Electrocatalytic CO2 reduction by M(bpy-R)(CO)4 (M = Mo, W; R = H, tBu) complexes. Electrochemical, spectroscopic, and computational studies and comparison with group 7 catalysts
Clark, Melissa L.; Grice, Kyle A.; Moore, Curtis E.; Rheingold, Arnold L.; Kubiak, Clifford P.; Chemical Science 5 (2014) 1894–; doi:10.1039/c3sc53470g

data_1514319
_publ_section_title
;
 Electrocatalytic CO2 reduction by M(bpy-R)(CO)4 (M = Mo, W; R = H, tBu)
 complexes. Electrochemical, spectroscopic, and computational studies and
 comparison with group 7 catalysts
;
_journal_issue                   5
_journal_name_full               'Chemical Science'
_journal_page_first              1894
_journal_paper_doi               10.1039/c3sc53470g
_journal_volume                  5
_journal_year                    2014
_chemical_formula_moiety         'C21 H24 N2 O3 W, 2(C12 H24 O6 K), C4 H8 O'
_chemical_formula_sum            'C49 H80 K2 N2 O16 W'
_chemical_formula_weight         1213.01
_chemical_name_systematic
; 
 ? 
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_symmetry_space_group_name_Hall  '-P 2ac 2n'
_symmetry_space_group_name_H-M   'P n m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2012
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   29.9821(16)
_cell_length_b                   15.8708(9)
_cell_length_c                   11.8370(6)
_cell_measurement_reflns_used    9971
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.39
_cell_measurement_theta_min      4.02
_cell_volume                     5632.5(5)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2012 (Sheldrick, 2012)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean '512 x 512'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device_type  'Bruker APEX CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1648
_diffrn_reflns_av_unetI/netI     0.0768
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            53271
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        68.000
_diffrn_reflns_theta_max         69.044
_diffrn_reflns_theta_min         2.948
_diffrn_source                   'Rotating Anode'
_exptl_absorpt_coefficient_mu    5.622
_exptl_absorpt_correction_T_max  0.7532
_exptl_absorpt_correction_T_min  0.4068
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            'Dark Red'
_exptl_crystal_density_diffrn    1.430
_exptl_crystal_description       Plate
_exptl_crystal_F_000             2508
_exptl_crystal_size_max          0.083
_exptl_crystal_size_mid          0.041
_exptl_crystal_size_min          0.005
_refine_diff_density_max         2.145
_refine_diff_density_min         -1.172
_refine_diff_density_rms         0.159
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     311
_refine_ls_number_reflns         5372
_refine_ls_number_restraints     75
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0968
_refine_ls_R_factor_gt           0.0770
_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^)+(0.0919P)^2^+35.8650P] 
 where P=(Fo^2^+2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1851
_refine_ls_wR_factor_ref         0.1980
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4327
_reflns_number_total             5372
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c3sc53470g2.cif
_cod_data_source_block           KAG_W_Dianion
_cod_database_code               1514319
_shelx_estimated_absorpt_t_min   0.653
_shelx_estimated_absorpt_t_max   0.972
_shelxl_version_number           2012-9
_shelx_res_checksum              95105
_shelx_hkl_checksum              71244