Calcium-Mediated C‒H and C‒F Bond Cleavage: Synthesis of Indenes and Perfluorodibenzopentalenes from 1,4-Dilithio-1,3-butadienes
Wei, Baosheng; Li, Heng; Zhang, Wen-Xiong; Xi, Zhenfeng; Organometallics 35 (2016) 1458–; doi:10.1021/acs.organomet.6b00073

data_4088429
_publ_section_title
;
 Calcium-Mediated C--H and C--F Bond Cleavage: Synthesis of Indenes and
 Perfluorodibenzopentalenes from 1,4-Dilithio-1,3-butadienes
;
_journal_issue                   10
_journal_name_full               Organometallics
_journal_page_first              1458
_journal_paper_doi               10.1021/acs.organomet.6b00073
_journal_volume                  35
_journal_year                    2016
_chemical_formula_moiety         'C44 H58 Li2 Si4'
_chemical_formula_sum            'C44 H58 Li2 Si4'
_chemical_formula_weight         713.14
_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'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-10-26
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 111.783(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.7464(5)
_cell_length_b                   26.0567(11)
_cell_length_c                   8.9188(5)
_cell_measurement_reflns_used    3648
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      29.2080
_cell_measurement_theta_min      3.9540
_cell_volume                     2103.3(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_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      100.01(10)
_diffrn_detector_area_resol_mean 10.3914
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega  -49.00   29.00   1.0000    2.9800
omega____ theta____ kappa____ phi______ frames
    -       11.5979  -57.0000   60.0000 78

  2 omega    3.00   77.00   1.0000    2.9800
omega____ theta____ kappa____ phi______ frames
    -       11.5979   19.0000 -150.0000 74

  3 omega   -5.00   27.00   1.0000    2.9800
omega____ theta____ kappa____ phi______ frames
    -      -12.3792  -99.0000  -60.0000 32
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0498540000
_diffrn_orient_matrix_UB_12      0.0067223000
_diffrn_orient_matrix_UB_13      -0.0379348000
_diffrn_orient_matrix_UB_21      -0.0028988000
_diffrn_orient_matrix_UB_22      0.0260323000
_diffrn_orient_matrix_UB_23      0.0219084000
_diffrn_orient_matrix_UB_31      0.0603522000
_diffrn_orient_matrix_UB_32      -0.0042976000
_diffrn_orient_matrix_UB_33      0.0735986000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0276
_diffrn_reflns_av_unetI/netI     0.0403
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            8956
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.021
_diffrn_reflns_theta_min         2.914
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.170
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62091
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.126
_exptl_crystal_description
;
;
_exptl_crystal_F_000             768
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.376
_refine_diff_density_min         -0.305
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     232
_refine_ls_number_reflns         4120
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0473
_refine_ls_R_factor_gt           0.0393
_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^)+(0.0345P)^2^+1.1252P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0908
_refine_ls_wR_factor_ref         0.0957
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3553
_reflns_number_total             4120
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00073_si_002.cif
_cod_data_source_block           12dec25f
_cod_database_code               4088429
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         'C H Si Ba O'
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.967
_reflns_odcompleteness_completeness 99.75
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.a Ternary CH refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B)
2.c Aromatic/amide H refined with riding coordinates:
 C18(H18), C19(H19), C20(H20), C21(H21), C22(H22)
2.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,
 H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C)
;
_olex2_submission_special_instructions 'No special instructions were received'