Reversible Heterolytic Cleavage of the H-H Bond by Molybdenum Complexes: Controlling the Dynamics of Exchange Between Proton and Hydride.
Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris; Journal of the American Chemical Society 139 (2017) 7376–7387; doi:10.1021/jacs.7b03053

data_4126053
_publ_section_title
;
 Reversible Heterolytic Cleavage of the H-H Bond by Molybdenum Complexes:
 Controlling the Dynamics of Exchange Between Proton and Hydride.
;
_journal_issue                   21
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7376
_journal_page_last               7387
_journal_paper_doi               10.1021/jacs.7b03053
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety         'C26 H49 Mo N2 O P2, C32 H12 B F24.17'
_chemical_formula_sum            'C58 H61 B F23.97 Mo N2 O P2'
_chemical_formula_weight         1426.20
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-06-02
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 106.004(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.5265(8)
_cell_length_b                   27.7730(16)
_cell_length_c                   16.8162(10)
_cell_measurement_reflns_used    9552
_cell_measurement_temperature    100
_cell_measurement_theta_max      33.75
_cell_measurement_theta_min      2.54
_cell_volume                     6072.5(6)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.988
_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  0.0572
_diffrn_reflns_av_unetI/netI     0.0375
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       43
_diffrn_reflns_limit_k_min       -43
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            181049
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         33.882
_diffrn_reflns_theta_min         1.458
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.385
_exptl_absorpt_correction_T_max  0.7467
_exptl_absorpt_correction_T_min  0.5666
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014) was used for absorption correction. wR2(int) was 0.1434 before and 0.0676 after correction. The Ratio of minimum to maximum transmission is 0.7588. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            'clear dark blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.560
_exptl_crystal_description       block
_exptl_crystal_F_000             2895
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.14
_refine_diff_density_max         2.023
_refine_diff_density_min         -1.034
_refine_diff_density_rms         0.110
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     868
_refine_ls_number_reflns         24251
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0746
_refine_ls_R_factor_gt           0.0558
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0597P)^2^+11.8271P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1366
_refine_ls_wR_factor_ref         0.1502
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19332
_reflns_number_total             24251
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b03053_si_002.cif
_cod_data_source_block           tButBuMo+
_cod_depositor_comments
'Adding full bibliography for 4126047--4126059.cif.'
_cod_database_code               4126053
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.874
_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. Rigid bond restraints
 F13, F15
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F14, F15
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F13A, F15A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F14A, F15A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F15, F15A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(F1) = Uanis(F1A)
Uanis(F2) = Uanis(F2A)
Uanis(F3) = Uanis(F3A)
Uanis(F4) = Uanis(F4A)
Uanis(F6) = Uanis(F6A)
Uanis(F6) = Uanis(F4A)
Uanis(F5) = Uanis(F6A)
Uanis(F5) = Uanis(F5A)
Uanis(F4) = Uanis(F5A)
Uanis(F13) = Uanis(F13A)
Uanis(F14) = Uanis(F14A)
4. Others
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(1)
 Sof(F3)=Sof(F1)=Sof(F2)=FVAR(1)
 Sof(F6A)=Sof(F4A)=Sof(F5A)=1-FVAR(2)
 Sof(F6)=Sof(F4)=Sof(F5)=FVAR(2)
 Sof(F9A)=Sof(F8A)=Sof(F7A)=1-FVAR(3)
 Sof(F9)=Sof(F8)=Sof(F7)=FVAR(3)
 Sof(F14A)=1-FVAR(4)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(4)
5.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C5(H5A,H5B), C2(H2A,H2B), C4(H4A,H4B)
5.b Aromatic/amide H refined with riding coordinates:
 C32(H32), C36(H36), C45(H45), C43(H43), C40(H40), C30(H30), C52(H52),
 C46(H46), C56(H56), C28(H28), C24(H24), C54(H54), C38(H38), C25(H25), C23(H23),
  C26(H26), C22(H22)
5.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C16(H16A,H16B,H16C), C11(H11A,H11B,H11C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C8(H8A,H8B,H8C), C13(H13A,
 H13B,H13C), C14(H14A,H14B,H14C), C17(H17A,H17B,H17C), C9(H9A,H9B,H9C), C7(H7A,
 H7B,H7C)
;
_shelx_res_checksum              48300
_shelx_hkl_checksum              51842
_olex2_submission_special_instructions 'No special instructions were received'