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_4088430
_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         'C30 H34 Si2'
_chemical_formula_sum            'C30 H34 Si2'
_chemical_formula_weight         450.75
_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
_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                85.577(7)
_cell_angle_beta                 88.528(7)
_cell_angle_gamma                86.739(8)
_cell_formula_units_Z            4
_cell_length_a                   11.0725(12)
_cell_length_b                   12.7749(13)
_cell_length_c                   18.5797(11)
_cell_measurement_reflns_used    2244
_cell_measurement_temperature    180.00(10)
_cell_measurement_theta_max      25.7860
_cell_measurement_theta_min      3.2850
_cell_volume                     2615.4(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      180.00(10)
_diffrn_detector_area_resol_mean 10.3914
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_details
;
  1 omega  -61.00   36.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       10.5454  -57.0000  -90.0000 97

  2 omega  -20.00   53.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       10.5454  -99.0000 -180.0000 73

  3 omega  -16.00   80.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       10.5454   57.0000   60.0000 96
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0264073000
_diffrn_orient_matrix_UB_12      0.0494312000
_diffrn_orient_matrix_UB_13      -0.0047260000
_diffrn_orient_matrix_UB_21      0.0570427000
_diffrn_orient_matrix_UB_22      -0.0244473000
_diffrn_orient_matrix_UB_23      0.0096109000
_diffrn_orient_matrix_UB_31      0.0129464000
_diffrn_orient_matrix_UB_32      -0.0083394000
_diffrn_orient_matrix_UB_33      -0.0367709000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0931
_diffrn_reflns_av_unetI/netI     0.1990
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            16731
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.021
_diffrn_reflns_theta_min         3.126
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.151
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.04397
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.145
_exptl_crystal_description       needle
_exptl_crystal_F_000             968
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.288
_refine_diff_density_min         -0.420
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.982
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     589
_refine_ls_number_reflns         10242
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.982
_refine_ls_R_factor_all          0.1996
_refine_ls_R_factor_gt           0.0829
_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^)+(0.0616P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1547
_refine_ls_wR_factor_ref         0.2089
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4618
_reflns_number_total             10242
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00073_si_002.cif
_cod_data_source_block           exp_5838
_cod_database_code               4088430
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C1 H1 Br1 P1 Pd1 O1'
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.985
_reflns_odcompleteness_completeness 99.27
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.97
_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:
 C13(H13), C43(H43)
2.b Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C54(H54A,H54B)
2.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C23(H23), C35(H35), C5(H5), C21(H21), C48(H48), C18(H18), C46(H46),
 C34(H34), C16(H16), C4(H4), C7(H7), C45(H45), C39(H39), C10(H10), C19(H19),
 C37(H37), C38(H38), C53(H53), C40(H40), C51(H51), C20(H20), C9(H9), C8(H8),
 C50(H50), C49(H49)
2.d Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C28(H28A,H28B,H28C), C58(H58A,H58B,H58C), C60(H60A,H60B,
 H60C), C29(H29A,H29B,H29C), C26(H26A,H26B,H26C), C30(H30A,H30B,H30C), C56(H56A,
 H56B,H56C), C27(H27A,H27B,H27C), C59(H59A,H59B,H59C), C55(H55A,H55B,H55C),
 C57(H57A,H57B,H57C)
;
_olex2_submission_special_instructions 'No special instructions were received'