Isolation and structural characterization of a titanacyclopropane as key intermediate in the double aryl Grignard addition to 2-(arylethynyl)pyridine derivatives.
Foschi, Francesco; Roth, Torsten; Enders, Markus; Wadepohl, Hubert; Clot, Eric; Gade, Lutz H.; Chemical communications (Cambridge, England) 54 (2018) 2228–2231; doi:10.1039/c8cc00478a

data_7121234
_publ_section_title
;
 Isolation and structural characterization of a titanacyclopropane as key
 intermediate in the double aryl Grignard addition to
 2-(arylethynyl)pyridine derivatives.
;
_journal_issue                   18
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              2228
_journal_page_last               2231
_journal_paper_doi               10.1039/c8cc00478a
_journal_volume                  54
_journal_year                    2018
_chemical_formula_moiety         'C37 H29 F3 N2 O Ti, 1.5(C7 H8)'
_chemical_formula_sum            'C47.5 H41 F3 N2 O Ti'
_chemical_formula_weight         760.72
_chemical_properties_physical    air-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'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_ff18
_audit_creation_date             2017-02-22
_audit_creation_method
;
Olex2 1.2
(compiled Aug 10 2017 17:44:14 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-01-17 deposited with the CCDC.
2018-02-05 downloaded from the CCDC.
;
_cell_angle_alpha                104.5042(12)
_cell_angle_beta                 103.2734(10)
_cell_angle_gamma                91.6813(10)
_cell_formula_units_Z            2
_cell_length_a                   9.83402(10)
_cell_length_b                   10.87734(15)
_cell_length_c                   19.1786(3)
_cell_measurement_reflns_used    34531
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      32.1440
_cell_measurement_theta_min      3.3430
_cell_volume                     1924.83(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material
'encif (Wadepohl, 2009-17); encifer 1.5.2 (CCDC, 2016)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_environment      'perfluoro polyether oil / N~2~'
_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 0.960
_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      7.00  96.00   0.50   15.00    --   27.02  57.00-120.00  178
  2  \w    -42.00  48.00   0.50   15.00    --   27.02 -57.00  90.00  180
  3  \w     -3.00  97.00   0.50   15.00    --   27.02  77.00 120.00  200
  4  \w    -20.00  69.00   0.50   15.00    --   27.02 -99.00  30.00  178
  5  \w    -20.00  69.00   0.50   15.00    --   27.02 -99.00-150.00  178
  6  \w    -45.00  53.00   0.50   15.00    --   27.02 -38.00 -30.00  196
  7  \w      2.00  99.00   0.50   15.00    --   27.02  38.00   0.00  194
  8  \w     -3.00  97.00   0.50   15.00    --   27.02  77.00  30.00  200
  9  \w    -43.00  57.00   0.50   15.00    --   27.02 -77.00 -90.00  200
 10  \w     -3.00  97.00   0.50   15.00    --   27.02  77.00-180.00  200
 11  \w      7.00  96.00   0.50   15.00    --   27.02  57.00   0.00  178
 12  \w    -42.00  48.00   0.50   15.00    --   27.02 -57.00 -90.00  180
 13  \w    -20.00  69.00   0.50   15.00    --   27.02 -99.00 150.00  178
 14  \w      2.00  99.00   0.50   15.00    --   27.02  38.00-180.00  194
 15  \w      2.00  99.00   0.50   15.00    --   27.02  38.00 -30.00  194
 16  \w     -3.00  97.00   0.50   15.00    --   27.02  77.00 -90.00  200
 17  \f      0.00 120.00   0.50   15.00  27.02  27.02  40.00    --   240
 18  \f      0.00 120.00   0.50   15.00  27.02  27.02 -60.00    --   240
 19  \f      0.00 120.00   0.50   15.00  27.02  27.02  60.00    --   240
 20  \f    120.00 240.00   0.50   15.00  27.02  27.02 -40.00    --   240
 21  \f    120.00 213.00   0.50   15.00  27.02  27.02  40.00    --   186
 22  \f      0.00 120.00   0.50   15.00  27.02  27.02 -40.00    --   240
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0030290000
_diffrn_orient_matrix_UB_12      -0.0668494000
_diffrn_orient_matrix_UB_13      -0.0045205000
_diffrn_orient_matrix_UB_21      -0.0726730000
_diffrn_orient_matrix_UB_22      -0.0013771000
_diffrn_orient_matrix_UB_23      -0.0012080000
_diffrn_orient_matrix_UB_31      -0.0157585000
_diffrn_orient_matrix_UB_32      -0.0102428000
_diffrn_orient_matrix_UB_33      -0.0391220000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0541
_diffrn_reflns_av_unetI/netI     0.0433
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            98052
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.443
_diffrn_reflns_theta_min         2.493
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.276
_exptl_absorpt_correction_T_max  0.9546
_exptl_absorpt_correction_T_min  0.9322
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
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    1.313
_exptl_crystal_description       block
_exptl_crystal_F_000             794
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.162
_exptl_crystal_size_min          0.142
_refine_diff_density_max         0.645
_refine_diff_density_min         -0.487
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     556
_refine_ls_number_reflns         13318
_refine_ls_number_restraints     141
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.0687
_refine_ls_R_factor_gt           0.0482
_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^)+(0.0748P)^2^+0.2469P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1186
_refine_ls_wR_factor_ref         0.1257
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10506
_reflns_number_total             13318
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc00478a2.cif
_cod_data_source_block           ga_ff18_4
_cod_depositor_comments
'Adding full bibliography for 7121234--7121240.cif.'
_cod_original_cell_volume        1924.82(4)
_cod_original_formula_sum        'C47.50 H41 F3 N2 O Ti'
_cod_database_code               7121234
_audit_block_refno               2824
_audit_block_usercomment         'FF371, block, black'
_shelx_estimated_absorpt_t_max   0.973
_shelx_estimated_absorpt_t_min   0.973
_shelxl_version_number           2018/1
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C51A-C57A \\sim C51B-C57B
 with sigma of 0.02
 C52A-C57A \\sim C56A-C57A \\sim C52B-C57B \\sim C56B-C57B
 with sigma of 0.02
3. Restrained atomic chiral volume
 C51A
 fixed at 0 with sigma of 0.1
 C51B
 fixed at 0 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C51A \\sim C52A \\sim C53A \\sim C54A \\sim C55A \\sim C56A \\sim C57A \\sim
C51B \\sim C52B \\sim C53B \\sim C54B \\sim C55B \\sim C56B \\sim C57B: within
0.5A with sigma of 0.02 and sigma for terminal atoms of 0.04
5. Rigid body (RIGU) restrains
 C51A, C52A, C53A, C54A, C55A, C56A, C57A, C51B, C52B, C53B, C54B, C55B, C56B,
 C57B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C51B)=Sof(C52B)=Sof(H52B)=Sof(C53B)=Sof(H53B)=Sof(C54B)=Sof(H54B)=
 Sof(C55B)=Sof(H55B)=Sof(C56B)=Sof(H56B)=Sof(C57B)=Sof(H57D)=Sof(H57E)=
 Sof(H57F)=1-FVAR(1)
 Sof(C51A)=Sof(C52A)=Sof(H52A)=Sof(C53A)=Sof(H53A)=Sof(C54A)=Sof(H54A)=
 Sof(C55A)=Sof(H55A)=Sof(C56A)=Sof(H56A)=Sof(C57A)=Sof(H57A)=Sof(H57B)=
 Sof(H57C)=FVAR(1)
 Fixed Sof: C61(0.5) C62(0.5) H62(0.5) C63(0.5) H63(0.5) C64(0.5) H64(0.5)
 C65(0.5) H65(0.5) C66(0.5) H66(0.5) C67(0.5) H67A(0.5) H67B(0.5) H67C(0.5)
7.a Ternary CH refined with riding coordinates:
 C35(H35)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C7(H7), C8(H8), C12(H12), C13(H13), C15(H15),
 C16(H16), C19(H19), C20(H20), C22(H22), C23(H23), C25(H25), C26(H26), C27(H27),
  C28(H28), C30(H30), C31(H31), C33(H33), C34(H34), C52A(H52A), C53A(H53A),
 C54A(H54A), C55A(H55A), C56A(H56A), C52B(H52B), C53B(H53B), C54B(H54B),
 C55B(H55B), C56B(H56B), C62(H62), C63(H63), C64(H64), C65(H65), C66(H66)
7.c Fitted hexagon refined as free rotating group:
 C51A(C52A,C53A,C54A,C55A,C56A), C51B(C52B,C53B,C54B,C55B,C56B), C61(C62,C63,
 C64,C65,C66)
7.d Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C57A(H57A,H57B,H57C), C57B(H57D,
 H57E,H57F), C67(H67A,H67B,H67C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.257
_oxdiff_exptl_absorpt_empirical_full_min 0.812
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
_twin_special_details
;
Component 2 rotated by 3.9300\%
 around [-0.68 0.73 0.09] (reciprocal) or [-0.74 0.67 0.03] (direct)
;
_shelx_res_checksum              53549
_cell_oxdiff_length_a            9.83402(10)
_cell_oxdiff_length_b            10.87734(15)
_cell_oxdiff_length_c            19.1786(3)
_cell_oxdiff_angle_alpha         104.5042(12)
_cell_oxdiff_angle_beta          103.2734(10)
_cell_oxdiff_angle_gamma         91.6813(10)
_cell_oxdiff_volume              1924.83(4)
_cell_oxdiff_measurement_reflns_used 34531