Zn-Promoted C-H Reductive Elimination and H<sub>2</sub> Activation via a Dual Unsaturated Heterobimetallic Ru-Zn Intermediate.
Miloserdov, Fedor M.; Rajabi, Nasir A.; Lowe, John P.; Mahon, Mary F.; Macgregor, Stuart A.; Whittlesey, Michael K.; Journal of the American Chemical Society 142 (2020) 6340–6349; doi:10.1021/jacs.0c01062

data_4134451
_publ_section_title
;
 Zn-Promoted C-H Reductive Elimination and H<sub>2</sub> Activation via a
 Dual Unsaturated Heterobimetallic Ru-Zn Intermediate.
;
_journal_issue                   13
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6340
_journal_page_last               6349
_journal_paper_doi               10.1021/jacs.0c01062
_journal_volume                  142
_journal_year                    2020
_chemical_formula_moiety         'C58.65 H53.95 Cl0.35 O P3 Ru Zn, 2(C4 H8 O)'
_chemical_formula_sum            'C66.65 H69.95 Cl0.35 O3 P3 Ru Zn'
_chemical_formula_weight         1190.73
_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     iterative
_audit_creation_date             2018-09-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                78.007(3)
_cell_angle_beta                 81.630(3)
_cell_angle_gamma                63.847(3)
_cell_formula_units_Z            2
_cell_length_a                   12.3741(4)
_cell_length_b                   12.7084(4)
_cell_length_c                   20.7440(6)
_cell_measurement_reflns_used    11027
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      29.0520
_cell_measurement_theta_min      3.8320
_cell_volume                     2858.80(17)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0734
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.829
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Xcalibur, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0236
_diffrn_reflns_av_unetI/netI     0.0479
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.829
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            25148
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.829
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.525
_diffrn_reflns_theta_min         3.435
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.831
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93209
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.383
_exptl_crystal_description       block
_exptl_crystal_F_000             1238
_exptl_crystal_size_max          0.414
_exptl_crystal_size_mid          0.348
_exptl_crystal_size_min          0.29
_refine_diff_density_max         0.544
_refine_diff_density_min         -0.467
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     780
_refine_ls_number_reflns         13245
_refine_ls_number_restraints     151
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0525
_refine_ls_R_factor_gt           0.0369
_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^)+(0.0260P)^2^+2.0624P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0734
_refine_ls_wR_factor_ref         0.0796
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10794
_reflns_number_total             13245
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01062_si_002.cif
_cod_data_source_block           e18mkw11
_cod_depositor_comments
'Adding full bibliography for 4134447--4134453.cif.'
_cod_database_code               4134451
_shelxl_version_number           2014-3
_chemical_oxdiff_usercomment     'yellow block'
_shelx_estimated_absorpt_t_max   0.795
_shelx_estimated_absorpt_t_min   0.725
_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
 O3-C64 \\sim O3A-C64A
 with sigma of 0.02
 O3-C67 \\sim O3A-C67A
 with sigma of 0.02
 C64-C65 \\sim C64A-C65A
 with sigma of 0.02
 C65-C66 \\sim C65A-C66A
 with sigma of 0.02
 C66-C67 \\sim C66A-C67A
 with sigma of 0.02
 O3-C65 \\sim O3A-C65A
 with sigma of 0.04
 O3-C66 \\sim O3A-C66A
 with sigma of 0.04
 C64-C66 \\sim C64A-C66A
 with sigma of 0.04
 C64-C67 \\sim C64A-C67A
 with sigma of 0.04
 C65-C67 \\sim C65A-C67A
 with sigma of 0.04
 C60A-O2 \\sim O2A-C63
 with sigma of 0.02
 O2-C60 \\sim C63-C61A
 with sigma of 0.02
 C60-C61 \\sim C61A-C62A
 with sigma of 0.02
 C60A-C60 \\sim O2A-C61A
 with sigma of 0.04
 C60A-C61 \\sim O2A-C62A
 with sigma of 0.04
 C62-C60A \\sim C63A-O2A
 with sigma of 0.02
 C62-C61 \\sim C63A-C62A
 with sigma of 0.02
 C62-O2 \\sim C63A-C63
 with sigma of 0.04
 C62-C60 \\sim C63A-C61A
 with sigma of 0.04
 O2A-C63A \\sim O2A-C60A \\sim O2-C63 \\sim O2-C60
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
O3 \\sim C64 \\sim C65 \\sim C66 \\sim C67: within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.01
O2 \\sim C60 \\sim C61 \\sim C62 \\sim C63: within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.01
O2A \\sim C60A \\sim C61A \\sim C62A \\sim C63A: within 2A with sigma of 0.02
and sigma for terminal atoms of 0.01
C67 \\sim O3A \\sim C64A \\sim C65A \\sim C66A: within 2A with sigma of 0.02
and sigma for terminal atoms of 0.01
Uanis(C63A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
4. Others
 Fixed Sof: Cl1(0.35) C1(0.65) H1A(0.65) H1B(0.65) H1C(0.65) O3(0.65)
 C64(0.65) H64A(0.65) H64B(0.65) C65(0.65) H65A(0.65) H65B(0.65) C66(0.65)
 H66A(0.65) H66B(0.65) C67(0.65) H67A(0.65) H67B(0.65) O2A(0.35) C60A(0.35)
 H60C(0.35) H60D(0.35) C61A(0.35) H61C(0.35) H61D(0.35) C62A(0.35) H62C(0.35)
 H62D(0.35) C63A(0.35) H63C(0.35) H63D(0.35) O2(0.65) C60(0.65) H60A(0.65)
 H60B(0.65) C61(0.65) H61A(0.65) H61B(0.65) C62(0.65) H62A(0.65) H62B(0.65)
 C63(0.65) H63A(0.65) H63B(0.65) O3A(0.35) C64A(0.35) H64C(0.35) H64D(0.35)
 C65A(0.35) H65C(0.35) H65D(0.35) C66A(0.35) H66C(0.35) H66D(0.35) C67A(0.35)
 H67C(0.35) H67D(0.35)
5.a Secondary CH2 refined with riding coordinates:
 C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B), C59(H59A,H59B), C64(H64A,
 H64B), C65(H65A,H65B), C66(H66A,H66B), C67(H67A,H67B), C60A(H60C,H60D),
 C61A(H61C,H61D), C62A(H62C,H62D), C63A(H63C,H63D), C60(H60A,H60B), C61(H61A,
 H61B), C62(H62A,H62B), C63(H63A,H63B), C64A(H64C,H64D), C65A(H65C,H65D),
 C66A(H66C,H66D), C67A(H67C,H67D)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C22(H22), C23(H23),
  C24(H24), C25(H25), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31),
 C33(H33), C34(H34), C35(H35), C36(H36), C37(H37), C39(H39), C40(H40), C41(H41),
  C42(H42), C43(H43), C45(H45), C46(H46), C47(H47), C48(H48), C49(H49),
 C51(H51), C52(H52), C53(H53), C54(H54), C55(H55)
5.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;