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_4133164
_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         'C31 H71 Cr I N2 O8 Si2, I, 1.13(C6), C6 H6'
_chemical_formula_sum            'C43.75 H77 Cr I2 N2 O8 Si2'
_chemical_formula_weight         1121.05
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-10-24
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 101.3700(10)
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   27.7924(18)
_cell_length_b                   9.4487(6)
_cell_length_c                   42.685(3)
_cell_measurement_reflns_used    9740
_cell_measurement_temperature    150
_cell_measurement_theta_max      30.54
_cell_measurement_theta_min      2.28
_cell_volume                     10989.2(13)
_computing_cell_refinement       'SAINT V8.38A (Bruker-AXS, 2016)'
_computing_data_reduction        'SAINT V8.38A (Bruker-AXS, 2016)'
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      150.0
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_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  0.0421
_diffrn_reflns_av_unetI/netI     0.0237
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -39
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       61
_diffrn_reflns_limit_l_min       -61
_diffrn_reflns_number            149998
_diffrn_reflns_theta_full        30.99
_diffrn_reflns_theta_max         30.99
_diffrn_reflns_theta_min         1.49
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.420
_exptl_absorpt_correction_T_max  0.7462
_exptl_absorpt_correction_T_min  0.6442
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1227 before and 0.0469 after correction. The Ratio of minimum to maximum transmission is 0.8633. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear bluish violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.355
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             4604
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.581
_refine_diff_density_min         -1.043
_refine_diff_density_rms         0.168
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.194
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     611
_refine_ls_number_reflns         17429
_refine_ls_number_restraints     68
_refine_ls_restrained_S_all      1.241
_refine_ls_R_factor_all          0.0567
_refine_ls_R_factor_gt           0.0456
_refine_ls_shift/su_max          0.011
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0460P)^2^+42.7197P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1117
_refine_ls_wR_factor_ref         0.1216
_reflns_number_gt                14988
_reflns_number_total             17429
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja8b08739_si_011.cif
_cod_data_source_block           c2c_a
_cod_original_cell_volume        10989.2(12)
_cod_database_code               4133164
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C01F-C015
 2.36 with sigma of 0.02
 C01B-C01G
 2.36 with sigma of 0.02
 C01F-C01B
 2.71 with sigma of 0.02
 C8AA-C01G
 1.36 with sigma of 0.02
 C015-C01B
 1.36 with sigma of 0.02
 C8AA-C01B
 1.36 with sigma of 0.02
 C01F-C00M
 1.36 with sigma of 0.02
 C015-C00M
 1.36 with sigma of 0.02
 C8AA-C00M
 2.71 with sigma of 0.01
 C01B-C00M
 2.3 with sigma of 0.01
 C00M-C01G
 2.3 with sigma of 0.01
 C8AA-C01F
 2.3 with sigma of 0.01
 C8AA-C015
 2.3 with sigma of 0.01
 C2AA-C1AA
 1.4 with sigma of 0.01
 C2AA-C3AA
 1.4 with sigma of 0.01
 C3AA-C3BA
 1.4 with sigma of 0.01
 C3BA-C4AA
 1.4 with sigma of 0.01
 C4AA-C5AA
 1.4 with sigma of 0.01
 C5AA-C1AA
 1.4 with sigma of 0.01
 C2AA-C4AA
 2.34 with sigma of 0.01
 C3BA-C1AA
 2.34 with sigma of 0.01
 C3AA-C4AA
 2.34 with sigma of 0.01
 C3AA-C1AA
 2.34 with sigma of 0.01
 C5AA-C3BA
 2.34 with sigma of 0.01
 C5AA-C2AA
 2.34 with sigma of 0.01
 C3AA-C5AA
 2.71 with sigma of 0.01
 C4AA-C1AA
 2.3 with sigma of 0.01
3. Restrained planarity
 C00M, C01B, C01F, C01G, C8AA, C015
 with sigma of 0.1
 C1AA, C2AA, C3AA, C3BA, C4AA
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C17) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C01H) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C1BA) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C19) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C18) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C01J) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
5. Others
 Fixed Sof: C0AA(0.5) H0AA(0.5) H0AB(0.5) H0AC(0.5) C0BA(0.5) H0BA(0.5)
 H0BB(0.5) H0BC(0.5) C1BA(0.5) H1BA(0.5) H1BB(0.5) H1BC(0.5) C01H(0.5)
 H01A(0.5) H01B(0.5) H01C(0.5) C01J(0.5) H01D(0.5) H01E(0.5) H01F(0.5)
 C9AA(0.5) H9AA(0.5) H9AB(0.5) H9AC(0.5) C17(0.5) H17A(0.5) H17B(0.5) H17C(0.5)
 C18(0.5) H18A(0.5) H18B(0.5) H18C(0.5) C19(0.5) H19A(0.5) H19B(0.5) H19C(0.5)
 C21(0.5) H21A(0.5) H21B(0.5) H21C(0.5) C22(0.5) H22A(0.5) H22B(0.5) H22C(0.5)
 C23(0.5) H23A(0.5) H23B(0.5) H23C(0.5) C00M(0.5) C1AA(0.25) C01B(0.5)
 C01F(0.5) C01G(0.5) C2AA(0.25) C3AA(0.25) C3BA(0.25) C4AA(0.25) C7AA(0.5)
 C8AA(0.5) C015(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B)
6.b Aromatic/amide H refined with riding coordinates:
 C32(H), C33(HA), C34(HB), C35(HC), C36(HD), C37(HE)
6.c Idealised Me refined as rotating group:
 C0AA(H0AA,H0AB,H0AC), C0BA(H0BA,H0BB,H0BC), C1BA(H1BA,H1BB,H1BC), C01H(H01A,
 H01B,H01C), C01J(H01D,H01E,H01F), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C6(H6A,H6B,
 H6C), C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), C9AA(H9AA,H9AB,H9AC), C10(H10A,H10B,
 H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,
 H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C),
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C25(H25A,H25B,
 H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C31(H31A,H31B,H31C)
;
_olex2_submission_special_instructions 'No special instructions were received'