Understanding the Relationship Between Kinetics and Thermodynamics in CO2 Hydrogenation Catalysis
Jeletic, Matthew S.; Hulley, Elliott B.; Helm, Monte L.; Mock, Michael T.; Appel, Aaron M.; Wiedner, Eric S.; Linehan, John C.; ACS Catalysis 7 (2017) 6008–; doi:10.1021/acscatal.7b01673

data_4516739
_publ_section_title
;
 Understanding the Relationship Between Kinetics and Thermodynamics in CO2
 Hydrogenation Catalysis
;
_journal_issue                   9
_journal_name_full               'ACS Catalysis'
_journal_page_first              6008
_journal_paper_doi               10.1021/acscatal.7b01673
_journal_volume                  7
_journal_year                    2017
_chemical_formula_moiety         'C24 H38 Co N2 P4, 2(B F4), 2(C2 H3 N)'
_chemical_formula_sum            'C28 H44 B2 Co F8 N4 P4'
_chemical_formula_weight         793.10
_chemical_name_systematic        '[(dmpbz)2Co(CH3CN)2][BF4]2,(CH3CN)2'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     heavy
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-01-11
_audit_creation_method
;
  Olex2 1.2
  (compiled Nov  5 2012 18:25:38, GUI svn.r4372)
;
_audit_update_record
;
2013-01-11 # Formatted by publCIF
;
_cell_angle_alpha                114.987(3)
_cell_angle_beta                 111.721(2)
_cell_angle_gamma                93.719(3)
_cell_formula_units_Z            1
_cell_length_a                   10.0889(5)
_cell_length_b                   10.4012(5)
_cell_length_c                   10.9505(6)
_cell_measurement_reflns_used    7205
_cell_measurement_temperature    140
_cell_measurement_theta_max      30.230
_cell_measurement_theta_min      2.252
_cell_volume                     933.62(9)
_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
;
XL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
olex2.solve (L.J. Bourhis, O.V. Dolomanov, R.J. Gildea, J.A.K. Howard,
H. Puschmann, in preparation, 2011)
;
_diffrn_ambient_temperature      140
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.986
_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  0.0309
_diffrn_reflns_av_unetI/netI     0.0334
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            17485
_diffrn_reflns_theta_full        28.29
_diffrn_reflns_theta_max         28.29
_diffrn_reflns_theta_min         2.24
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.697
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9265
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0545 before and 0.0410 after correction.
The Ratio of minimum to maximum transmission is 0.9265.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear light violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.411
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             409
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.640
_refine_diff_density_min         -0.268
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     220
_refine_ls_number_reflns         4572
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0458
_refine_ls_R_factor_gt           0.0333
_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^)+(0.0416P)^2^+0.3301P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0800
_refine_ls_wR_factor_ref         0.0860
_reflns_number_gt                3747
_reflns_number_total             4572
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            cs7b01673_si_001.cif
_cod_data_source_block           Co(dmpbz)2
_cod_original_cell_volume        933.62(8)
_cod_database_code               4516739
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H4 of C4, H3 of C3, H2 of C2, H5 of C5
 At 1.5 times of:
  {H7A,H7B,H7C} of C7, {H10A,H10B,H10C} of C10, {H9A,H9B,H9C} of C9, {H8A,H8B,
  H8C} of C8, {H13A,H13B,H13C} of C13, {H12A,H12B,H12C} of C12
2.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C5(H5), C3(H3), C4(H4)
2.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C10(H10A,H10B,H10C), C9(H9A,H9B,H9C), C8(H8A,H8B,H8C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C)
;