Synthesis, Cycloaddition, and Cycloreversion Reactions of Mononuclear Titanocene‒oxo Complexes
Nguyen, Trang T.; Kortman, Gregory D.; Hull, Kami L.; Organometallics 35 (2016) 1713–; doi:10.1021/acs.organomet.6b00111

data_4086504
_publ_contact_author
; 
Kami L. Hull
University of Illinois 
361 RAL, Box 23-5
600 South Mathews Avenue 
Urbana, Illinois  61801 
USA 
;
_publ_section_title
;
 Synthesis, Cycloaddition, and Cycloreversion Reactions of Mononuclear
 Titanocene--oxo Complexes
;
_journal_issue                   11
_journal_name_full               Organometallics
_journal_page_first              1713
_journal_paper_doi               10.1021/acs.organomet.6b00111
_journal_volume                  35
_journal_year                    2016
_chemical_formula_sum            'C29 H33 F6 N O Ti'
_chemical_formula_weight         573.46
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-09-22
_audit_creation_method
; 
Olex2 1.2 
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998) 
;
_audit_update_record
; 
? 
;
_cell_angle_alpha                90
_cell_angle_beta                 95.9403(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.8912(3)
_cell_length_b                   17.7648(6)
_cell_length_c                   15.3595(5)
_cell_measurement_reflns_used    9647
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      28.40
_cell_measurement_theta_min      2.29
_cell_volume                     2684.41(15)
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2014.9-0 (Bruker, 2014)'
_computing_data_reduction
; 
SAINT V8.34A, XPREP v2014/2, SADABS V2014/4, TWINABS V2012/1 
(Bruker, 2012 & 2014) 
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement
; 
SHELX-2014-6 (Sheldrick, 2014) 
Olex2 1.2.6 (Dolomanov et. al., 2009) 
;
_computing_structure_solution    'SHELX-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      296(2)
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'Bruker Kappa/ApexII CCD'
_diffrn_measurement_device_type  'Rigaku Saturn724+ (2x2 bin mode)'
_diffrn_measurement_method       'profile data from \f and \w scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_wavelength_id  cm07q_0m
_diffrn_reflns_av_R_equivalents  0.0478
_diffrn_reflns_av_unetI/netI     0.0223
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            6741
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.420
_diffrn_reflns_theta_min         1.758
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.384
_exptl_absorpt_correction_T_max  0.94497
_exptl_absorpt_correction_T_min  0.88522
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details   'SADABS V2014/4 (Bruker, 2014)'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.419
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1192
_exptl_crystal_id                cm07q_0m
_exptl_crystal_preparation
; 
The data crystal was mounted using oil (Parantone-N, Exxon) to a 
0.3 mm cryo-loop (Hampton Research) with the (1 -3 -6) scattering 
planes roughly normal to the spindle axis. 
;
_exptl_crystal_size_max          0.352
_exptl_crystal_size_mid          0.278
_exptl_crystal_size_min          0.158
_refine_diff_density_max         0.456
_refine_diff_density_min         -0.427
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     416
_refine_ls_number_reflns         6741
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0368
_refine_ls_R_factor_gt           0.0311
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0485P)^2^+1.1567P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0860
_refine_ls_wR_factor_ref         0.0887
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5965
_reflns_number_total             6741
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00111_si_002.cif
_cod_data_source_block           cm07q_0m
_cod_depositor_comments
'Adding full bibliography for 4086503--4086505.cif.'
_cod_database_code               4086504
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.942
_shelx_estimated_absorpt_t_min   0.877
_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. Uiso/Uaniso restraints and constraints 
Uanis(O1) = Uanis(O1A) 
Uanis(N1) = Uanis(N1A) 
3. Others 
 Sof(F1A)=Sof(F3A)=Sof(F2A)=1-FVAR(1) 
 Sof(F1)=Sof(F3)=Sof(F2)=FVAR(1) 
 Sof(F5A)=Sof(F6A)=Sof(F4A)=1-FVAR(2) 
 Sof(F6)=Sof(F4)=Sof(F5)=FVAR(2) 
 Sof(O1A)=Sof(N1A)=1-FVAR(3) 
 Sof(O1)=Sof(N1)=FVAR(3) 
4.a Aromatic/amide H refined with riding coordinates: 
 C27(H27), C23(H23), C25(H25) 
4.b Idealised Me refined as rotating group: 
 C19(H19A,H19B,H19C), C7(H7A,H7B,H7C), C18(H18A,H18B,H18C), C20(H20A,H20B, 
 H20C), C9(H9A,H9B,H9C), C6(H6A,H6B,H6C), C17(H17A,H17B,H17C), C8(H8A,H8B,H8C), 
 C16(H16A,H16B,H16C), C10(H10A,H10B,H10C) 
;
_shelx_res_checksum              34689
_shelx_hkl_checksum              53326
_olex2_submission_special_instructions 'No special instructions were received'