Synthesis, Characterization, and Heterobimetallic Cooperation in a Titanium-Chromium Catalyst for Highly Branched Polyethylenes
Shaofeng Liu; Alessandro Motta; Massimiliano Delferro; Tobin J. Marks; Journal of the American Chemical Society 135 (2013) 8830–8833; doi:10.1021/ja4039505

data_4119951
_publ_contact_author_address
;
Department of Chemistry, Northwestern University, 
Evanston, Illinois 60208-3113, United States
;
_publ_contact_author_email       t-marks@northwestern.edu
_publ_contact_author_name        'Tobin J. Marks'
_publ_section_title
;
 Synthesis, Characterization, and Heterobimetallic Cooperation in a
 Titanium-Chromium Catalyst for Highly Branched Polyethylenes
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8830
_journal_page_last               8833
_journal_paper_doi               10.1021/ja4039505
_journal_volume                  135
_journal_year                    2013
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C25 H42 Cl2 N2 S2 Si Ti'
_chemical_formula_sum            'C25 H42 Cl2 N2 S2 Si Ti'
_chemical_formula_weight         581.61
_chemical_name_common            {Ti--Cr}
_chemical_name_systematic        'CGCTiCl2-SNSCrCl2 '
_chemical_properties_physical
'air-sensitive, moisture-sensitive, oxygen-sensitive, paramagnetic'
_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_cell_setting           triclinic
_symmetry_Int_Tables_number      2
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     heavy
_audit_creation_date             2013-01-28
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:17:34, GUI svn.r4385)
;
_cell_angle_alpha                105.948(5)
_cell_angle_beta                 100.518(5)
_cell_angle_gamma                104.942(4)
_cell_formula_units_Z            2
_cell_length_a                   8.3754(4)
_cell_length_b                   13.8729(7)
_cell_length_c                   15.0533(9)
_cell_measurement_reflns_used    2810
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      64.04
_cell_measurement_theta_min      3.17
_cell_volume                     1563.27(16)
_computing_cell_refinement       'SAINT V7.23A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2.1-4 (Bruker, 2007)'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
XS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100.01
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.844
_diffrn_measured_fraction_theta_max 0.956
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'Quazar optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0726
_diffrn_reflns_av_unetI/netI     0.0885
_diffrn_reflns_Laue_measured_fraction_full 0.844
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            8673
_diffrn_reflns_point_group_measured_fraction_full 0.844
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         62.381
_diffrn_reflns_theta_min         3.174
_diffrn_source                   microsource
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.618
_exptl_absorpt_correction_T_max  0.7525
_exptl_absorpt_correction_T_min  0.4428
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0917 before and 0.0565 after correction.
The Ratio of minimum to maximum transmission is 0.5884.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.236
_exptl_crystal_description       needle
_exptl_crystal_F_000             616
_exptl_crystal_recrystallization_method Hexane
_exptl_crystal_size_max          0.422
_exptl_crystal_size_mid          0.047
_exptl_crystal_size_min          0.045
_refine_diff_density_max         1.964
_refine_diff_density_min         -0.952
_refine_diff_density_rms         0.157
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.266
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     338
_refine_ls_number_reflns         4761
_refine_ls_number_restraints     51
_refine_ls_restrained_S_all      1.274
_refine_ls_R_factor_all          0.1569
_refine_ls_R_factor_gt           0.1167
_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^)+(0.2000P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3195
_refine_ls_wR_factor_ref         0.3538
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3131
_reflns_number_total             4761
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja4039505_si_002.cif
_cod_data_source_block           n2398
_cod_original_cell_volume        1563.26(15)
_cod_database_code               4119951
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  {H18A,H18B} of C18, {H19A,H19B} of C19, {H23A,H23B} of C23, {H17A,H17B} of
  C17, {H20A,H20B} of C20, {H16A,H16B} of C16, {H24A,H24B} of C24, {H22A,H22B}
  of C22, {H20C,H20D} of C20A, {H19C,H19D} of C19A, H7 of C7, H6 of C6, H5 of
  C5, H4 of C4, H1 of C1
 At 1.5 times of:
  {H13D,H13E,H13F} of C13A, {H25A,H25B,H25C} of C25, {H21A,H21B,H21C} of C21,
  {H15D,H15E,H15F} of C15A, {H14D,H14E,H14F} of C14A, {H21D,H21E,H21F} of C21A,
  {H15A,H15B,H15C} of C15, {H14A,H14B,H14C} of C14, {H13A,H13B,H13C} of C13,
  {H11A,H11B,H11C} of C11, {H10A,H10B,H10C} of C10
2. Restrained distances
 C15A-C12 - C14-C12 - C14A-C12 - C13-C12 - C13A-C12 - C15-C12
 with sigma of 0.02
 C19-C18 - C19A-C18 - C20-C21 - C20A-C21A
 with sigma of 0.02
 S1A-C19A - S1-C19 - S1A-C20A - S1-C20
 with sigma of 0.02
3. Rigid bond restraints
 C14A, C14, C15A, C15, C13A, C13
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C14A - C14 - C15A - C15 - C13A - C13: within 1.7A with sigma of 0.01 and sigma 
for terminal atoms of 0.02
Uanis(S1) = Uanis(S1A)
Uanis(C19) = Uanis(C19A) = Uanis(C20A) = Uanis(C21A) = Uanis(C20) = Uanis(C21)
5. others
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=1-Sof(H13A)=1-Sof(H13A)=1-Sof(H13A)=1-
 Sof(H13A)=1-Sof(H13A)=1-Sof(H13A)=1-Sof(H13A)=1-Sof(H13A)=1-Sof(H13A)=1-
 Sof(H13A)=1-Sof(H13A)=1-Sof(H13A)
 1-Sof(S1A)=Sof(S1A)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(H20A)=Sof(H20B)=
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=1-Sof(S1A)=1-Sof(S1A)=1-Sof(S1A)=1-
 Sof(S1A)=1-Sof(S1A)=1-Sof(S1A)=1-Sof(S1A)=1-Sof(S1A)=1-Sof(S1A)=1-Sof(S1A)
6.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,
 H20B), C19A(H19C,H19D), C20A(H20C,H20D), C22(H22A,H22B), C23(H23A,H23B),
 C24(H24A,H24B)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C5(H5), C6(H6), C7(H7)
6.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C14(H14A,H14B,
 H14C), C15(H15A,H15B,H15C), C13A(H13D,H13E,H13F), C14A(H14D,H14E,H14F),
 C15A(H15D,H15E,H15F), C21(H21A,H21B,H21C), C21A(H21D,H21E,H21F), C25(H25A,H25B,
 H25C)
;
_shelx_estimated_absorpt_t_max   0.786
_shelx_estimated_absorpt_t_min   0.200
_shelx_res_checksum              66677
_shelxl_version_number           2012-9