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_4084912
_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         'C71 H58 O4 P3 Ru, C24 H20 B, 1(C H2 Cl2)'
_chemical_formula_sum            'C96 H80 B Cl2 O4 P3 Ru'
_chemical_formula_weight         1573.03
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-12-16
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_cell_angle_alpha                100.054(3)
_cell_angle_beta                 92.041(3)
_cell_angle_gamma                110.548(3)
_cell_formula_units_Z            2
_cell_length_a                   12.5833(4)
_cell_length_b                   13.1462(4)
_cell_length_c                   25.7463(9)
_cell_measurement_reflns_used    10258
_cell_measurement_temperature    110.00(14)
_cell_measurement_theta_max      27.7000
_cell_measurement_theta_min      3.1260
_cell_volume                     3905.1(2)
_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, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      110.00(14)
_diffrn_detector_area_resol_mean 16.1450
_diffrn_measured_fraction_theta_full 0.9879
_diffrn_measured_fraction_theta_max 0.814
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0423596000
_diffrn_orient_matrix_UB_12      0.0066060000
_diffrn_orient_matrix_UB_13      0.0205558000
_diffrn_orient_matrix_UB_21      0.0271224000
_diffrn_orient_matrix_UB_22      0.0563843000
_diffrn_orient_matrix_UB_23      -0.0017489000
_diffrn_orient_matrix_UB_31      -0.0336800000
_diffrn_orient_matrix_UB_32      0.0153465000
_diffrn_orient_matrix_UB_33      0.0191307000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0400
_diffrn_reflns_av_unetI/netI     0.0808
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            27562
_diffrn_reflns_theta_full        25.01
_diffrn_reflns_theta_max         28.06
_diffrn_reflns_theta_min         3.08
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.385
_exptl_absorpt_correction_T_max  0.989
_exptl_absorpt_correction_T_min  0.956
_exptl_absorpt_correction_type   analytical
_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)
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 yellowish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.338
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1632
_exptl_crystal_size_max          0.1465
_exptl_crystal_size_mid          0.078
_exptl_crystal_size_min          0.0329
_refine_diff_density_max         0.673
_refine_diff_density_min         -0.602
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1040
_refine_ls_number_reflns         15480
_refine_ls_number_restraints     70
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0762
_refine_ls_R_factor_gt           0.0516
_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^)+(0.0348P)^2^+1.3793P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0995
_refine_ls_wR_factor_ref         0.1120
_reflns_number_gt                11659
_reflns_number_total             15480
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            om5010429_si_002.cif
_cod_data_source_block           '[3b]BPh4.CH2Cl2'
_cod_depositor_comments
'Adding full bibliography for 4084912--4084917.cif.'
_cod_database_code               4084912
_chemical_oxdiff_formula         'C96 H80 B1 Cl2 O4 P3 Ru1'
_chemical_oxdiff_usercomment     'Lizzie Smith ejs313'
_reflns_odcompleteness_completeness 98.79
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.01
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C96-Cl1 = C96-Cl2
 1.745 with sigma of 0.001
 C96A-Cl2A = C96A-Cl1A
 1.745 with sigma of 0.001
 C96B-Cl1B = C96B-Cl2B
 1.745 with sigma of 0.001
 Cl1-Cl2
 2.9 with sigma of 0.001
 Cl1B-Cl2B
 2.9 with sigma of 0.001
 Cl2A-Cl1A
 2.9 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C3) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C6) \\sim
Ueq, Uanis(C7) \\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(C4A) \\sim Ueq,
Uanis(C5A) \\sim Ueq, Uanis(C6A) \\sim Ueq, Uanis(C7A) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(O3) = Uanis(O3A)
Uanis(O4) = Uanis(O4A)
Uanis(C8) = Uanis(C8A)
Uanis(C16) = Uanis(C16A)
Uanis(C17) = Uanis(C17A)
Uanis(C15) = Uanis(C15A)
Uanis(C1) = Uanis(C1A)
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(P1) = Uanis(P1A)
Uanis(C18A) = Uanis(C18)
Uanis(C23) = Uanis(C23A)
Uanis(C20) = Uanis(C20A)
Uanis(C21) = Uanis(C21A)
Uanis(C19) = Uanis(C19A)
Uanis(C22) = Uanis(C22A)
Uanis(O1) = Uanis(O1A)
Uanis(Cl2) = Uanis(Cl1A)
Uanis(Cl1) = Uanis(Cl2B)
Uanis(Cl2A) = Uanis(Cl1B)
Uanis(C96) = Uanis(C96A) = Uanis(C96B)
4. Others
 1*[Sof(C96)+Sof(H96A)+Sof(H96B)+Sof(Cl1)+Sof(Cl2)]+1*[Sof(C96A)+Sof(H96C)+
 Sof(H96D)+Sof(Cl2A)+Sof(Cl1A)]+1*[Sof(C96B)+Sof(H96E)+Sof(H96F)+Sof(Cl1B)+
 Sof(Cl2B)]=1 with esd of 0.001
 Sof(C1A)=Sof(C2A)=Sof(C7A)=Sof(H7A)=Sof(C6A)=Sof(H6A)=Sof(C5A)=Sof(H5A)=
 Sof(C4A)=Sof(H4A)=Sof(C3A)=Sof(H3A)=Sof(C8A)=Sof(C15A)=Sof(C16A)=Sof(H16A)=
 Sof(C17A)=Sof(H17C)=Sof(H17D)=Sof(C18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=
 Sof(H20A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(H22A)=Sof(C23A)=Sof(H23A)=Sof(O1A)=
 Sof(O2A)=Sof(O3A)=Sof(O4A)=Sof(P1A)=1-FVAR(1)
 Sof(C1)=Sof(C2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=Sof(C6)=
 Sof(H6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(C15)=Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17A)=
 Sof(H17B)=Sof(C18)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=
 Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=Sof(O1)=Sof(O2)=Sof(O3)=Sof(O4)=Sof(P1)=
 FVAR(1)
 Sof(C96)=Sof(H96A)=Sof(H96B)=Sof(Cl1)=Sof(Cl2)=FVAR(2)
 Sof(C96A)=Sof(H96C)=Sof(H96D)=Sof(Cl2A)=Sof(Cl1A)=FVAR(3)
 Sof(C96B)=Sof(H96E)=Sof(H96F)=Sof(Cl1B)=Sof(Cl2B)=FVAR(4)
5.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C17A(H17C,H17D), C96(H96A,H96B), C96A(H96C,H96D), C96B(H96E,
 H96F)
5.b Aromatic/amide H refined with riding coordinates:
 C7A(H7A), C6A(H6A), C5A(H5A), C4A(H4A), C3A(H3A), C3(H3), C4(H4), C5(H5),
 C6(H6), C7(H7), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16),
 C16A(H16A), C19A(H19A), C20A(H20A), C21A(H21A), C22A(H22A), C23A(H23A),
 C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C25(H25), C26(H26), C27(H27),
  C28(H28), C29(H29), C31(H31), C32(H32), C33(H33), C34(H34), C35(H35),
 C37(H37), C38(H38), C39(H39), C40(H40), C41(H41), C43(H43), C44(H44), C45(H45),
  C46(H46), C47(H47), C49(H49), C50(H50), C51(H51), C52(H52), C53(H53),
 C55(H55), C56(H56), C57(H57), C58(H58), C59(H59), C61(H61), C62(H62), C63(H63),
  C64(H64), C65(H65), C67(H67), C68(H68), C69(H69), C70(H70), C71(H71),
 C73(H73), C74(H74), C75(H75), C76(H76), C77(H77), C79(H79), C80(H80), C81(H81),
  C82(H82), C83(H83), C85(H85), C86(H86), C87(H87), C88(H88), C89(H89),
 C91(H91), C92(H92), C93(H93), C94(H94), C95(H95)
5.c Fitted hexagon refined as free rotating group:
 C2A(C7A,C6A,C5A,C4A,C3A), C18A(C19A,C20A,C21A,C22A,C23A)
;