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_4126052
_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         'C32 H45 Mo N2 O P2, C32 H12 B F24.02'
_chemical_formula_sum            'C64 H57 B F24.03 Mo N2 O P2'
_chemical_formula_weight         1495.44
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2014-04-21
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_cell_angle_alpha                90
_cell_angle_beta                 116.837(8)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   41.684(3)
_cell_length_b                   13.0435(10)
_cell_length_c                   27.362(3)
_cell_measurement_reflns_used    7750
_cell_measurement_temperature    100
_cell_volume                     13275(2)
_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, 2008)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_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  0.1361
_diffrn_reflns_av_unetI/netI     0.1089
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       54
_diffrn_reflns_limit_h_min       -54
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            113248
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.032
_diffrn_reflns_theta_min         1.654
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.356
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6362
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0742 before and 0.0638 after correction.
The Ratio of minimum to maximum transmission is 0.8533.
The \l/2 correction factor is 0.0015.
;
_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    1.497
_exptl_crystal_description       block
_exptl_crystal_F_000             6050
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.105
_exptl_crystal_size_min          0.078
_refine_diff_density_max         0.835
_refine_diff_density_min         -0.845
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.008
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     921
_refine_ls_number_reflns         15978
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.008
_refine_ls_R_factor_all          0.1263
_refine_ls_R_factor_gt           0.0559
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0527P)^2^+10.3852P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1087
_refine_ls_wR_factor_ref         0.1321
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9196
_reflns_number_total             15978
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b03053_si_002.cif
_cod_data_source_block           tBuBnMo+
_cod_depositor_comments
'Adding full bibliography for 4126047--4126059.cif.'
_cod_original_cell_volume        13274(2)
_cod_database_code               4126052
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.973
_shelx_estimated_absorpt_t_min   0.955
_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. Others
 Sof(F4A)=Sof(F6A)=Sof(F5A)=1-FVAR(1)
 Sof(F6)=Sof(F5)=Sof(F4)=FVAR(1)
 Sof(F3)=Sof(F1)=Sof(F2)=FVAR(2)
 Fixed Sof: F7(0.33333) F8(0.33333) F9(0.33333)
3.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C1(H1A,H1B), C4(H4A,H4B), C13(H13A,H13B), C3(H3A,H3B), C20(H20A,
 H20B)
3.b Aromatic/amide H refined with riding coordinates:
 C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C22(H22), C23(H23),
 C24(H24), C25(H25), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31),
  C36(H36), C34(H34), C42(H42), C38(H38), C53(H53), C51(H51), C49(H49),
 C61(H61), C59(H59), C57(H57), C46(H46), C44(H44)
3.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C10(H10A,H10B,H10C), C8(H8A,H8B,H8C), C7(H7A,H7B,H7C),
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C)
;
_shelx_res_checksum              43039
_shelx_hkl_checksum              4823
_olex2_computing_structure_refinement_long 'ShelXL (Sheldrick, 2008)'