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_4516740
_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         'C22 H51 Co N P4, 2(B F4)'
_chemical_formula_sum            'C22 H51 B2 Co F8 N P4'
_chemical_formula_weight         686.06
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2013-07-25
_audit_creation_method
;
  Olex2 1.2
  (compiled 2013.03.22 svn.r2654, GUI svn.r4446)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.503(2)
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   15.0848(6)
_cell_length_b                   20.0234(7)
_cell_length_c                   32.3058(14)
_cell_measurement_reflns_used    9873
_cell_measurement_temperature    164
_cell_measurement_theta_max      27.90
_cell_measurement_theta_min      2.30
_cell_volume                     9754.6(7)
_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
;
olex2.solve (L.J. Bourhis, O.V. Dolomanov, R.J. Gildea, J.A.K. Howard,
H. Puschmann, in preparation, 2011)
;
_diffrn_ambient_temperature      164
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_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  0.0526
_diffrn_reflns_av_unetI/netI     0.0435
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            167778
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.006
_diffrn_reflns_theta_min         1.197
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.785
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9348
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0631 before and 0.0574 after correction.
The Ratio of minimum to maximum transmission is 0.9348.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear light green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.401
_exptl_crystal_description       block
_exptl_crystal_F_000             4308
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.13
_refine_diff_density_max         2.291
_refine_diff_density_min         -1.568
_refine_diff_density_rms         0.108
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1012
_refine_ls_number_reflns         23438
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0893
_refine_ls_R_factor_gt           0.0603
_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^)+(0.0756P)^2^+26.4127P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1555
_refine_ls_wR_factor_ref         0.1747
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16764
_reflns_number_total             23438
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs7b01673_si_001.cif
_cod_data_source_block           Co(depe)2
_cod_database_code               4516740
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(F8) = Uanis(F5) = Uanis(F6) = Uanis(F7)
Uanis(F20) = Uanis(F17) = Uanis(F19) = Uanis(F18)
Uanis(C34) = Uanis(C24)
3.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C9(H9A,H9B),
 C11(H11A,H11B), C13(H13A,H13B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B),
  C19(H19A,H19B), C23(H23A,H23B), C25(H25A,H25B), C27(H27A,H27B), C28(H28A,
 H28B), C29(H29A,H29B), C31(H31A,H31B), C33(H33A,H33B), C35(H35A,H35B),
 C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B), C41(H41A,H41B), C45(H45A,H45B),
  C47(H47A,H47B), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B), C53(H53A,
 H53B), C55(H55A,H55B), C57(H57A,H57B), C59(H59A,H59B), C60(H60A,H60B),
 C61(H61A,H61B), C63(H63A,H63B)
3.b Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C),
 C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C18(H18A,H18B,H18C), C20(H20A,H20B,
 H20C), C22(H22A,H22B,H22C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C30(H30A,
 H30B,H30C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C36(H36A,H36B,H36C),
 C40(H40A,H40B,H40C), C42(H42A,H42B,H42C), C44(H44A,H44B,H44C), C46(H46A,H46B,
 H46C), C48(H48A,H48B,H48C), C52(H52A,H52B,H52C), C54(H54A,H54B,H54C), C56(H56A,
 H56B,H56C), C58(H58A,H58B,H58C), C62(H62A,H62B,H62C), C64(H64A,H64B,H64C),
 C66(H66A,H66B,H66C)
;
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.905
_shelx_hkl_checksum              7101
_shelx_res_checksum              32316
_shelxl_version_number           2013-2