The Mechanism of Acceptorless Amine Double Dehydrogenation byN,N,N-Amide Ruthenium(II) Hydrides: A Combined Experimental and Computational Study
Hale, Lillian V. A.; Malakar, Tanmay; Tseng, Kuei-Nin T.; Zimmerman, Paul M.; Paul, Ankan; Szymczak, Nathaniel K.; ACS Catalysis 6 (2016) 4799–; doi:10.1021/acscatal.6b01465

data_4516697
_publ_section_title
;
 The Mechanism of Acceptorless Amine Double Dehydrogenation byN,N,N-Amide
 Ruthenium(II) Hydrides: A Combined Experimental and Computational Study
;
_journal_issue                   8
_journal_name_full               'ACS Catalysis'
_journal_page_first              4799
_journal_paper_doi               10.1021/acscatal.6b01465
_journal_volume                  6
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         '4(C42 H39 Cl N5 P Ru)'
_chemical_formula_sum            'C168 H156 Cl4 N20 P4 Ru4'
_chemical_formula_weight         3125.09
_space_group_crystal_system      tetragonal
_space_group_IT_number           81
_space_group_name_Hall           'P -4'
_space_group_name_H-M_alt        'P -4'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-04-01
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            1
_cell_length_a                   19.0698(4)
_cell_length_b                   19.0698(4)
_cell_length_c                   9.8294(7)
_cell_measurement_reflns_used    44166
_cell_measurement_temperature    85
_cell_measurement_theta_max      68.30
_cell_measurement_theta_min      6.60
_cell_volume                     3574.5(3)
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      85
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Rigaku Saturn70 CCD'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54187
_diffrn_reflns_av_R_equivalents  0.0674
_diffrn_reflns_av_unetI/netI     0.0438
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            55704
_diffrn_reflns_theta_full        68.20
_diffrn_reflns_theta_max         68.20
_diffrn_reflns_theta_min         6.57
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    4.956
_exptl_absorpt_correction_T_max  0.9521
_exptl_absorpt_correction_T_min  0.4226
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Jacobson, R. (1998) Private communication'
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.452
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1608
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.586
_refine_diff_density_min         -0.965
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.010(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.139
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     463
_refine_ls_number_reflns         6534
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.139
_refine_ls_R_factor_all          0.0381
_refine_ls_R_factor_gt           0.0374
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0415P)^2^+4.3953P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0931
_refine_ls_wR_factor_ref         0.0936
_reflns_number_gt                6351
_reflns_number_total             6534
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            cs6b01465_si_003.cif
_cod_data_source_block           lh3105
_cod_database_code               4516697
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 P1, C13, C37
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
3.a Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C14(H14), C15(H15), C16(H16), C17(H17), C21(H21),
 C22(H22), C23(H23), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30), C32(H32),
  C33(H33), C34(H34), C35(H35), C36(H36), C38(H38), C39(H39), C40(H40),
 C41(H41), C42(H42)
3.b Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C)
;
_olex2_submission_special_instructions 'No special instructions were received'