Unveiling the Takai Olefination Reagent via Tris( tert-butoxy)siloxy Variants.
Werner, Daniel; Anwander, Reiner; Journal of the American Chemical Society 140 (2018) 14334–14341; doi:10.1021/jacs.8b08739

data_4133162
_publ_section_title
;
 Unveiling the Takai Olefination Reagent via Tris( tert-butoxy)siloxy
 Variants.
;
_journal_issue                   43
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14334
_journal_page_last               14341
_journal_paper_doi               10.1021/jacs.8b08739
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C48 H108 Cr2 I O16 Si4, C1.5 H3.5'
_chemical_formula_sum            'C49.5 H111.5 Cr2 I O16 Si4'
_chemical_formula_weight         1306.15
_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_creation_date             2017-11-07
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                80.7633(9)
_cell_angle_beta                 80.5611(9)
_cell_angle_gamma                62.7355(9)
_cell_formula_units_Z            2
_cell_length_a                   13.3190(8)
_cell_length_b                   13.6739(8)
_cell_length_c                   21.8226(13)
_cell_measurement_reflns_used    9890
_cell_measurement_temperature    100.1
_cell_measurement_theta_max      27.12
_cell_measurement_theta_min      2.19
_cell_volume                     3468.4(4)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      100.1
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0434
_diffrn_reflns_av_unetI/netI     0.0435
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            49689
_diffrn_reflns_theta_full        27.19
_diffrn_reflns_theta_max         27.19
_diffrn_reflns_theta_min         0.95
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.882
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6683
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1253 before and 0.0462 after correction. The Ratio of minimum to maximum transmission is 0.8964. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.251
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Hexagon
_exptl_crystal_F_000             1387
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         2.017
_refine_diff_density_min         -0.737
_refine_diff_density_rms         0.228
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.132
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     714
_refine_ls_number_reflns         15420
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.132
_refine_ls_R_factor_all          0.0453
_refine_ls_R_factor_gt           0.0339
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0597P)^2^+1.8307P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0964
_refine_ls_wR_factor_ref         0.1144
_reflns_number_gt                13033
_reflns_number_total             15420
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja8b08739_si_007.cif
_cod_data_source_block           6a
_cod_original_formula_sum        'C49.50 H111.50 Cr2 I O16 Si4'
_cod_database_code               4133162
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C40A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C40) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C39A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.001
3. Others
 Fixed Sof: C39(0.5) H39A(0.5) H39B(0.5) H39C(0.5) C39A(0.5) H39D(0.5)
 H39E(0.5) H39F(0.5) C40(0.5) H40A(0.5) H40B(0.5) H40C(0.5) C40A(0.5) H40D(0.5)
 H40E(0.5) H40F(0.5) C50(0.5) H50B(0.25) H50A(0.25) H50D(0.25) H50C(0.25)
 C49(0.25) H49A(0.25) H49B(0.25) H49C(0.25) C0AA(0.5) H0AB(0.5) H0AA(0.5)
 C49A(0.25) H49D(0.25) H49E(0.25) H49F(0.25)
4.a Secondary CH2 refined with riding coordinates:
 C50(H50A,H50B), C50(H50C,H50D), C0AA(H0AA,H0AB)
4.b Idealised Me refined as rotating group:
 C43(H43A,H43B,H43C), C2(H2A,H2B,H2C), C32(H32A,H32B,H32C), C6(H6A,H6B,H6C),
 C38(H38A,H38B,H38C), C8(H8A,H8B,H8C), C42(H42A,H42B,H42C), C16(H16A,H16B,H16C),
  C28(H28A,H28B,H28C), C26(H26A,H26B,H26C), C11(H11A,H11B,H11C), C35(H35A,H35B,
 H35C), C7(H7A,H7B,H7C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C22(H22A,
 H22B,H22C), C30(H30A,H30B,H30C), C20(H20A,H20B,H20C), C23(H23A,H23B,H23C),
 C44(H44A,H44B,H44C), C27(H27A,H27B,H27C), C19(H19A,H19B,H19C), C34(H34A,H34B,
 H34C), C36(H36A,H36B,H36C), C24(H24A,H24B,H24C), C12(H12A,H12B,H12C), C39(H39A,
 H39B,H39C), C31(H31A,H31B,H31C), C4(H4A,H4B,H4C), C10(H10A,H10B,H10C), C3(H3A,
 H3B,H3C), C48(H48A,H48B,H48C), C47(H47A,H47B,H47C), C18(H18A,H18B,H18C),
 C46(H46A,H46B,H46C), C39A(H39D,H39E,H39F), C40(H40A,H40B,H40C), C40A(H40D,H40E,
 H40F), C49(H49A,H49B,H49C), C49A(H49D,H49E,H49F)
;
_olex2_submission_special_instructions 'No special instructions were received'