Synthesis of Phosphonium-Substituted Vinylidene Complexes from [HC\τb CCH2PPh3]+: Exploring the Competition between Allene and Vinylidene Formation.
Smith, Elizabeth J.; Pridmore, Natalie E.; Whitwood, Adrian C.; Lynam, Jason M.; Organometallics 33 (2014) 7260–; doi:10.1021/om5010429

data_4084915
_publ_section_title
;
 Synthesis of Phosphonium-Substituted Vinylidene Complexes from [HC\\tb
 CCH2PPh3]+: Exploring the Competition between Allene and Vinylidene
 Formation.
;
_journal_issue                   24
_journal_name_full               Organometallics
_journal_page_first              7260
_journal_paper_doi               10.1021/om5010429
_journal_volume                  33
_journal_year                    2014
_chemical_formula_moiety         'C39 H34 P2, 2(B F4)'
_chemical_formula_sum            'C39 H34 B2 F8 P2'
_chemical_formula_weight         738.22
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-12-15
_audit_creation_method
;
Olex2 1.2
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_cell_angle_alpha                65.358(5)
_cell_angle_beta                 75.008(4)
_cell_angle_gamma                83.678(4)
_cell_formula_units_Z            2
_cell_length_a                   9.9081(4)
_cell_length_b                   13.7516(7)
_cell_length_c                   14.6581(8)
_cell_measurement_reflns_used    4084
_cell_measurement_temperature    110.05(10)
_cell_measurement_theta_max      28.4710
_cell_measurement_theta_min      3.2590
_cell_volume                     1753.52(17)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      110.05(10)
_diffrn_detector_area_resol_mean 16.1450
_diffrn_measured_fraction_theta_full 0.9830
_diffrn_measured_fraction_theta_max 0.823
_diffrn_measurement_details
;
  1 omega    1.00   88.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -       19.1763   57.0000 -150.0000 87

  2 omega   23.00   61.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -       19.1763  -99.0000   90.0000 38

  3 omega  -11.00   88.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -       19.1763   77.0000  -30.0000 99

  4 omega  -18.00   32.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -       19.1763   19.0000  150.0000 50
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0223751000
_diffrn_orient_matrix_UB_12      0.0304887000
_diffrn_orient_matrix_UB_13      0.0301200000
_diffrn_orient_matrix_UB_21      0.0706523000
_diffrn_orient_matrix_UB_22      0.0094894000
_diffrn_orient_matrix_UB_23      -0.0039822000
_diffrn_orient_matrix_UB_31      0.0000188000
_diffrn_orient_matrix_UB_32      0.0469112000
_diffrn_orient_matrix_UB_33      -0.0455811000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0225
_diffrn_reflns_av_unetI/netI     0.0554
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            11775
_diffrn_reflns_theta_full        26.32
_diffrn_reflns_theta_max         29.19
_diffrn_reflns_theta_min         2.90
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.196
_exptl_absorpt_correction_T_max  0.996
_exptl_absorpt_correction_T_min  0.965
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.398
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plank
_exptl_crystal_F_000             760
_exptl_crystal_size_max          0.3396
_exptl_crystal_size_mid          0.0895
_exptl_crystal_size_min          0.0229
_refine_diff_density_max         1.335
_refine_diff_density_min         -0.995
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     496
_refine_ls_number_reflns         7817
_refine_ls_number_restraints     68
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0981
_refine_ls_R_factor_gt           0.0765
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0478P)^2^+5.1572P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1706
_refine_ls_wR_factor_ref         0.1828
_reflns_number_gt                6191
_reflns_number_total             7817
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            om5010429_si_002.cif
_cod_data_source_block           '[8](BF4)2'
_cod_depositor_comments
'Adding full bibliography for 4084912--4084917.cif.'
_cod_database_code               4084915
_chemical_oxdiff_formula         'C39 H34 P2 B2 F8'
_chemical_oxdiff_usercomment     'Lizzie's ejs278-3'
_reflns_odcompleteness_completeness 98.30
_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
2. Shared sites
{F5, F5A}
{B2, B2A}
3. Restrained distances
 B1-F1 \\sim B1A-F1A \\sim B1-F2 \\sim B1A-F2A \\sim B1-F3 \\sim B1A-F3A \\sim
B1-F4 \\sim B1A-F4A
 with sigma of 0.001
 B2-F5 \\sim B2A-F5A \\sim B2-F6 \\sim B2A-F6A \\sim B2-F7 \\sim B2A-F7A \\sim
B2-F8 \\sim B2A-F8A
 with sigma of 0.001
4. Uiso/Uaniso restraints and constraints
Uanis(B2) \\sim Ueq, Uanis(B2A) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(F2) = Uanis(F2A)
Uanis(F4) = Uanis(F4A)
Uanis(F3) = Uanis(F3A)
Uanis(F1) = Uanis(F1A)
Uanis(B1) = Uanis(B1A)
Uanis(F8) = Uanis(F8A)
Uanis(F6) = Uanis(F6A)
Uanis(F7) = Uanis(F7A)
Uanis(F5) = Uanis(F5A)
Uanis(B2) = Uanis(B2A)
5. Others
 Sof(H2A)=Sof(H2B)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=1-FVAR(1)
 Sof(H1A)=Sof(H1B)=Sof(C3)=Sof(H3A)=Sof(H3B)=FVAR(1)
 Sof(B1A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=1-FVAR(2)
 Sof(B1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=FVAR(2)
 Sof(B2A)=Sof(F5A)=Sof(F6A)=Sof(F7A)=Sof(F8A)=1-FVAR(3)
 Sof(B2)=Sof(F5)=Sof(F6)=Sof(F7)=Sof(F8)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B)
6.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C23(H23),
  C24(H24), C25(H25), C26(H26), C27(H27), C29(H29), C30(H30), C31(H31),
 C32(H32), C33(H33), C35(H35), C36(H36), C37(H37), C38(H38), C39(H39)
6.c X=CH2 refined with riding coordinates:
 C3(H3A,H3B), C3A(H3AA,H3AB)
;