Mechanistic insight into the ruthenium-catalysed anti-Markovnikov hydration of alkynes using a self-assembled complex: a crucial role for ligand-assisted proton shuttle processes.
Breit, Bernhard; Gellrich, Urs; Li, Timothy; Lynam, Jason M.; Milner, Lucy M.; Pridmore, Natalie E.; Slattery, John M.; Whitwood, Adrian C.; Dalton transactions (Cambridge, England : 2003) 43 (2014) 11277–11285; doi:10.1039/c4dt00712c

data_7030952
_publ_section_title
;
 Mechanistic insight into the ruthenium-catalysed anti-Markovnikov
 hydration of alkynes using a self-assembled complex: a crucial role for
 ligand-assisted proton shuttle processes.
;
_journal_issue                   29
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              11277
_journal_page_last               11285
_journal_paper_doi               10.1039/c4dt00712c
_journal_volume                  43
_journal_year                    2014
_chemical_formula_moiety
'C57 H49 F3 N3 O2 P2 Ru, 0.5(C H2 Cl2), F6 P, 0.2(C4 H10 O)'
_chemical_formula_sum            'C58.3 H52 Cl F9 N3 O2.2 P3 Ru'
_chemical_formula_weight         1230.26
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-03-07
_audit_creation_method
;
Olex2 1.2
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.205(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.0193(7)
_cell_length_b                   15.7635(7)
_cell_length_c                   31.3450(14)
_cell_measurement_reflns_used    5581
_cell_measurement_temperature    109.95(10)
_cell_measurement_theta_max      25.3160
_cell_measurement_theta_min      3.2820
_cell_volume                     11157.2(8)
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      109.95(10)
_diffrn_detector_area_resol_mean 16.1450
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.838
_diffrn_measurement_details
;
  1 omega  -19.00   27.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.1830  -99.0000 -120.0000 46

  2 omega  -90.00  -44.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.1830 -178.0000   90.0000 46

  3 omega  -57.00   65.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       16.4330    0.0000 -150.0000 122
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0026248000
_diffrn_orient_matrix_UB_12      -0.0201479000
_diffrn_orient_matrix_UB_13      -0.0197785000
_diffrn_orient_matrix_UB_21      0.0101534000
_diffrn_orient_matrix_UB_22      -0.0375246000
_diffrn_orient_matrix_UB_23      0.0115785000
_diffrn_orient_matrix_UB_31      -0.0295868000
_diffrn_orient_matrix_UB_32      -0.0146799000
_diffrn_orient_matrix_UB_33      -0.0025479000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0345
_diffrn_reflns_av_unetI/netI     0.0722
_diffrn_reflns_Laue_measured_fraction_full 0.974
_diffrn_reflns_Laue_measured_fraction_max 0.838
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            23119
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.838
_diffrn_reflns_theta_full        25.10
_diffrn_reflns_theta_max         28.078
_diffrn_reflns_theta_min         2.902
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.491
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82102
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31) 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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.465
_exptl_crystal_description       block
_exptl_crystal_F_000             5019.2
_exptl_crystal_size_max          0.181
_exptl_crystal_size_mid          0.1127
_exptl_crystal_size_min          0.0908
_refine_diff_density_max         0.723
_refine_diff_density_min         -0.695
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     775
_refine_ls_number_reflns         11380
_refine_ls_number_restraints     92
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0996
_refine_ls_R_factor_gt           0.0639
_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^)+(0.0280P)^2^+62.5382P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1192
_refine_ls_wR_factor_ref         0.1336
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8152
_reflns_number_total             11380
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4dt00712c2.cif
_cod_data_source_block           jml1236
_cod_depositor_comments          'Adding full bibliography for 7030952.cif.'
_cod_original_cell_volume        11157.1(8)
_cod_original_formula_sum        'C58.30 H52 Cl F9 N3 O2.20 P3 Ru'
_cod_database_code               7030952
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C58.3 H52 Cl1 F9 N3 O2.2 P3 Ru1'
_chemical_oxdiff_usercomment     'Lucy M-13'
_reflns_odcompleteness_completeness 99.74
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.10
_olex2_refinement_description
;
1. Restrained distances
 C61-C60
 1.51 with sigma of 0.01
 C63-C62
 1.51 with sigma of 0.01
 C62-O3 = O3-C61
 1.43 with sigma of 0.01
 Cl3-C59 = C58-Cl1 = C58-Cl2 = C59-Cl4
 1.745 with sigma of 0.02
2. Uiso/Uaniso restraints and constraints
Uanis(C31A) \\sim Ueq, Uanis(C31B) \\sim Ueq, Uanis(C35B) \\sim Ueq,
Uanis(C35A) \\sim Ueq, Uanis(C30A) \\sim Ueq, Uanis(C30B) \\sim Ueq,
Uanis(C34A) \\sim Ueq, Uanis(C34B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C33A) \\sim Ueq, Uanis(C33B) \\sim Ueq: with sigma of 0.05 and sigma for
terminal atoms of 0.1
Uanis(C61) \\sim Ueq, Uanis(C62) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C63) \\sim Ueq, Uanis(O3) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C34A) = Uanis(C34B)
Uanis(C35A) = Uanis(C35B)
Uanis(C31A) = Uanis(C31B)
Uanis(C30A) = Uanis(C30B)
Uanis(C32A) = Uanis(C32B)
Uanis(C33A) = Uanis(C33B)
Uanis(O3) = Uanis(C63)
Uanis(Cl3) = Uanis(C58) = Uanis(Cl4) = Uanis(C59)
3. Others
 Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(Cl3)=Sof(Cl4)=0.5*(1-FVAR(2))
 Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(Cl1)=Sof(Cl2)=0.5*FVAR(2)
 Fixed Sof: C30A(0.5) C30B(0.5) C31A(0.5) H31A(0.5) C31B(0.5) H31B(0.5)
 C32A(0.5) H32A(0.5) C32B(0.5) H32B(0.5) C33A(0.5) H33A(0.5) C33B(0.5)
 H33B(0.5) C34A(0.5) H34A(0.5) C34B(0.5) H34B(0.5) C35A(0.5) H35A(0.5)
 C35B(0.5) H35B(0.5) C60(0.2) H60A(0.2) H60B(0.2) H60C(0.2) C61(0.2) H61A(0.2)
 H61B(0.2) C62(0.2) H62A(0.2) H62B(0.2) C63(0.2) H63A(0.2) H63B(0.2) H63C(0.2)
 O3(0.2)
;
_olex2_computing_structure_refinement_long 'ShelXL (Sheldrick, 2008)'