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_4516668
_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         'C56 H47 Cl2 N5 P2 Ru, C H2 Cl2'
_chemical_formula_sum            'C57 H49 Cl4 N5 P2 Ru'
_chemical_formula_weight         1108.82
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_cell_setting           orthorhombic
_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_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   21.7779(4)
_cell_length_b                   23.4319(16)
_cell_length_c                   9.6235(2)
_cell_measurement_reflns_used    20589
_cell_measurement_temperature    85(2)
_cell_measurement_theta_max      68.30
_cell_measurement_theta_min      2.80
_cell_volume                     4910.8(4)
_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 14.629
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.1211
_diffrn_reflns_av_sigmaI/netI    0.0969
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            40325
_diffrn_reflns_theta_full        68.23
_diffrn_reflns_theta_max         68.23
_diffrn_reflns_theta_min         2.77
_exptl_absorpt_coefficient_mu    5.558
_exptl_absorpt_correction_T_max  0.6647
_exptl_absorpt_correction_T_min  0.4700
_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    1.500
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             2272
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.377
_refine_diff_density_min         -2.045
_refine_diff_density_rms         0.161
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.164(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.129
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     629
_refine_ls_number_reflns         8819
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.128
_refine_ls_R_factor_all          0.0855
_refine_ls_R_factor_gt           0.0793
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1524P)^2^+1.1901P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2204
_refine_ls_wR_factor_ref         0.2324
_reflns_number_gt                7772
_reflns_number_total             8819
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            cs5b00952_si_002.cif
_cod_data_source_block           kt2094
_cod_original_sg_symbol_H-M      Pna2(1)
_cod_database_code               4516668