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_4084913
_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
'C60.85 H53.77 Br0.08 O3.85 P3 Ru, B F4, 1.02(C H2 Cl2)'
_chemical_formula_sum
'C61.87 H55.81 B Br0.08 Cl2.04 F4 O3.85 P3 Ru'
_chemical_formula_weight         1219.82
_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             2014-10-13
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                94.638(4)
_cell_angle_beta                 92.883(4)
_cell_angle_gamma                103.829(4)
_cell_formula_units_Z            2
_cell_length_a                   11.7606(6)
_cell_length_b                   15.4442(7)
_cell_length_c                   17.4519(8)
_cell_measurement_reflns_used    9678
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      29.6980
_cell_measurement_theta_min      3.2380
_cell_volume                     3059.9(3)
_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  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      110.00(10)
_diffrn_detector_area_resol_mean 16.1450
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.871
_diffrn_measurement_details
;
  1 omega  -34.00   45.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      -20.7727   77.0000  120.0000 79

  2 omega  -84.00    5.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      -20.7727  -37.0000 -120.0000 89

  3 omega  -30.00   14.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      -20.7727  -90.0000  -92.0000 44

  4 omega  -65.00   41.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      -20.7727   19.0000   90.0000 106

  5 omega   35.00   63.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       22.1789  -99.0000  150.0000 28

  6 omega   50.00   98.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       22.1789  178.0000  -60.0000 48

  7 omega   19.00   63.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       22.1789  -99.0000   60.0000 44
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0438704000
_diffrn_orient_matrix_UB_12      0.0171322000
_diffrn_orient_matrix_UB_13      0.0304551000
_diffrn_orient_matrix_UB_21      0.0252108000
_diffrn_orient_matrix_UB_22      0.0360237000
_diffrn_orient_matrix_UB_23      -0.0214196000
_diffrn_orient_matrix_UB_31      -0.0363008000
_diffrn_orient_matrix_UB_32      0.0258175000
_diffrn_orient_matrix_UB_33      0.0168840000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0370
_diffrn_reflns_av_unetI/netI     0.0666
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.871
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            28839
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.871
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.306
_diffrn_reflns_theta_min         2.847
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.529
_exptl_absorpt_correction_T_max  0.968
_exptl_absorpt_correction_T_min  0.906
_exptl_absorpt_correction_type   analytical
_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)
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 orangish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.324
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1250.3
_exptl_crystal_size_max          0.3103
_exptl_crystal_size_mid          0.1944
_exptl_crystal_size_min          0.06
_refine_diff_density_max         2.866
_refine_diff_density_min         -1.089
_refine_diff_density_rms         0.143
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     749
_refine_ls_number_reflns         15989
_refine_ls_number_restraints     25
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0935
_refine_ls_R_factor_gt           0.0724
_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^)+(0.0960P)^2^+10.3335P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1976
_refine_ls_wR_factor_ref         0.2128
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12544
_reflns_number_total             15989
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5010429_si_002.cif
_cod_data_source_block           '[4a]0.9[6a]0.1BF4.CH2Cl2'
_cod_depositor_comments
'Adding full bibliography for 4084912--4084917.cif.'
_cod_database_code               4084913
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C63H58B1F4O4P3Ru1 Cl4'
_chemical_oxdiff_usercomment     'Lizzie ejs230'
_reflns_odcompleteness_completeness 99.73
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.82
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C62-Cl1 = C62-Cl2
 1.745 with sigma of 0.005
 C62A-Cl1A = C62A-Cl2A
 1.745 with sigma of 0.005
 C62B-Cl1B = C62B-Cl2B
 1.745 with sigma of 0.005
 C62C-Cl1C = C62C-Cl2C
 1.745 with sigma of 0.005
 Cl1-Cl2
 2.9 with sigma of 0.01
 Cl1A-Cl2A
 2.9 with sigma of 0.01
 Cl1B-Cl2B
 2.9 with sigma of 0.01
 Cl1C-Cl2C
 2.9 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C3) \\sim Ueq, Uanis(Br1) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C3) = Uanis(Br1)
Uanis(Cl1) = Uanis(Cl1A)
Uanis(C62) = Uanis(C62A)
Uanis(Cl2) = Uanis(Cl2A)
Uanis(Cl2B) = Uanis(Cl2C)
Uanis(Cl1B) = Uanis(Cl1C)
Uanis(C62B) = Uanis(C62C)
4. Others
 1*[Sof(C62)+Sof(H62C)+Sof(H62D)+Sof(Cl1)+Sof(Cl2)]+1*[Sof(C62A)+Sof(H62E)+
 Sof(H62F)+Sof(Cl1A)+Sof(Cl2A)]+1*[Sof(C62B)+Sof(H62G)+Sof(H62H)+Sof(Cl1B)+
 Sof(Cl2B)]+1*[Sof(C62C)+Sof(H62A)+Sof(H62B)+Sof(Cl1C)+Sof(Cl2C)]=1 with esd of
 0.002
 Sof(Br1)=1-FVAR(1)
 Sof(C3)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(O3)=Sof(O4)=FVAR(1)
 Sof(C62)=Sof(H62C)=Sof(H62D)=Sof(Cl1)=Sof(Cl2)=FVAR(2)
 Sof(C62A)=Sof(H62E)=Sof(H62F)=Sof(Cl1A)=Sof(Cl2A)=FVAR(3)
 Sof(C62B)=Sof(H62G)=Sof(H62H)=Sof(Cl1B)=Sof(Cl2B)=FVAR(4)
 Sof(C62C)=Sof(H62A)=Sof(H62B)=Sof(Cl1C)=Sof(Cl2C)=FVAR(5)
5.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B)
5.b Aromatic/amide H refined with riding coordinates:
 C7(H7)
;
_olex2_computing_structure_refinement_long 'ShelXL (Sheldrick, 2008)'
_olex2_exptl_crystal_mounting_method 'Oil on loop'
_olex2_submission_special_instructions 'No special instructions were received'