The Reductive Activation of CO2 Across a Ti=Ti Double Bond: Synthetic, Structural, and Mechanistic Studies.
Kilpatrick, Alexander F. R.; Green, Jennifer C.; Cloke, F Geoffrey N; Organometallics 34 (2015) 4816–4829; doi:10.1021/acs.organomet.5b00315

data_4086017
_publ_section_title
;
 The Reductive Activation of CO2 Across a Ti=Ti Double Bond: Synthetic,
 Structural, and Mechanistic Studies.
;
_journal_issue                   20
_journal_name_full               Organometallics
_journal_page_first              4816
_journal_page_last               4829
_journal_paper_doi               10.1021/acs.organomet.5b00315
_journal_volume                  34
_journal_year                    2015
_chemical_formula_moiety         'C52 H90 O Si4 Ti2'
_chemical_formula_sum            'C52 H90 O Si4 Ti2'
_chemical_formula_weight         939.39
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-01-26
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                90
_cell_angle_beta                 120.393(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.0529(11)
_cell_length_b                   11.2699(4)
_cell_length_c                   22.7761(10)
_cell_measurement_reflns_used    9243
_cell_measurement_temperature    173
_cell_measurement_theta_max      28.2730
_cell_measurement_theta_min      3.1430
_cell_volume                     5325.5(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_molecular_graphics    'Ortep for Windows (Farrugia, 2012)'
_computing_publication_material
;
Olex2 (Dolomanov et al., 2009) and WinGX  (Farrugia, 2012) publication routines
;
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_solution
;
SUPERFLIP (Platinus & Chapuis, 2007)
;
_diffrn_ambient_temperature      173.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1033
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_details
;
  1 omega  -94.00   56.00   1.0000   62.5000
omega____ theta____ kappa____ phi______ frames
    -      -23.2243    0.0000   30.0000 150

  2 omega  -50.00   20.00   1.0000   62.5000
omega____ theta____ kappa____ phi______ frames
    -      -23.2243   38.0000 -180.0000 70

  3 omega  -15.00   49.00   1.0000   62.5000
omega____ theta____ kappa____ phi______ frames
    -      -23.2243   57.0000   30.0000 64

  4 omega  -45.00   19.00   1.0000   62.5000
omega____ theta____ kappa____ phi______ frames
    -      -23.2243   57.0000  -90.0000 64

  5 omega   57.00  110.00   1.0000   62.5000
omega____ theta____ kappa____ phi______ frames
    -       23.5368  178.0000   60.0000 53

  6 omega   61.00  108.00   1.0000   62.5000
omega____ theta____ kappa____ phi______ frames
    -       23.5368  178.0000  -60.0000 47

  7 omega  -25.00   15.00   1.0000   62.5000
omega____ theta____ kappa____ phi______ frames
    -       23.5368  100.0000  135.0000 40

  8 omega   57.00  104.00   1.0000   62.5000
omega____ theta____ kappa____ phi______ frames
    -       23.5368  178.0000  150.0000 47
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0039642000
_diffrn_orient_matrix_UB_12      0.0625228000
_diffrn_orient_matrix_UB_13      -0.0023595000
_diffrn_orient_matrix_UB_21      -0.0321872000
_diffrn_orient_matrix_UB_22      -0.0067702000
_diffrn_orient_matrix_UB_23      -0.0072316000
_diffrn_orient_matrix_UB_31      0.0108274000
_diffrn_orient_matrix_UB_32      0.0028598000
_diffrn_orient_matrix_UB_33      0.0352770000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0343
_diffrn_reflns_av_unetI/netI     0.0299
_diffrn_reflns_laue_measured_fraction_full 0.998
_diffrn_reflns_laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            22693
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         3.151
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.424
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87423
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.172
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2040
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.810
_refine_diff_density_min         -0.411
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     277
_refine_ls_number_reflns         5988
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0530
_refine_ls_R_factor_gt           0.0427
_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^)+(0.0643P)^2^+6.3586P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1170
_refine_ls_wR_factor_ref         0.1243
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5011
_reflns_number_total             5988
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00315_si_003.cif
_cod_data_source_block           Compound5
_cod_depositor_comments
;Adding full bibliography for 4086017--4086022.cif.

 Adding full bibliography for 4086017--4086022.cif.
;
_cod_database_code               4086017
_chemical_oxdiff_formula         'C52 H92 Ti2 Si4 O1'
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.920
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Others
 Sof(C14B)=Sof(H14D)=Sof(H14E)=Sof(H14F)=1-FVAR(1)
 Sof(C14A)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C9(H9), C15(H15), C44(H44), C47(H47), C50(H50)
3.b Me refined with riding coordinates:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C14A(H14A,H14B,
 H14C), C14B(H14D,H14E,H14F), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C),
 C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C48(H48A,H48B,H48C), C49(H49A,H49B,
 H49C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C32(H32), C33(H33)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'