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_4515577
_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         'C19 H43 N O2 P2 Ru, C2 H6 O'
_chemical_formula_sum            'C21 H49 N O3 P2 Ru'
_chemical_formula_weight         526.62
_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   mixed
_audit_creation_date             2016-07-29
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.948(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.2573(9)
_cell_length_b                   13.3386(8)
_cell_length_c                   15.3535(10)
_cell_measurement_reflns_used    9456
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      33.09
_cell_measurement_theta_min      2.50
_cell_volume                     2711.4(3)
_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)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_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  0.0410
_diffrn_reflns_av_unetI/netI     0.0309
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            10465
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         33.175
_diffrn_reflns_theta_min         1.980
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.715
_exptl_absorpt_correction_T_max  0.746534
_exptl_absorpt_correction_T_min  0.688878
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.0994 before and 0.0348 after correction.
 The Ratio of minimum to maximum transmission not present.
 The \l/2 correction factor is Not present
 
For component 2:
 wR2(int) was 0.0988 before and 0.0524 after correction.
 The Ratio of minimum to maximum transmission is 0.92.
 The \l/2 correction factor is Not present

Final HKLF 4 output contains 91835 reflections, Rint = 0.0412
 (33538 with I > 3sig(I), Rint = 0.0296)
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.290
_exptl_crystal_description       block
_exptl_crystal_F_000             1120
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.864
_refine_diff_density_min         -1.042
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     274
_refine_ls_number_reflns         10465
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0470
_refine_ls_R_factor_gt           0.0376
_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^)+(0.0345P)^2^+5.4293P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0883
_refine_ls_wR_factor_ref         0.0927
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9342
_reflns_number_total             10465
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b00995_si_004.cif
_cod_data_source_block           mo_dhng249_5
_cod_database_code               4515577
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.8631 0.1369
2. 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, All O(H) groups
3.a Free rotating group:
 O3(C20,C21,H20A,H20B,H21A,H21B,H21C)
3.b Ternary CH refined with riding coordinates:
 C11(H11), C14(H14), C1(H1A), C4(H4)
3.c Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C7(H7A,H7B), C8(H8A,H8B), C18(H18A,H18B)
3.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C12(H12A,H12B,
 H12C), C6(H6A,H6B,H6C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C2(H2A,H2B,H2C),
 C19(H19A,H19B,H19C)
3.e Idealised tetrahedral OH refined as rotating group:
 O3(H3)
;
_shelx_res_checksum              63527
_shelx_hkl_checksum              60457
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'