High Catalytic Rates for Hydrogen Production Using Nickel Electrocatalysts with Seven-Membered Cyclic Diphosphine Ligands Containing One Pendant Amine
Michael P. Stewart; Ming-Hsun Ho; Stefan Wiese; Mary Lou Lindstrom; Colleen E. Thogerson; Simone Raugei; R. Morris Bullock; Monte L. Helm; Journal of the American Chemical Society 135 (2013) 6033–6046; doi:10.1021/ja400181a

data_4119612
_publ_contact_author_email       monte.helm@pnnl.gov
_publ_section_title
;
 High Catalytic Rates for Hydrogen Production Using Nickel
 Electrocatalysts with Seven-Membered Cyclic Diphosphine Ligands
 Containing One Pendant Amine
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6033
_journal_page_last               6046
_journal_paper_doi               10.1021/ja400181a
_journal_volume                  135
_journal_year                    2013
_chemical_formula_moiety         'C46 H44 F6 N2 Ni P4, 2(B F4)'
_chemical_formula_sum            'C46 H44 B2 F14 N2 Ni P4'
_chemical_formula_weight         1095.04
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2012-11-09
_audit_creation_method
;
  Olex2 1.2
  (compiled 2012.11.06 svn.r2526, GUI svn.r4372)
;
_audit_update_record
;
2012-12-26 # Formatted by publCIF
;
_cell_angle_alpha                90.00
_cell_angle_beta                 97.294(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   10.1020(7)
_cell_length_b                   12.1935(9)
_cell_length_c                   19.6115(14)
_cell_measurement_reflns_used    9934
_cell_measurement_temperature    297
_cell_measurement_theta_max      25.43
_cell_measurement_theta_min      2.68
_cell_volume                     2396.2(3)
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      297
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0353
_diffrn_reflns_av_unetI/netI     0.0237
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            46395
_diffrn_reflns_theta_full        27.96
_diffrn_reflns_theta_max         27.96
_diffrn_reflns_theta_min         1.97
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.629
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8897
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0607 before and 0.0457 after correction.
The Ratio of minimum to maximum transmission is 0.8897.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.518
_exptl_crystal_description       block
_exptl_crystal_F_000             1116
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.782
_refine_diff_density_min         -0.408
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     378
_refine_ls_number_reflns         5762
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0624
_refine_ls_R_factor_gt           0.0439
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0704P)^2^+1.0755P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1158
_refine_ls_wR_factor_ref         0.1300
_reflns_number_gt                4408
_reflns_number_total             5762
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja400181a_si_002_5.cif
_cod_data_source_block           helm116_0m
_cod_database_code               4119612
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H15 of C16, H14 of C15, H7 of C22, H13 of C14, H8 of C21, H6 of C23, H16 of
  C17, H12 of C13, H9 of C20, H21 of C9, H18 of C6, {H2A,H2B} of C2, H22 of C10,
   H10 of C19, H19 of C7, {H3A,H3B} of C4, {H4A,H4B} of C1, {H1A,H1B} of C3
2. others
 Sof(F1)=Sof(F3)=Sof(F2)=1-Sof(F3)=1-Sof(F3)=1-Sof(F3)
 Sof(F5)=Sof(F6)=Sof(F7)=Sof(F4)=1-Sof(F6)=1-Sof(F6)=1-Sof(F6)=1-Sof(F6)
3.a Secondary CH2 refined with riding coordinates:
 C4(H3A,H3B), C1(H4A,H4B), C3(H1A,H1B), C2(H2A,H2B)
3.b Aromatic/amide H refined with riding coordinates:
 C10(H22), C19(H10), C7(H19), C6(H18), C9(H21), C20(H9), C13(H12), C17(H16),
 C23(H6), C21(H8), C14(H13), C22(H7), C15(H14), C16(H15)
;