EPR detection and characterisation of a paramagnetic Mo(iii) dihydride intermediate involved in electrocatalytic hydrogen evolution.
Prior, Christopher; Webster, Lee R.; Ibrahim, Saad K.; Wright, Joseph A.; Alghamdi, Ali F.; Oganesyan, Vasily S.; Pickett, Christopher J.; Dalton transactions (Cambridge, England : 2003) 45 (2016) 2399–2403; doi:10.1039/c5dt04432d

data_7037867
_publ_section_title
;
 EPR detection and characterisation of a paramagnetic Mo(iii) dihydride
 intermediate involved in electrocatalytic hydrogen evolution.
;
_journal_issue                   6
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              2399
_journal_page_last               2403
_journal_paper_doi               10.1039/c5dt04432d
_journal_volume                  45
_journal_year                    2016
_chemical_formula_moiety         'C53 H51 Mo O2 P4, C24 H20 B'
_chemical_formula_structural     '[(H)2Mo(dppe)2(O2CH)][BPh4]'
_chemical_formula_sum            'C77 H71 B Mo O2 P4'
_chemical_formula_weight         1258.96
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_method           SHELXL-2014/7
_audit_update_record
;
2015-12-13 deposited with the CCDC.
2015-12-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.3380(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.4817(5)
_cell_length_b                   20.7047(5)
_cell_length_c                   17.5343(5)
_cell_measurement_reflns_used    100347
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      27.48
_cell_measurement_theta_min      2.91
_cell_volume                     6335.8(3)
_computing_cell_refinement
'DENZO (Otwinowski & Minor, 1997) & COLLECT (Hooft, 1998)'
_computing_data_collection       'COLLECT (Hooft, 1998)'
_computing_data_reduction
'DENZO (Otwinowski & Minor, 1997) & COLLECT (Hooft, 1998)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1993)'
_computing_publication_material
;
SHELXL-2014/7 (Sheldrick, 2015), PLATON (Spek, 2003), WinGX (Farrugia, 1999)
and enCIFer (Allen et al., 2004)
;
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT-2014/5 (Sheldrick, 2015)'
_diffrn_ambient_temperature      120(2)
_diffrn_detector_area_resol_mean '4096x4096pixels / 62x62mm'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type
'Bruker-Nonius APEX II CCD camera on \k-goniostat'
_diffrn_measurement_method       '\f & \w scans'
_diffrn_radiation_monochromator  '10cm confocal mirrors'
_diffrn_radiation_source         'Bruker-Nonius FR591 rotating anode'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0952
_diffrn_reflns_av_unetI/netI     0.0945
_diffrn_reflns_laue_measured_fraction_full 0.996
_diffrn_reflns_laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            50365
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         3.048
_exptl_absorpt_coefficient_mu    0.356
_exptl_absorpt_correction_T_max  0.9929
_exptl_absorpt_correction_T_min  0.7990
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   '(SADABS 2007/2; Sheldrick, 2007)'
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.320
_exptl_crystal_description       blade
_exptl_crystal_F_000             2624
_exptl_crystal_size_max          0.050
_exptl_crystal_size_mid          0.040
_exptl_crystal_size_min          0.020
_refine_diff_density_max         1.000
_refine_diff_density_min         -0.458
_refine_diff_density_rms         0.115
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     790
_refine_ls_number_reflns         11116
_refine_ls_number_restraints     73
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.1500
_refine_ls_R_factor_gt           0.0886
_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^)+47.1810P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1560
_refine_ls_wR_factor_ref         0.1764
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7278
_reflns_number_total             11116
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5dt04432d2.cif
_cod_data_source_block           Mo
_cod_depositor_comments
'Adding full bibliography for 7037867--7037868.cif.'
_cod_database_code               7037867
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.982
_shelx_estimated_absorpt_t_max   0.993
_shelx_res_checksum              78783