Isonitrile ruthenium and iron PNP complexes: synthesis, characterization and catalytic assessment for base-free dehydrogenative coupling of alcohols.
Nguyen, Duc Hanh; Merel, Delphine; Merle, Nicolas; Trivelli, Xavier; Capet, Frédéric; Gauvin, Régis M; Dalton transactions (Cambridge, England : 2003) 50 (2021) 10067–10081; doi:10.1039/d1dt01722e

data_7707791
_publ_section_title
;
 Isonitrile ruthenium and iron PNP complexes: synthesis, characterization
 and catalytic assessment for base-free dehydrogenative coupling of
 alcohols.
;
_journal_issue                   29
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10067
_journal_page_last               10081
_journal_paper_doi               10.1039/d1dt01722e
_journal_volume                  50
_journal_year                    2021
_chemical_formula_moiety         'C42 H96 N4 Na P4 Ru2, C8 H20 B'
_chemical_formula_sum            'C50 H116 B N4 Na P4 Ru2'
_chemical_formula_weight         1133.28
_chemical_name_systematic        '[Ru(H)2(t-BuNC)(PNPH)]2(NaBEt4)'
_chemical_properties_physical    Air-sensitive
_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     dual
_audit_creation_date             2018-12-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-05-29 deposited with the CCDC.	2021-06-24 downloaded from the CCDC.
;
_cell_angle_alpha                101.844(2)
_cell_angle_beta                 98.888(2)
_cell_angle_gamma                105.898(2)
_cell_formula_units_Z            2
_cell_length_a                   11.5328(4)
_cell_length_b                   16.0190(6)
_cell_length_c                   18.2909(7)
_cell_measurement_reflns_used    9829
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.67
_cell_measurement_theta_min      2.30
_cell_volume                     3100.0(2)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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 0.994
_diffrn_measured_fraction_theta_max 0.990
_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  0.0262
_diffrn_reflns_av_unetI/netI     0.0190
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            78371
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.680
_diffrn_reflns_theta_min         1.369
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.630
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.7083
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0760 before and 0.0388 after correction. The Ratio of minimum to maximum transmission is 0.9504. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.214
_exptl_crystal_description       plate
_exptl_crystal_F_000             1216
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.248
_exptl_crystal_size_mid          0.232
_exptl_crystal_size_min          0.188
_refine_diff_density_max         3.235
_refine_diff_density_min         -0.931
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     607
_refine_ls_number_reflns         11677
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0547
_refine_ls_R_factor_gt           0.0463
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0584P)^2^+9.4745P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1141
_refine_ls_wR_factor_ref         0.1227
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10239
_reflns_number_total             11677
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt01722e2.cif
_cod_data_source_block           dhng542
_cod_depositor_comments
'Adding full bibliography for 7707785--7707792.cif.'
_cod_database_code               7707791
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.891
_shelx_estimated_absorpt_t_min   0.859
_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
 Ru1-HC
 1.62 with sigma of 0.01
 C20A-C18 \\sim C20B-C18
 with sigma of 0.01
 C18-C21A \\sim C18-C21B
 with sigma of 0.01
 C18-C19A \\sim C18-C19B
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uiso(C21B) = Uiso(C21A)
Uiso(C20A) = Uiso(C20B)
Uiso(C19A) = Uiso(C19B)
4. Others
 Sof(C21B)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C19B)=Sof(H19D)=Sof(H19E)=
 Sof(H19F)=Sof(C20B)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(1)
 Sof(C20A)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C21A)=Sof(H21A)=Sof(H21B)=
 Sof(H21C)=Sof(C19A)=Sof(H19A)=Sof(H19B)=Sof(H19C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C22(H22), C35(H35), C25(H25), C32(H32), C1(H1A), C14(H14), C11(H11), C4(H4)
5.b Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B), C31(H31A,H31B), C45(H45A,H45B), C9(H9A,H9B), C43(H43A,H43B),
 C10(H10A,H10B), C30(H30A,H30B), C8(H8A,H8B), C7(H7A,H7B), C47(H47A,H47B),
 C49(H49A,H49B), C29(H29A,H29B)
5.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C33(H33A,H33B,H33C), C37(H37A,H37B,
 H37C), C34(H34A,H34B,H34C), C46(H46A,H46B,H46C), C36(H36A,H36B,H36C), C27(H27A,
 H27B,H27C), C44(H44A,H44B,H44C), C26(H26A,H26B,H26C), C15(H15A,H15B,H15C),
 C5(H5A,H5B,H5C), C3(H3A,H3B,H3C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C),
 C2(H2A,H2B,H2C), C16(H16A,H16B,H16C), C6(H6A,H6B,H6C), C40(H40A,H40B,H40C),
 C13(H13A,H13B,H13C), C50(H50A,H50B,H50C), C48(H48A,H48B,H48C), C12(H12A,H12B,
 H12C), C20A(H20A,H20B,H20C), C21A(H21A,H21B,H21C), C19A(H19A,H19B,H19C),
 C21B(H21D,H21E,H21F), C19B(H19D,H19E,H19F), C20B(H20D,H20E,H20F)
;
_shelx_res_checksum              29233
_shelx_hkl_checksum              63961
_olex2_submission_special_instructions 'No special instructions were received'