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_4516698
_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_formula_moiety         '4(C46 H41 N6 P Ru)'
_chemical_formula_sum            'C184 H164 N24 P4 Ru4'
_chemical_formula_weight         3239.55
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_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                 90.769(6)
_cell_angle_gamma                90.00
_cell_formula_units_Z            1
_cell_length_a                   12.9692(2)
_cell_length_b                   16.8857(3)
_cell_length_c                   17.2680(12)
_cell_measurement_reflns_used    23782
_cell_measurement_temperature    85
_cell_measurement_theta_max      68.2
_cell_measurement_theta_min      2.60
_cell_volume                     3781.2(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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      85
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.1160
_diffrn_reflns_av_unetI/netI     0.0721
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            56862
_diffrn_reflns_theta_full        68.25
_diffrn_reflns_theta_max         68.25
_diffrn_reflns_theta_min         3.66
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    4.081
_exptl_absorpt_correction_T_max  0.922
_exptl_absorpt_correction_T_min  0.537
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Jacobson, R. (1998) Private communication'
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.423
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             1672
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.516
_refine_diff_density_min         -2.135
_refine_diff_density_rms         0.144
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     489
_refine_ls_number_reflns         6924
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.0832
_refine_ls_R_factor_gt           0.0788
_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^)+(0.1369P)^2^+9.3932P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2150
_refine_ls_wR_factor_ref         0.2205
_reflns_number_gt                6249
_reflns_number_total             6924
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            cs6b01465_si_003.cif
_cod_data_source_block           shelx
_cod_database_code               4516698
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 N6(H6A,H6B), C1(H1A,H1B), C21(H21A,H21B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C11(H11), C12(H12), C16(H16),
 C17(H17), C18(H18), C23(H23), C24(H24), C26(H26), C27(H27), C30(H30), C31(H31),
  C32(H32), C33(H33), C34(H34), C36(H36), C37(H37), C38(H38), C39(H39),
 C40(H40), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46)
2.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C28(H28A,H28B,H28C)
;
_olex2_submission_special_instructions 'No special instructions were received'