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_4126057
_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
'C34 H35 Mo N2 O P2, C32 H12 B F24, 4.5(C6 H5 F)'
_chemical_formula_sum            'C93 H69.5 B F28.5 Mo N2 O P2'
_chemical_formula_weight         1941.19
_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             2015-09-29
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                68.854(3)
_cell_angle_beta                 82.049(3)
_cell_angle_gamma                73.290(3)
_cell_formula_units_Z            2
_cell_length_a                   12.7123(6)
_cell_length_b                   17.4489(8)
_cell_length_c                   21.6927(11)
_cell_measurement_reflns_used    9824
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.245
_cell_measurement_theta_min      2.322
_cell_volume                     4295.0(4)
_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, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.991
_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  0.0607
_diffrn_reflns_av_unetI/netI     0.0712
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            90231
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.698
_diffrn_reflns_theta_min         1.345
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.302
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.6915
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0705 before and 0.0639 after correction.
The Ratio of minimum to maximum transmission is 0.9271.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.501
_exptl_crystal_description       block
_exptl_crystal_F_000             1966
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.067
_refine_diff_density_max         1.271
_refine_diff_density_min         -0.895
_refine_diff_density_rms         0.102
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1187
_refine_ls_number_reflns         24161
_refine_ls_number_restraints     172
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0978
_refine_ls_R_factor_gt           0.0618
_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^)+(0.0912P)^2^+3.9058P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1582
_refine_ls_wR_factor_ref         0.1807
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16782
_reflns_number_total             24161
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b03053_si_002.cif
_cod_data_source_block           PhPhMoHNH+
_cod_depositor_comments
'Adding full bibliography for 4126047--4126059.cif.'
_cod_original_formula_sum        'C93 H69.50 B F28.50 Mo N2 O P2'
_cod_database_code               4126057
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.948
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2. Restrained distances
 Mo1-H1A
 1.61 with sigma of 0.01
 Mo1-H1
 1.65 with sigma of 0.01
 H1A-C1'
 2.32 with sigma of 0.01
 H1-C1
 2.32 with sigma of 0.04
 Mo1-O1 \\sim Mo1-O1'
 with sigma of 0.02
 Mo1-C1' \\sim Mo1-C1
 with sigma of 0.02
 C1'-O1' \\sim C1-O1
 with sigma of 0.04
 Mo1-H1A \\sim Mo1-H1
 with sigma of 0.02
 C1'-H1A \\sim C1-H1
 with sigma of 0.02
3. Rigid bond restraints
 C36, C37, C38, C39, C40, C41
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C44, C45, C46, C47, C48, C49
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C52, C53, C54, C55, C56, C57
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C60, C61, C62, C63, C64, C65
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C100, C101, C102, C103, C104, C105
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C201, C202, C203, C204, C205, C206
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C500, C501, C502, C503, C504, C505
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C401, C402, C403, C404, C405, C406
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C151, C152, C153
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F41, C201, C202, C203, C204, C205, C206
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F66, C401, C402, C403, C404, C405, C406
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F53, C500, C501, C502, C503, C504, C505
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F100, C151, C152, C153, C154, C155, C156
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1', Mo1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1, Mo1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C3, C4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C4, C5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C5, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C2, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C2, C3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C1' \\sim O1': within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.04
C1 \\sim O1: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(O1) \\sim Ueq: with sigma of 0.006 and sigma for terminal atoms of 0.012
Uanis(O1') \\sim Ueq: with sigma of 0.006 and sigma for terminal atoms of 0.012
Uanis(C1') \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(C1) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(C151) = Uanis(C154)
Uanis(C152) = Uanis(C155)
Uanis(C1') = Uanis(C1)
5. Others
 Sof(C1')=Sof(O1')=1-FVAR(1)
 Sof(C1)=Sof(O1)=FVAR(1)
 Sof(H1)=1-FVAR(2)
 Sof(H1A)=FVAR(2)
 Fixed Sof: F100(0.5) C151(0.5) H151(0.5) C152(0.5) H152(0.5) C153(0.5)
 C154(0.5) H154(0.5) C155(0.5) H155(0.5) C156(0.5) H156(0.5)
6.a Ternary CH refined with riding coordinates:
 N1(H2)
6.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H0AA), C3(H3), C4(H4), C5(H5), C6(H6), C12(H12), C13(H13), C14(H14),
 C15(H15), C16(H16), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C24(H24),
  C25(H25), C26(H26), C27(H27), C28(H28), C30(H30), C31(H31), C32(H32),
 C33(H33), C34(H34), C37(H37), C39(H39), C41(H41), C45(H45), C47(H47), C49(H49),
  C53(H53), C55(H55), C57(H57), C61(H61), C63(H63), C65(H65), C101(H101),
 C102(H102), C103(H103), C104(H104), C105(H105), C202(H202), C203(H203),
 C204(H204), C205(H205), C206(H206), C402(H402), C403(H403), C404(H404),
 C405(H405), C406(H406), C501(H501), C502(H502), C503(H503), C504(H504),
 C505(H505), C151(H151), C152(H152), C154(H154), C155(H155), C156(H156)
6.d Fitted hexagon refined as free rotating group:
 C151(C152,C153,C154,C155,C156)
;
_shelx_res_checksum              98781
_shelx_hkl_checksum              24539
_olex2_submission_special_instructions 'No special instructions were received'