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_4084914
_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         'C64 H53 Br O2 P3 Ru, 2(C1 H2 Cl2), B F4'
_chemical_formula_sum            'C66 H57 B Br Cl4 F4 O2 P3 Ru'
_chemical_formula_weight         1384.61
_chemical_name_systematic
;
 ?
;
_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
_audit_creation_date             2014-01-09
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_cell_angle_alpha                95.303(2)
_cell_angle_beta                 104.015(2)
_cell_angle_gamma                97.399(2)
_cell_formula_units_Z            2
_cell_length_a                   11.8805(3)
_cell_length_b                   13.4688(3)
_cell_length_c                   20.1628(5)
_cell_measurement_reflns_used    9269
_cell_measurement_temperature    110.05(10)
_cell_measurement_theta_max      31.8830
_cell_measurement_theta_min      3.2970
_cell_volume                     3078.54(13)
_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
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
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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 0.998
_diffrn_measured_fraction_theta_max 0.887
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0484695000
_diffrn_orient_matrix_UB_12      -0.0380597000
_diffrn_orient_matrix_UB_13      -0.0162208000
_diffrn_orient_matrix_UB_21      0.0387733000
_diffrn_orient_matrix_UB_22      -0.0357562000
_diffrn_orient_matrix_UB_23      -0.0006227000
_diffrn_orient_matrix_UB_31      -0.0053717000
_diffrn_orient_matrix_UB_32      -0.0118473000
_diffrn_orient_matrix_UB_33      0.0327596000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0246
_diffrn_reflns_av_unetI/netI     0.0505
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.887
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            30601
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.887
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         32.171
_diffrn_reflns_theta_min         2.838
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.212
_exptl_absorpt_correction_T_max  0.902
_exptl_absorpt_correction_T_min  0.873
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.494
_exptl_crystal_description       block
_exptl_crystal_F_000             1404
_exptl_crystal_recrystallization_method DCM:ether
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.178
_exptl_crystal_size_min          0.1073
_refine_diff_density_max         2.408
_refine_diff_density_min         -2.187
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     862
_refine_ls_number_reflns         19292
_refine_ls_number_restraints     85
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0797
_refine_ls_R_factor_gt           0.0565
_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^)+(0.0559P)^2^+7.9394P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1322
_refine_ls_wR_factor_ref         0.1463
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14922
_reflns_number_total             19292
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5010429_si_002.cif
_cod_data_source_block           '[6b]BF4.(CH2Cl2)2'
_cod_depositor_comments
'Adding full bibliography for 4084912--4084917.cif.'
_cod_original_cell_volume        3078.56(13)
_cod_database_code               4084914
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C65 H54 Br1 Cl2 O2 P3 Ru1'
_chemical_oxdiff_usercomment     EJS317A
_reflns_odcompleteness_completeness 99.66
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.01
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Shared sites
{Cl4, Cl4A}
{B2, B2A}
{B1, C67, C67A}
{Cl5, Cl5A}
{C66, C66A}
3. Restrained distances
 C65A-Cl1A = C65A-Cl2A
 1.745 with sigma of 0.01
 Cl3A-Cl4A
 2.9 with sigma of 0.01
 Cl3-C66 = Cl4-C66 = Cl3A-C66A = Cl4A-C66A
 1.745 with sigma of 0.01
 Cl6-C67 = C67-Cl5 = Cl6A-C67A = C67A-Cl5A
 1.745 with sigma of 0.005
 Cl1A-Cl2A = Cl3-Cl4 = Cl3A-Cl4A = Cl5-Cl6 = Cl5A-Cl6A
 2.9 with sigma of 0.02
 F1-F2 \\sim F1-F3 \\sim F1-F4 \\sim F2-F3 \\sim F2-F4 \\sim F3-F4
 with sigma of 0.02
 B1-F1 \\sim B1-F2 \\sim B1-F3 \\sim B1-F4
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C67) \\sim Ueq, Uanis(B1) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F5) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F7A) \\sim
Ueq, Uanis(F5A) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of
0.01
Uanis(F6A) \\sim Ueq: with sigma of 0.03 and sigma for terminal atoms of 0.06
Uanis(C65) = Uanis(C65A)
Uanis(C17) = Uanis(C17A)
Uanis(C18) = Uanis(C18A)
Uanis(C19) = Uanis(C19A)
Uanis(C20) = Uanis(C20A)
Uanis(C21) = Uanis(C21A)
Uanis(C22) = Uanis(C22A)
Uanis(C12) = Uanis(C12A)
Uanis(C13) = Uanis(C13A)
Uanis(C14) = Uanis(C14A)
Uanis(C15) = Uanis(C15A)
Uanis(C16) = Uanis(C16A)
Uanis(C2) = Uanis(C2A)
Uanis(C3) = Uanis(C3A)
Uanis(C4) = Uanis(C4A)
Uanis(C5) = Uanis(C5A)
Uanis(C6) = Uanis(C6A)
Uanis(C7) = Uanis(C7A)
Uanis(C11A) = Uanis(C11)
Uanis(Cl2) = Uanis(Cl2A)
Uanis(Cl1) = Uanis(Cl1A)
Uanis(B2) = Uanis(B2A)
Uanis(F8A) = Uanis(F1)
Uanis(B1) = Uanis(C67) = Uanis(C67A)
Uiso(Cl5) = Uiso(Cl5A)
Uanis(C66) = Uanis(C66A)
Uanis(Cl4) = Uanis(Cl4A)
Uanis(Cl3) = Uanis(Cl3A)
Uanis(Cl6) = Uanis(Cl6A)
5. Others
 Sof(Cl1A)=Sof(Cl2A)=Sof(C65A)=Sof(H65C)=Sof(H65D)=1-FVAR(1)
 Sof(Cl1)=Sof(Cl2)=Sof(C65)=Sof(H65A)=Sof(H65B)=FVAR(1)
 Sof(C17A)=Sof(C22A)=Sof(H22A)=Sof(C21A)=Sof(H21A)=Sof(C20A)=Sof(H20A)=
 Sof(C19A)=Sof(H19A)=Sof(C18A)=Sof(H18A)=1-FVAR(2)
 Sof(C17)=Sof(C18)=Sof(H18)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20)=Sof(C21)=
 Sof(H21)=Sof(C22)=Sof(H22)=FVAR(2)
 Sof(C11A)=Sof(C16A)=Sof(H16A)=Sof(C15A)=Sof(H15A)=Sof(C14A)=Sof(H14A)=
 Sof(C13A)=Sof(H13A)=Sof(C12A)=Sof(H12A)=1-FVAR(3)
 Sof(C11)=Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14)=Sof(C15)=
 Sof(H15)=Sof(C16)=Sof(H16)=FVAR(3)
 Sof(C2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=
 Sof(H6A)=Sof(C7A)=Sof(H7A)=1-FVAR(4)
 Sof(C2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=
 Sof(C7)=Sof(H7)=FVAR(4)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(B1)=1-FVAR(5)
 Sof(Cl3)=Sof(Cl4)=Sof(C66)=Sof(H66A)=Sof(H66B)=0.9*(1-FVAR(6))
 Sof(Cl3A)=Sof(Cl4A)=Sof(C66A)=Sof(H66C)=Sof(H66D)=0.1*(1-FVAR(6))
 Sof(Cl5A)=Sof(Cl6A)=Sof(C67A)=Sof(H67C)=Sof(H67D)=0.17*FVAR(6)
 Sof(F5)=Sof(F6)=Sof(F7)=Sof(F8)=Sof(B2)=Sof(F5A)=Sof(F6A)=Sof(F7A)=Sof(F8A)=
 Sof(B2A)=0.5*FVAR(6)
 Sof(Cl5)=Sof(Cl6)=Sof(C67)=Sof(H67A)=Sof(H67B)=0.83*FVAR(6)
6.a Everything fixed:
 Cl6A
6.b Riding coordinates:
 C66A(H66C,H66D)
6.c Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C67(H67A,H67B), C67A(H67C,H67D), C65(H65A,H65B), C65A(H65C,H65D),
  C66(H66A,H66B)
6.d Aromatic/amide H refined with riding coordinates:
 C3A(H3A), C4A(H4A), C5A(H5A), C6A(H6A), C7A(H7A), C3(H3), C4(H4), C5(H5),
 C6(H6), C7(H7), C10(H10), C16A(H16A), C15A(H15A), C14A(H14A), C13A(H13A),
 C12A(H12A), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C22A(H22A),
 C21A(H21A), C20A(H20A), C19A(H19A), C18A(H18A), C18(H18), C19(H19), C20(H20),
 C21(H21), C22(H22), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28), C30(H30),
  C31(H31), C32(H32), C33(H33), C34(H34), C36(H36), C37(H37), C38(H38),
 C39(H39), C40(H40), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46), C48(H48),
  C49(H49), C50(H50), C51(H51), C52(H52), C54(H54), C55(H55), C56(H56),
 C57(H57), C58(H58), C60(H60), C61(H61), C62(H62), C63(H63), C64(H64)
6.e Fitted hexagon refined as free rotating group:
 C2A(C3A,C4A,C5A,C6A,C7A), C11A(C16A,C15A,C14A,C13A,C12A), C17A(C22A,C21A,C20A,
 C19A,C18A)
;