Deeper Mechanistic Insight into Ru Pincer-Mediated Acceptorless Dehydrogenative Coupling of Alcohols: Exchanges, Intermediates, and Deactivation Species
Nguyen, Duc Hanh; Trivelli, Xavier; Capet, Frédéric; Swesi, Youssef; Favre-Réguillon, Alain; Vanoye, Laurent; Dumeignil, Franck; Gauvin, Régis M.; ACS Catalysis 8 (2018) 4719–; doi:10.1021/acscatal.8b00995

data_4515578
_publ_section_title
;
 Deeper Mechanistic Insight into Ru Pincer-Mediated Acceptorless
 Dehydrogenative Coupling of Alcohols: Exchanges, Intermediates, and
 Deactivation Species
;
_journal_issue                   5
_journal_name_full               'ACS Catalysis'
_journal_page_first              4719
_journal_paper_doi               10.1021/acscatal.8b00995
_journal_volume                  8
_journal_year                    2018
_chemical_formula_moiety         '3(C17 H39 N O2 P2 Ru), 4(H2 O)'
_chemical_formula_sum            'C51 H125 N3 O10 P6 Ru3'
_chemical_formula_weight         1429.56
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-07-26
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                88.609(2)
_cell_angle_beta                 71.881(2)
_cell_angle_gamma                62.8250(10)
_cell_formula_units_Z            2
_cell_length_a                   15.1793(5)
_cell_length_b                   16.5074(8)
_cell_length_c                   16.6640(6)
_cell_measurement_reflns_used    9544
_cell_measurement_temperature    100.01
_cell_measurement_theta_max      32.96
_cell_measurement_theta_min      2.38
_cell_volume                     3496.0(2)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015b)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100.01
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0271
_diffrn_reflns_av_unetI/netI     0.0130
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            177321
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.283
_diffrn_reflns_theta_min         1.298
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.825
_exptl_absorpt_correction_T_max  0.7465
_exptl_absorpt_correction_T_min  0.7050
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0596 before and 0.0420 after correction.
The Ratio of minimum to maximum transmission is 0.9444.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.358
_exptl_crystal_description       block
_exptl_crystal_F_000             1508
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.24
_refine_diff_density_max         1.749
_refine_diff_density_min         -1.040
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     773
_refine_ls_number_reflns         17335
_refine_ls_number_restraints     11
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0221
_refine_ls_R_factor_gt           0.0198
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0183P)^2^+2.8952P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0468
_refine_ls_wR_factor_ref         0.0481
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16221
_reflns_number_total             17335
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b00995_si_002.cif
_cod_data_source_block           dhng209
_cod_database_code               4515578
_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
 O2-H2 = O4-H4A = O6_$1-H6_$1 = O4W-H4WB = O4W-H4WA = O3W-H3WA = O3W-H3WB =
 O2W-H2WA = O2W-H2WB = O1W-H1WA = O1W-H1WB
 0.82 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C15A) = Uanis(C15B)
Uanis(C16A) = Uanis(C16B)
Uanis(C14A) = Uanis(C14B)
Uanis(C13B) = Uanis(C13A)
Uanis(C11B) = Uanis(C11A)
Uanis(C12B) = Uanis(C12A)
4. Others
 Sof(C15B)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16B)=Sof(H16D)=Sof(H16E)=
 Sof(H16F)=Sof(C14B)=Sof(H14B)=Sof(C11B)=Sof(H11B)=Sof(C12B)=Sof(H12D)=
 Sof(H12E)=Sof(H12F)=Sof(C13B)=Sof(H13D)=Sof(H13E)=Sof(H13F)=1-FVAR(1)
 Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16A)=
 Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C11A)=Sof(H11A)=Sof(C13A)=Sof(H13A)=
 Sof(H13B)=Sof(H13C)=Sof(C12A)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C4(H4), C1(H1A), C45(H45), C35(H35), C38(H38), C48(H48), C18(H18), C21(H21),
 C28(H28), C31(H31), C14A(H14A), C14B(H14B), C11A(H11A), C11B(H11B)
5.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C9(H9A,H9B), C10(H10A,H10B), C8(H8A,H8B), C44(H44A,H44B),
 C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B), C27(H27A,H27B), C26(H26A,H26B),
  C25(H25A,H25B), C24(H24A,H24B)
5.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C6(H6A,H6B,H6C), C5(H5A,H5B,H5C), C40(H40A,
 H40B,H40C), C39(H39A,H39B,H39C), C50(H50A,H50B,H50C), C49(H49A,H49B,H49C),
 C46(H46A,H46B,H46C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C47(H47A,H47B,
 H47C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C19(H19A,H19B,H19C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C),
 C20(H20A,H20B,H20C), C15A(H15A,H15B,H15C), C16A(H16A,H16B,H16C), C15B(H15D,
 H15E,H15F), C16B(H16D,H16E,H16F), C13A(H13A,H13B,H13C), C12A(H12A,H12B,H12C),
 C12B(H12D,H12E,H12F), C13B(H13D,H13E,H13F)
;
_shelx_res_checksum              42208
_shelx_hkl_checksum              20684
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'