Scope and Mechanistic Analysis for Chemoselective Hydrogenolysis of Carbonyl Compounds Catalyzed by a Cationic Ruthenium Hydride Complex with a Tunable Phenol Ligand.
Kalutharage, Nishantha; Yi, Chae S.; Journal of the American Chemical Society 137 (2015) 11105–11114; doi:10.1021/jacs.5b06097

data_4124361
_publ_section_title
;
 Scope and Mechanistic Analysis for Chemoselective Hydrogenolysis of
 Carbonyl Compounds Catalyzed by a Cationic Ruthenium Hydride Complex with
 a Tunable Phenol Ligand.
;
_journal_issue                   34
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11105
_journal_page_last               11114
_journal_paper_doi               10.1021/jacs.5b06097
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety         'C54 H81 O6 P2 Ru2, B F4, 0.78(C1 H2 Cl2)'
_chemical_formula_sum            'C54.78 H82.57 B Cl1.57 F4 O6 P2 Ru2'
_chemical_formula_weight         1243.55
_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   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-02-04
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 107.1132(19)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   19.8500(4)
_cell_length_b                   17.9759(3)
_cell_length_c                   16.6953(3)
_cell_measurement_reflns_used    16594
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      29.1800
_cell_measurement_theta_min      3.1120
_cell_volume                     5693.49(19)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2013)'
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector_area_resol_mean 10.3756
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.896
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0076497000
_diffrn_orient_matrix_UB_12      -0.0351813000
_diffrn_orient_matrix_UB_13      -0.0144855000
_diffrn_orient_matrix_UB_21      -0.0342935000
_diffrn_orient_matrix_UB_22      -0.0125731000
_diffrn_orient_matrix_UB_23      -0.0018336000
_diffrn_orient_matrix_UB_31      -0.0128043000
_diffrn_orient_matrix_UB_32      0.0126768000
_diffrn_orient_matrix_UB_33      -0.0419878000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0353
_diffrn_reflns_av_unetI/netI     0.0322
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            32469
_diffrn_reflns_theta_full        27.00
_diffrn_reflns_theta_max         29.47
_diffrn_reflns_theta_min         2.81
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.720
_exptl_absorpt_correction_T_max  0.961
_exptl_absorpt_correction_T_min  0.777
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.451
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             2579
_exptl_crystal_size_max          0.6545
_exptl_crystal_size_mid          0.082
_exptl_crystal_size_min          0.0667
_refine_diff_density_max         0.850
_refine_diff_density_min         -0.602
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     389
_refine_ls_number_reflns         7101
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.103
_refine_ls_R_factor_all          0.0401
_refine_ls_R_factor_gt           0.0324
_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^)+(0.0249P)^2^+12.8253P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0730
_refine_ls_wR_factor_ref         0.0766
_reflns_number_gt                6206
_reflns_number_total             7101
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja5b06097_si_004.cif
_cod_data_source_block           yi2r
_cod_original_cell_volume        5693.49(17)
_cod_database_code               4124361
_chemical_oxdiff_formula         'Ru B F4 C27 O3 H42 P'
_reflns_odcompleteness_completeness 99.82
_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
 B1-F1 = B1-F2 = B1-F3 = B1-F4
 1.30896 with sigma of 0.02
 C1S-Cl1 = C1S-Cl2 = C2S-Cl3 = C2S-Cl4
 1.74271 with sigma of 0.02
3. Rigid bond restraints
 B1, F1, F2, F3, F4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1S, Cl1, Cl2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C2S, Cl3, Cl4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C1S) = Uanis(C2S)
5. Others
 Sof(Cl1)=Sof(Cl2)=Sof(C1S)=Sof(H1SA)=Sof(H1SB)=FVAR(1)
 Sof(Cl3)=Sof(Cl4)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=FVAR(4)
 Fixed Sof: F1(0.5) F2(0.5) F3(0.5) F4(0.5) B1(0.5)
6.a Ternary CH refined with riding coordinates:
 C9(H9), C15(H15), C21(H21)
6.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,
 H14B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B),
 C20(H20A,H20B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B),
  C26(H26A,H26B), C2S(H2SA,H2SB), C1S(H1SA,H1SB)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6)
6.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C)
;