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_4082142
_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_formula_moiety
'B F4, C45 H43 O4 P2 Ru, 0.85(C3 H6 O1), 0.15(C4 H10 O)'
_chemical_formula_sum            'C48.15 H49.6 B F4 O5 P2 Ru'
_chemical_formula_weight         958.04
_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             2013-06-19
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                109.732(3)
_cell_angle_beta                 90.580(3)
_cell_angle_gamma                107.771(3)
_cell_formula_units_Z            4
_cell_length_a                   13.7465(5)
_cell_length_b                   18.7040(7)
_cell_length_c                   19.7169(6)
_cell_measurement_reflns_used    12385
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      25.9729
_cell_measurement_theta_min      2.8725
_cell_volume                     4507.8(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
;
SHELXH, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      110.00(10)
_diffrn_detector_area_resol_mean 16.1450
_diffrn_measured_fraction_theta_full 0.809
_diffrn_measured_fraction_theta_max 0.809
_diffrn_measurement_details
;
  1 omega  -10.00   80.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       11.2330   57.0000   60.0000 90

  2 omega   -3.00   80.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       11.2330   57.0000 -180.0000 83

  3 omega  -58.00   33.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       11.2330  -57.0000  -90.0000 91

  4 omega  -31.00   10.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       -9.8267   57.0000  150.0000 41

  5 omega  -20.00   53.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       11.2330  -99.0000   60.0000 73
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0289999000
_diffrn_orient_matrix_UB_12      -0.0230221000
_diffrn_orient_matrix_UB_13      0.0065318000
_diffrn_orient_matrix_UB_21      0.0064305000
_diffrn_orient_matrix_UB_22      -0.0136452000
_diffrn_orient_matrix_UB_23      -0.0373163000
_diffrn_orient_matrix_UB_31      0.0457988000
_diffrn_orient_matrix_UB_32      0.0331668000
_diffrn_orient_matrix_UB_33      0.0068839000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0000
_diffrn_reflns_av_unetI/netI     0.0509
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            24811
_diffrn_reflns_theta_full        26.11
_diffrn_reflns_theta_max         26.11
_diffrn_reflns_theta_min         2.89
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.481
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87341
_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            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.412
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1974
_exptl_crystal_size_max          0.2626
_exptl_crystal_size_mid          0.193
_exptl_crystal_size_min          0.1579
_refine_diff_density_max         1.301
_refine_diff_density_min         -1.210
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1118
_refine_ls_number_reflns         24811
_refine_ls_number_restraints     72
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0647
_refine_ls_R_factor_gt           0.0460
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0729P)^2^+2.5417P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1211
_refine_ls_wR_factor_ref         0.1280
_reflns_number_gt                19141
_reflns_number_total             24811
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            om4009247_si_001.cif
_cod_data_source_block           '[3b]BF4.CH3COCH3'
_cod_original_formula_sum        'C48.15 H49.60 B F4 O5 P2 Ru'
_cod_database_code               4082142
_chemical_oxdiff_formula         C45h43B1F4O4P2Ru1
_chemical_oxdiff_usercomment     ejs88-2
_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
 C98-O11 = C99-O11
 1.43 with sigma of 0.01
 C95A-C94A = C94A-C96A = C97-C98 = C99-C100
 1.52 with sigma of 0.01
 C94-O10
 1.21 with sigma of 0.01
 C95-C94 = C94-C96
 1.52 with sigma of 0.01
 O9-C91 = O9A-C91A
 1.21 with sigma of 0.01
 C94A-O10A = C91A-O9A
 1.21 with sigma of 0.01
 C93-C91 = C91A-C93A = C92A-C91A = C92-C91
 1.52 with sigma of 0.01
 C96A-C95A
 2.58 with sigma of 0.01
 C98-C99
 2.39 with sigma of 0.04
 C97-O11 = C100-O11
 2.41 with sigma of 0.04
 C95-C96
 2.58 with sigma of 0.01
 C96A-O10A = C95A-O10A
 2.4 with sigma of 0.01
 C95-O10 = C96-O10
 2.4 with sigma of 0.01
 C92-C93 = C92A-C93A
 2.58 with sigma of 0.01
 C92-O9 = C92A-O9A = C93-O9 = C93A-O9A
 2.4 with sigma of 0.01
3. Restrained planarity
 C94A, C95A, C96A, O10A
 with sigma of 0.05
 C94, C95, C96, C94, O10
 with sigma of 0.05
 C91, C92, C93, O9
 with sigma of 0.05
 C91A, C92A, C93A, O9A
 with sigma of 0.05
4. Uiso/Uaniso restraints and constraints
Uanis(O9) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C66A) = Uanis(C66)
Uanis(C65) = Uanis(C65A)
Uanis(C64A) = Uanis(C64)
Uanis(C63A) = Uanis(C63)
Uanis(C62A) = Uanis(C62)
Uanis(C61A) = Uanis(C61)
Uiso(C96) = Uiso(C99)
Uiso(O10) = Uiso(C98)
Uiso(C94) = Uiso(O11)
Uanis(C91A) = Uanis(C91) = Uanis(O9A)
Uanis(O9) = Uanis(C92A)
Uanis(C93A) = Uanis(C93) = Uanis(C92A) = Uanis(C92)
Uanis(C58) = Uanis(C58A)
Uanis(C57) = Uanis(C57A)
Uanis(C59) = Uanis(C59A)
Uanis(C60) = Uanis(C60A)
5. Others
 1*[Sof(C94A)+Sof(C95A)+Sof(H95D)+Sof(H95E)+Sof(H95F)+Sof(C96A)+Sof(H96D)+
 Sof(H96E)+Sof(H96F)+Sof(O10A)]+1*[Sof(C94)+Sof(C95)+Sof(H95A)+Sof(H95B)+
 Sof(H95C)+Sof(C96)+Sof(H96A)+Sof(H96B)+Sof(H96C)+Sof(O10)]+1*[Sof(C97)+
 Sof(H97A)+Sof(H97B)+Sof(H97C)+Sof(C98)+Sof(H98A)+Sof(H98B)+Sof(C99)+Sof(H99A)+
 Sof(H99B)+Sof(C100)+Sof(H10A)+Sof(H10B)+Sof(H10C)+Sof(O11)]=1 with esd of 0.001
 Sof(C55)=Sof(C56)=Sof(H56)=Sof(C57)=Sof(H57)=Sof(C58)=Sof(H58)=Sof(C59)=
 Sof(H59)=Sof(C60)=Sof(H60)=1-FVAR(1)
 Sof(C55A)=Sof(C56A)=Sof(H56A)=Sof(C57A)=Sof(H57A)=Sof(C58A)=Sof(H58A)=
 Sof(C59A)=Sof(H59A)=Sof(C60A)=Sof(H60A)=FVAR(1)
 Sof(C61A)=Sof(C62A)=Sof(H62A)=Sof(C63A)=Sof(H63A)=Sof(C64A)=Sof(H64A)=
 Sof(C65A)=Sof(H65A)=Sof(C66A)=Sof(H66A)=1-FVAR(2)
 Sof(C61)=Sof(C62)=Sof(H62)=Sof(C63)=Sof(H63)=Sof(C64)=Sof(H64)=Sof(C65)=
 Sof(H65)=Sof(C66)=Sof(H66)=FVAR(2)
 Sof(C91)=Sof(C92)=Sof(H92A)=Sof(H92B)=Sof(H92C)=Sof(C93)=Sof(H93A)=Sof(H93B)=
 Sof(H93C)=Sof(O9)=1-FVAR(3)
 Sof(C91A)=Sof(C92A)=Sof(H92D)=Sof(H92E)=Sof(H92F)=Sof(C93A)=Sof(H93D)=
 Sof(H93E)=Sof(H93F)=Sof(O9A)=FVAR(3)
 Sof(C94A)=Sof(C95A)=Sof(H95D)=Sof(H95E)=Sof(H95F)=Sof(C96A)=Sof(H96D)=
 Sof(H96E)=Sof(H96F)=Sof(O10A)=FVAR(4)
 Sof(C94)=Sof(C95)=Sof(H95A)=Sof(H95B)=Sof(H95C)=Sof(C96)=Sof(H96A)=Sof(H96B)=
 Sof(H96C)=Sof(O10)=FVAR(5)
 Sof(C97)=Sof(H97A)=Sof(H97B)=Sof(H97C)=Sof(C98)=Sof(H98A)=Sof(H98B)=Sof(C99)=
 Sof(H99A)=Sof(H99B)=Sof(C100)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(O11)=FVAR(6)
 Fixed Uiso: C94(0.1) C94A(0.1) C95(0.1) C95A(0.1) C96(0.1) C96A(0.1) C97(0.1)
 C98(0.1) C99(0.1) C100(0.1) O10(0.1) O10A(0.1) O11(0.1)
6.a Secondary CH2 refined with riding coordinates:
 C98(H98A,H98B), C99(H99A,H99B)
6.b Me refined with riding coordinates:
 C92A(H92D,H92E,H92F), C93(H93A,H93B,H93C), C93A(H93D,H93E,H93F), C95(H95A,
 H95B,H95C), C95A(H95D,H95E,H95F), C96(H96A,H96B,H96C), C96A(H96D,H96E,H96F),
 C97(H97A,H97B,H97C), C100(H10A,H10B,H10C)
6.c Aromatic/amide H refined with riding coordinates:
 C6(H6), 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), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45),
  C51(H51), C56(H56), C57(H57), C58(H58), C59(H59), C60(H60), C56A(H56A),
 C57A(H57A), C58A(H58A), C59A(H59A), C60A(H60A), C62(H62), C63(H63), C64(H64),
 C65(H65), C66(H66), C62A(H62A), C63A(H63A), C64A(H64A), C65A(H65A), C66A(H66A),
  C68(H68), C69(H69), C70(H70), C71(H71), C72(H72), C74(H74), C75(H75),
 C76(H76), C77(H77), C78(H78), C80(H80), C81(H81), C82(H82), C83(H83), C84(H84),
  C86(H86), C87(H87), C88(H88), C89(H89), C90(H90)
6.d Fitted hexagon refined as free rotating group:
 C55(C56,C57,C58,C59,C60), C55A(C56A,C57A,C58A,C59A,C60A), C61(C62,C63,C64,C65,
 C66), C61A(C62A,C63A,C64A,C65A,C66A)
6.e Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C47(H47A,
 H47B,H47C), C49(H49A,H49B,H49C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C),
 C92(H92A,H92B,H92C)
;