Mapping the Elimination of Water from Hydroxyvinylidene Complexes of Ruthenium(II): Access to Allenylidene and Vinylvinylidene Complexes in a Stepwise Fashion
Smith, Elizabeth J.; Johnson, David G.; Thatcher, Robert J.; Whitwood, Adrian C.; Lynam, Jason M.; Organometallics 32 (2013) 7407–; doi:10.1021/om4009247

data_4082141
_publ_section_title
;
 Mapping the Elimination of Water from Hydroxyvinylidene Complexes of
 Ruthenium(II): Access to Allenylidene and Vinylvinylidene Complexes in a
 Stepwise Fashion
;
_journal_issue                   24
_journal_name_full               Organometallics
_journal_page_first              7407
_journal_paper_doi               10.1021/om4009247
_journal_volume                  32
_journal_year                    2013
_chemical_absolute_configuration ad
_chemical_formula_moiety         'B F4, C55 H47 O4 P2 Ru, 1.5(C H2 Cl2)'
_chemical_formula_sum            'C56.5 H50 B Cl3 F4 O4 P2 Ru'
_chemical_formula_weight         1149.13
_chemical_name_systematic
;
 ? 
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_space_group_name_Hall  'P 2c -2n'
_symmetry_space_group_name_H-M   'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-06-10
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   21.0188(5)
_cell_length_b                   11.7455(4)
_cell_length_c                   22.0402(7)
_cell_measurement_reflns_used    9137
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      28.9683
_cell_measurement_theta_min      2.9306
_cell_volume                     5441.2(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
XS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_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 0.873
_diffrn_measurement_details
;
  1 omega  -43.00   53.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      -17.6140   37.0000 -180.0000 96

  2 omega   -2.00   39.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -       19.0202   58.0000   15.0000 41

  3 omega   13.00   89.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -       19.0202   77.0000   30.0000 76
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0132701000
_diffrn_orient_matrix_UB_12      0.0337315000
_diffrn_orient_matrix_UB_13      0.0235182000
_diffrn_orient_matrix_UB_21      0.0191004000
_diffrn_orient_matrix_UB_22      0.0466229000
_diffrn_orient_matrix_UB_23      -0.0091929000
_diffrn_orient_matrix_UB_31      -0.0244361000
_diffrn_orient_matrix_UB_32      0.0181741000
_diffrn_orient_matrix_UB_33      -0.0199807000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0269
_diffrn_reflns_av_unetI/netI     0.0408
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            23021
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         29.04
_diffrn_reflns_theta_min         3.19
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.553
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.95402
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.403
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2348
_exptl_crystal_size_max          0.1965
_exptl_crystal_size_mid          0.1423
_exptl_crystal_size_min          0.1033
_refine_diff_density_max         1.299
_refine_diff_density_min         -2.061
_refine_diff_density_rms         0.111
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.00(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.147
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     719
_refine_ls_number_reflns         10726
_refine_ls_number_restraints     126
_refine_ls_restrained_S_all      1.144
_refine_ls_R_factor_all          0.0718
_refine_ls_R_factor_gt           0.0647
_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^)+(0.0407P)^2^+27.0219P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1514
_refine_ls_wR_factor_ref         0.1559
_reflns_number_gt                9781
_reflns_number_total             10726
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            om4009247_si_001.cif
_cod_data_source_block           '[3a]BF4.(CH2Cl2)1.5'
_cod_original_formula_sum        'C56.50 H50 B Cl3 F4 O4 P2 Ru'
_cod_database_code               4082141
_chemical_oxdiff_formula         C55H47O4P2Ru1
_reflns_odcompleteness_completeness 99.68
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C56-Cl1 = C56A-Cl1A = C56-Cl2 = C56A-Cl2A
 1.745 with sigma of 0.005
 Cl1-Cl2 = Cl1A-Cl2A
 2.9 with sigma of 0.005
 C5-C6A \\sim C5-C6
 with sigma of 0.02
 C6A-C7A \\sim C6-C7
 with sigma of 0.02
 Cl3-C57 \\sim Cl4-C57
 with sigma of 0.01
 Cl2-C56 \\sim Cl2A-C56 \\sim Cl1A-C56 \\sim Cl1-C56
 with sigma of 0.01
 F4-B1 \\sim F3-B1 \\sim F1-B1 \\sim F2-B1
 with sigma of 0.01
 F4-F3 \\sim F1-F2 \\sim F2-F4 \\sim F3-F1
 with sigma of 0.02
 C8A-C7A \\sim C8-C7
 with sigma of 0.02
 C14-C7 \\sim C14A-C7A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C15A) \\sim Ueq, Uanis(C17A) \\sim Ueq, Uanis(C8A) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C13A) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C12A) \\sim Ueq, Uanis(C9A) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C11A) \\sim Ueq, Uanis(C11) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C19) \\sim Ueq, Uanis(C19A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C7) = Uanis(C7A)
Uanis(C6) = Uanis(C6A)
Uanis(Cl2) = Uanis(Cl2A)
Uanis(Cl1) = Uanis(Cl1A)
Uanis(C56) = Uanis(C56A)
Uanis(C8) = Uanis(C8A)
Uanis(C13) = Uanis(C13A)
Uanis(C9) = Uanis(C9A)
Uanis(C10) = Uanis(C10A)
Uanis(C12) = Uanis(C12A)
Uanis(C11) = Uanis(C11A)
Uanis(C19) = Uanis(C19A)
4. Others
 Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(C8A)=Sof(C13A)=Sof(H13A)=Sof(C12A)=Sof(H12A)=
 Sof(C11A)=Sof(H11A)=Sof(C10A)=Sof(H10A)=Sof(C9A)=Sof(H9A)=Sof(C14A)=Sof(C15A)=
 Sof(H15A)=Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18A)=
 Sof(C19A)=Sof(H19A)=1-FVAR(1)
 Sof(C6)=Sof(H6)=Sof(C7)=Sof(C8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=Sof(C11)=
 Sof(H11)=Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(C15)=Sof(H15)=
 Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18)=Sof(C19)=Sof(H19)=FVAR(1)
 Sof(C56A)=Sof(H56C)=Sof(H56D)=Sof(Cl1A)=Sof(Cl2A)=1-FVAR(2)
 Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(Cl1)=Sof(Cl2)=FVAR(2)
 Fixed Sof: C57(0.5) H57A(0.5) H57B(0.5) Cl3(0.5) Cl4(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C56(H56A,H56B), C56A(H56C,H56D), C57(H57A,H57B)
5.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C6A(H6A), C13A(H13A), C12A(H12A), C11A(H11A), C10A(H10A), C9A(H9A),
 C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C15A(H15A), C16A(H16A),
 C17A(H17A), C18A(H18A), C19A(H19A), C15(H15), C16(H16), C17(H17), C18(H18),
 C19(H19), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), C27(H27), C28(H28),
  C29(H29), C30(H30), C31(H31), C33(H33), C34(H34), C35(H35), C36(H36),
 C37(H37), C39(H39), C40(H40), C41(H41), C42(H42), C43(H43), C45(H45), C46(H46),
  C47(H47), C48(H48), C49(H49), C51(H51), C52(H52), C53(H53), C54(H54), C55(H55)
5.c Fitted hexagon refined as free rotating group:
 C8A(C13A,C12A,C11A,C10A,C9A), C14A(C15A,C16A,C17A,C18A,C19A)
5.d Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C4(H4A,H4B,H4C)
;