Mechanism of N,N,N-Amide Ruthenium(II) Hydride Mediated Acceptorless Alcohol Dehydrogenation: Inner-Sphere β-H Elimination versus Outer-Sphere Bifunctional Metal‒Ligand Cooperativity
Tseng, Kuei-Nin T.; Kampf, Jeff W.; Szymczak, Nathaniel K.; ACS Catalysis 5 (2015) 5468–; doi:10.1021/acscatal.5b00952

data_4516669
_publ_section_title
;
 Mechanism of N,N,N-Amide Ruthenium(II) Hydride Mediated Acceptorless
 Alcohol Dehydrogenation: Inner-Sphere \b-H Elimination versus
 Outer-Sphere Bifunctional Metal--Ligand Cooperativity
;
_journal_issue                   9
_journal_name_full               'ACS Catalysis'
_journal_page_first              5468
_journal_paper_doi               10.1021/acscatal.5b00952
_journal_volume                  5
_journal_year                    2015
_chemical_formula_moiety         'C76 H60 N10 P2 Ru2, 0.5(C6 H6), 3(C6 H6)'
_chemical_formula_sum            'C97 H81 N10 P2 Ru2'
_chemical_formula_weight         1650.80
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                71.991(5)
_cell_angle_beta                 73.730(5)
_cell_angle_gamma                81.086(6)
_cell_formula_units_Z            2
_cell_length_a                   13.7897(3)
_cell_length_b                   15.8415(3)
_cell_length_c                   19.6154(14)
_cell_measurement_reflns_used    45432
_cell_measurement_temperature    85(2)
_cell_measurement_theta_max      68.30
_cell_measurement_theta_min      2.40
_cell_volume                     3900.9(3)
_computing_cell_refinement       'CrystalClear-SM Expert 2.0 r12'
_computing_data_collection
'CrystalClear-SM Expert 2.0 r12 (Rigaku, 2011)'
_computing_data_reduction        'CrystalClear-SM Expert 2.0 r12'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      85(2)
_diffrn_detector_area_resol_mean 29.257
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device_type  'Rigaku Saturn944+ CCD'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  confocal
_diffrn_radiation_source         'micro-focus rotating anode'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1607
_diffrn_reflns_av_sigmaI/netI    0.0880
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            111779
_diffrn_reflns_theta_full        68.24
_diffrn_reflns_theta_max         68.24
_diffrn_reflns_theta_min         2.94
_exptl_absorpt_coefficient_mu    3.961
_exptl_absorpt_correction_T_max  0.9250
_exptl_absorpt_correction_T_min  0.7970
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
    Higashi, T. (1995). Program for Absorption Correction.
    Rigaku Corporation, Tokyo, Japan.
;
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    1.405
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1702
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         2.576
_refine_diff_density_min         -2.494
_refine_diff_density_rms         0.174
_refine_ls_extinction_coef       0.00216(13)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1084
_refine_ls_number_reflns         14107
_refine_ls_number_restraints     204
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.1001
_refine_ls_R_factor_gt           0.0869
_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^)+(0.1570P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2298
_refine_ls_wR_factor_ref         0.2419
_reflns_number_gt                10758
_reflns_number_total             14107
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            cs5b00952_si_002.cif
_cod_data_source_block           kt3103
_cod_database_code               4516669