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_4126059
_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         'C30 H43 Mo N2 O P2, C32 H12 B F24, C3 H2 F0.5'
_chemical_formula_sum            'C65 H57 B F24.5 Mo N2 O P2'
_chemical_formula_weight         1516.31
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2015-12-18
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                107.945(3)
_cell_angle_beta                 96.254(4)
_cell_angle_gamma                98.054(3)
_cell_formula_units_Z            2
_cell_length_a                   9.3013(8)
_cell_length_b                   17.9188(14)
_cell_length_c                   20.2670(17)
_cell_measurement_reflns_used    9833
_cell_measurement_temperature    100
_cell_measurement_theta_max      29.837
_cell_measurement_theta_min      2.312
_cell_volume                     3140.1(5)
_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, 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.999
_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  0.0473
_diffrn_reflns_av_unetI/netI     0.0703
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            82161
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.785
_diffrn_reflns_theta_min         1.329
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.379
_exptl_absorpt_correction_T_max  0.7464
_exptl_absorpt_correction_T_min  0.6828
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0729 before and 0.0497 after correction.
The Ratio of minimum to maximum transmission is 0.9148.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.604
_exptl_crystal_description       needle
_exptl_crystal_F_000             1533
_exptl_crystal_size_max          0.238
_exptl_crystal_size_mid          0.086
_exptl_crystal_size_min          0.056
_refine_diff_density_max         1.042
_refine_diff_density_min         -0.998
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     903
_refine_ls_number_reflns         22976
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0874
_refine_ls_R_factor_gt           0.0483
_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^)+(0.0600P)^2^+0.4514P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1139
_refine_ls_wR_factor_ref         0.1274
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15276
_reflns_number_total             22976
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b03053_si_002.cif
_cod_data_source_block           tBuPhMoHNH+
_cod_depositor_comments
'Adding full bibliography for 4126047--4126059.cif.'
_cod_original_formula_sum        'C65 H57 B F24.50 Mo N2 O P2'
_cod_database_code               4126059
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.979
_shelx_estimated_absorpt_t_min   0.915
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C37-C32 \\sim C28A-C32
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C37) = Uanis(C28A)
Uanis(F6) = Uanis(F6A)
Uanis(F5) = Uanis(F5A)
4. Others
 Sof(F5A)=Sof(F6A)=Sof(C28A)=Sof(F4A)=1-FVAR(1)
 Sof(F4)=Sof(F5)=Sof(F6)=Sof(C37)=FVAR(1)
 Fixed Sof: F25(0.5)
5.a Ternary CH refined with riding coordinates:
 N1(H2)
5.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B), C2(H2A,H2B), C3(H3A,H3B)
5.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C16(H16), C15(H15), C14(H14), C13(H13), C12(H12),
 C29(H29), C28(H28), C27(H27), C26(H26), C25(H25), C9(H9), C10(H10), C39(H39),
 C55(H55), C33(H33), C35(H35), C59(H59), C57(H57), C41(H41), C43(H43), C51(H51),
  C49(H49), C47(H47), C31(H31), C62(H62), C64(H64)
5.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C18(H18A,H18B,H18C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C20(H20A,H20B,H20C), C19(H19A,H19B,H19C)
;
_shelx_res_checksum              88694
_shelx_hkl_checksum              24546
_olex2_submission_special_instructions 'No special instructions were received'