w    -20.00  73.00   0.50   15.00    --   30.69 -99.00 -90.00  186
  5  \w     -8.00  49.00   0.50   15.00    --   30.69 -38.00  90.00  114
  6  \w     59.00  99.00   0.50   15.00    --   30.69  77.00  30.00   80
  7  \w      2.00 101.00   0.50   15.00    --   30.69  77.00 -90.00  198
  8  \w      6.00  51.00   0.50   15.00    --   30.69  77.00 150.00   90
  9  \w     67.00 101.00   0.50   15.00    --   30.69  77.00 150.00   68
 10  \w     33.00  73.00   0.50   15.00    --   30.69 -99.00-180.00   80
 11  \w    -19.00  73.00   0.50   15.00    --   30.69 -99.00  30.00  184
 12  \w      4.00  51.00   0.50   15.00    --   30.69  77.00   0.00   94
 13  \w      1.00  34.00   0.50   15.00    --   30.69  77.00  90.00   66
 14  \w     11.00  41.00   0.50   15.00    --   30.69  57.00-120.00   60
 15  \w    -23.00  48.00   0.50   15.00    --   30.69 -57.00 -90.00  142
 16  \w    -26.00  18.00   0.50   15.00    --   30.69 -57.00-180.00   88
 17  \w     12.00  98.00   0.50   15.00    --   30.69  38.00 150.00  172
 18  \w    -32.00  48.00   0.50   15.00    --   30.69 -57.00  60.00  160
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'Agilent SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0617356000
_diffrn_orient_matrix_UB_12      -0.0166101000
_diffrn_orient_matrix_UB_13      0.0112154000
_diffrn_orient_matrix_UB_21      -0.0258266000
_diffrn_orient_matrix_UB_22      0.0555216000
_diffrn_orient_matrix_UB_23      -0.0202250000
_diffrn_orient_matrix_UB_31      -0.0050744000
_diffrn_orient_matrix_UB_32      -0.0223989000
_diffrn_orient_matrix_UB_33      -0.0330363000
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~2,3~
_diffrn_reflns_av_R_equivalents  0.0556
_diffrn_reflns_av_unetI/netI     0.0574
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.950
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            72683
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.950
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         34.208
_diffrn_reflns_theta_min         2.532
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.384
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.686
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.175
_exptl_crystal_description       irregular
_exptl_crystal_F_000             836
_exptl_crystal_size_max          0.187
_exptl_crystal_size_mid          0.170
_exptl_crystal_size_min          0.072
_platon_squeeze_details
'see: P. v. d. Sluis, A. L. Spek,  Acta Cryst. 1990, A46, 194.'
_refine_diff_density_max         0.394
_refine_diff_density_min         -0.336
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     560
_refine_ls_number_reflns         17217
_refine_ls_number_restraints     311
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0771
_refine_ls_R_factor_gt           0.0501
_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^)+(0.0490P)^2^+0.4050P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1114
_refine_ls_wR_factor_ref         0.1239
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12431
_reflns_number_total             17217
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00978_si_003.cif
_cod_data_source_block           ro_dr33_sq
_cod_original_cell_volume        2185.00(9)
_cod_database_code               4518617
_audit_block_refno               3682
_audit_block_usercomment         'DAR-DA--450, irregular, black'
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     32.50
_shelxl_version_number           2018/3
_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. Shared sites
{N4A, C17B}
{N4B, C17A}
3. Uiso/Uaniso restraints and constraints
C17A \\sim C17B \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7
\\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15
\\sim C16 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24
\\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32
\\sim C41A \\sim C42A \\sim C43A \\sim C44A \\sim C45A \\sim C46A \\sim C47A
\\sim C48A \\sim C49A \\sim C50A \\sim C41B \\sim C42B \\sim C43B \\sim C44B
\\sim C45B \\sim C46B \\sim C47B \\sim C48B \\sim C49B \\sim C50B \\sim N5A
\\sim N6A \\sim N5B \\sim N6B \\sim N1 \\sim N2 \\sim N3 \\sim N4A \\sim N4B
\\sim Fe1A \\sim Fe1B: within 1A with sigma of 0.01 and sigma for terminal
atoms of 0.01 within 1A
Uanis(Fe1A) = Uanis(Fe1B)
Uanis(N5A) = Uanis(N5B)
Uanis(N4A) = Uanis(C17B)
Uanis(N4B) = Uanis(C17A)
4. Rigid body (RIGU) restrains
 Fe1A, N5A, N6A, Fe1B, N5B, N6B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C41A, C42A, C43A, C44A, C45A, C46A, C47A, C48A, C49A, C50A, C41B, C42B, C43B,
 C44B, C45B, C46B, C47B, C48B, C49B, C50B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{Fe1A, N5A, N6A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{Fe1B, N5B, N6B}
{C41A, C42A, C43A, C44A, C45A, C46A, C47A, C48A, C49A, C50A} sigma for 1-2:
0.02, 1-3: 0.04
as in
{C41B, C42B, C43B, C44B, C45B, C46B, C47B, C48B, C49B, C50B}
6. Others
 Sof(C41B)=Sof(C42B)=Sof(H42C)=Sof(H42D)=Sof(C43B)=Sof(H43B)=Sof(C44B)=
 Sof(H44C)=Sof(H44D)=Sof(C45B)=Sof(H45B)=Sof(C46B)=Sof(H46C)=Sof(H46D)=
 Sof(C47B)=Sof(H47C)=Sof(H47D)=Sof(C48B)=Sof(H48B)=Sof(C49B)=Sof(H49C)=
 Sof(H49D)=Sof(C50B)=Sof(H50C)=Sof(H50D)=1-FVAR(1)
 Sof(C41A)=Sof(C42A)=Sof(H42A)=Sof(H42B)=Sof(C43A)=Sof(H43A)=Sof(C44A)=
 Sof(H44A)=Sof(H44B)=Sof(C45A)=Sof(H45A)=Sof(C46A)=Sof(H46A)=Sof(H46B)=
 Sof(C47A)=Sof(H47A)=Sof(H47B)=Sof(C48A)=Sof(H48A)=Sof(C49A)=Sof(H49A)=
 Sof(H49B)=Sof(C50A)=Sof(H50A)=Sof(H50B)=FVAR(1)
 Sof(C17B)=Sof(H17B)=Sof(N4B)=1-FVAR(2)
 Sof(N4A)=Sof(C17A)=Sof(H17A)=FVAR(2)
 Sof(Fe1B)=Sof(N5B)=Sof(N6B)=1-FVAR(3)
 Sof(Fe1A)=Sof(N5A)=Sof(N6A)=FVAR(3)
7.a Ternary CH refined with riding coordinates:
 C7(H7), C14(H14), C23(H23), C30(H30), C43A(H43A), C45A(H45A), C48A(H48A),
 C43B(H43B), C45B(H45B), C48B(H48B)
7.b Secondary CH2 refined with riding coordinates:
 C42A(H42A,H42B), C44A(H44A,H44B), C46A(H46A,H46B), C47A(H47A,H47B), C49A(H49A,
 H49B), C50A(H50A,H50B), C42B(H42C,H42D), C44B(H44C,H44D), C46B(H46C,H46D),
 C47B(H47C,H47D), C49B(H49C,H49D), C50B(H50C,H50D)
7.c Aromatic/amide H refined with riding coordinates:
 C17A(H17A), C17B(H17B), C10(H10), C11(H11), C12(H12), C26(H26), C27(H27),
 C28(H28)
7.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C15(H15A,H15B,H15C),
 C16(H16A,H16B,H16C), C20(H20A,H20B,H20C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C)
;
_shelx_hkl_checksum              14476
_shelx_fab_checksum              12063
_platon_squeeze_void_probe_radius 1.20
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.232
_oxdiff_exptl_absorpt_empirical_full_min 0.876
_shelx_res_checksum              65361
_cell_oxdiff_measurement_reflns_used 15588