Cobalt-Catalyzed Hydrogenations via Olefin Cobaltate and Hydride Intermediates
Sandl, Sebastian; Maier, Thomas M.; van Leest, Nicolaas P.; Kröncke, Susanne; Chakraborty, Uttam; Demeshko, Serhiy; Koszinowski, Konrad; de Bruin, Bas; Meyer, Franc; Bodensteiner, Michael; Herrmann, Carmen; Wolf, Robert; Jacobi von Wangelin, Axel; ACS Catalysis 9 (2019) 7596–; doi:10.1021/acscatal.9b01584

data_4514648
_publ_section_title
;
 Cobalt-Catalyzed Hydrogenations via Olefin Cobaltate and Hydride
 Intermediates
;
_journal_issue                   8
_journal_name_full               'ACS Catalysis'
_journal_page_first              7596
_journal_paper_doi               10.1021/acscatal.9b01584
_journal_volume                  9
_journal_year                    2019
_chemical_formula_moiety         'C72 H83 Co2 N4, C16 H34 Li O4'
_chemical_formula_sum            'C90 H121 Co2 Li N4 O4.5'
_chemical_formula_weight         1455.70
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-09-21
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   25.0102(2)
_cell_length_b                   21.4146(2)
_cell_length_c                   30.8908(3)
_cell_measurement_reflns_used    38474
_cell_measurement_temperature    138.2(6)
_cell_measurement_theta_max      74.5100
_cell_measurement_theta_min      3.0050
_cell_volume                     16544.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.37b (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.37b (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.37b (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      138.2(6)
_diffrn_detector_area_resol_mean 4.1818
_diffrn_detector_type            TitanS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -50.00  26.00   1.00   20.00    --  -44.56  38.00-120.00   76
  2  \w   -124.00 -79.00   1.00   20.00    --  -44.56 -99.00-150.00   45
  3  \w    -25.00  69.00   1.00   20.00    --   44.56 -57.00  60.00   94
  4  \w     33.00 135.00   1.00   90.00    --  104.50 -77.00 -30.00  102
  5  \w     73.00 176.00   1.00   90.00    --  104.50 125.00   0.00  103
  6  \w     36.00  98.00   1.00   90.00    --  104.50 -45.00-180.00   62
  7  \w     36.00  98.00   1.00   90.00    --  104.50 -45.00-150.00   62
  8  \w     68.00 178.00   1.00   90.00    --  104.50  15.00  90.00  110
  9  \w     32.00  91.00   1.00   90.00    --  104.50 -30.00 120.00   59
 10  \w   -114.00 -21.00   1.00   20.00    --  -44.56 -57.00-150.00   93
 11  \w   -116.00 -14.00   1.00   20.00    --  -44.56 -77.00 120.00  102
 12  \w   -116.00 -14.00   1.00   20.00    --  -44.56 -77.00 -30.00  102
 13  \w     81.00 146.00   1.00   90.00    --  104.50  30.00-150.00   65
 14  \w     81.00 177.00   1.00   90.00    --  104.50  30.00 -60.00   96
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'GV1000, TitanS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0511
_diffrn_reflns_av_unetI/netI     0.0253
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            126831
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.682
_diffrn_reflns_theta_min         2.861
_exptl_absorpt_coefficient_mu    3.532
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.539
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.37b (Rigaku Oxford Diffraction, 2017)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark green'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.169
_exptl_crystal_description       block
_exptl_crystal_F_000             6256
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of hexane, thf and ether  by slow evaporation'
_exptl_crystal_size_max          0.309
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.159
_refine_diff_density_max         1.419
_refine_diff_density_min         -0.609
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1175
_refine_ls_number_reflns         16725
_refine_ls_number_restraints     686
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0690
_refine_ls_R_factor_gt           0.0623
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1146P)^2^+14.6636P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1797
_refine_ls_wR_factor_ref         0.1864
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14835
_reflns_number_total             16725
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b01584_si_002.cif
_cod_data_source_block           ssc16c
_cod_original_formula_sum        'C90 H121 Co2 Li N4 O4.50'
_cod_database_code               4514648
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.604
_shelx_estimated_absorpt_t_min   0.408
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O2-C8AA \\sim O2-C0BA \\sim O2-C5AA \\sim O2-C4AA
 with sigma of 0.02
 C9AA-C0BA \\sim C9AA-C1BA \\sim C8AA-C1BA \\sim C7AA-C4AA \\sim C7AA-C6AA
\\sim C6AA-C5AA
 with sigma of 0.02
 C4AA-C6AA \\sim C5AA-C7AA \\sim C8AA-C9AA \\sim C0BA-C1BA
 with sigma of 0.02
 O4A-C81A \\sim O4A-C84A
 with sigma of 0.02
 O4A-C81A \\sim O4A-C84A \\sim O4A-C84 \\sim O4A-C81
 with sigma of 0.01
 C83A-C82A \\sim C84A-C83A \\sim C82A-C81A \\sim C82-C81 \\sim C83-C82 \\sim
C84-C83
 with sigma of 0.01
 C2AA-C0AA \\sim C1AA-C0AA \\sim C75-C74 \\sim C75-C73 \\sim C74-C4BA
 with sigma of 0.02
 C68A-C67B \\sim C69A-C67B \\sim C68-C67A \\sim C69-C67A
 with sigma of 0.01
 C67A-C66A \\sim C67B-C66
 with sigma of 0.01
 C70A-C62A \\sim C70B-C62
 with sigma of 0.01
 C72A-C70A \\sim C72B-C70B \\sim C71A-C70A \\sim C71B-C70B
 with sigma of 0.01
 C71A-C70A \\sim C71B-C70B \\sim C72A-C70A \\sim C72B-C70B
 with sigma of 0.01
 H7BB-H4BA \\sim H4BA-H7BC
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
C55 \\sim C57 \\sim C56: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.01
C33 \\sim C31 \\sim C32: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.01
C35 \\sim C34 \\sim C36: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.01
C19 \\sim C21A \\sim C21 \\sim C20A \\sim C20: within 1.7A with sigma of 0.01
and sigma for terminal atoms of 0.01
C5AA \\sim C6AA \\sim C7AA \\sim C4AA \\sim C8AA \\sim C1BA \\sim C9AA \\sim
C0BA: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.01
C81A \\sim C81 \\sim C82A \\sim C82 \\sim C83 \\sim C83A \\sim C84 \\sim C84A:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.01
C22 \\sim C23A \\sim C23 \\sim C24 \\sim C24A: within 1.7A with sigma of 0.01
and sigma for terminal atoms of 0.01
C67A \\sim C69 \\sim C68: within 1.7A with sigma of 0.001 and sigma for
terminal atoms of 0.001
C74 \\sim C4BA \\sim C2AA \\sim C0AA \\sim C1AA \\sim C75 \\sim C73 \\sim O5:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.01
C3BA \\sim C2BA: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.01
C61 \\sim C66 \\sim C65 \\sim C64 \\sim C63 \\sim C62: within 1.7A with sigma
of 0.001 and sigma for terminal atoms of 0.001
C62A \\sim C61 \\sim C66A \\sim C65A \\sim C64A \\sim C63A: within 1.7A with
sigma of 0.001 and sigma for terminal atoms of 0.001
C67B \\sim C68A \\sim C69A: within 1.7A with sigma of 0.001 and sigma for
terminal atoms of 0.001
C67A \\sim C68 \\sim C69: within 1.7A with sigma of 0.001 and sigma for
terminal atoms of 0.001
C60A \\sim C60 \\sim C58 \\sim C59 \\sim C59A: within 1.7A with sigma of 0.01
and sigma for terminal atoms of 0.01
C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C49: within 1.7A with sigma
of 0.005 and sigma for terminal atoms of 0.005
C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30: within 1.7A with sigma
of 0.005 and sigma for terminal atoms of 0.005
C71A \\sim C70A \\sim C72A: within 1.7A with sigma of 0.001 and sigma for
terminal atoms of 0.001
C70B \\sim C72B \\sim C71B: within 1.7A with sigma of 0.001 and sigma for
terminal atoms of 0.001
O3 \\sim C6BA \\sim C7BA: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.01
4. Others
 Sof(H22A)=Sof(H19A)=1-FVAR(1)
 Sof(H22)=Sof(H19)=FVAR(1)
 Sof(H58A)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=Sof(C20)=Sof(H20A)=Sof(H20B)=
 Sof(H20C)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C24A)=Sof(H24D)=Sof(H24E)=
 Sof(H24F)=Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C59A)=Sof(H59D)=
 Sof(H59E)=Sof(H59F)=Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=Sof(C69)=Sof(H69A)=
 Sof(H69B)=Sof(H69C)=Sof(C72A)=Sof(H72A)=Sof(H72B)=Sof(H72C)=Sof(C71A)=
 Sof(H71A)=Sof(H71B)=Sof(H71C)=Sof(C67A)=Sof(H67A)=Sof(C66A)=Sof(C65A)=
 Sof(H65A)=Sof(C64A)=Sof(H64A)=Sof(C63A)=Sof(H63A)=Sof(C62A)=Sof(C70A)=
 Sof(H70A)=1-FVAR(2)
 Sof(H58)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=Sof(C66)=Sof(C65)=Sof(H65)=
 Sof(C64)=Sof(H64)=Sof(C63)=Sof(H63)=Sof(C62)=Sof(C23)=Sof(H23A)=Sof(H23B)=
 Sof(H23C)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C21A)=Sof(H21D)=Sof(H21E)=
 Sof(H21F)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C60A)=Sof(H60D)=
 Sof(H60E)=Sof(H60F)=Sof(C67B)=Sof(H67B)=Sof(C69A)=Sof(H69D)=Sof(H69E)=
 Sof(H69F)=Sof(C68A)=Sof(H68D)=Sof(H68E)=Sof(H68F)=Sof(C70B)=Sof(H70B)=
 Sof(C71B)=Sof(H71D)=Sof(H71E)=Sof(H71F)=Sof(C72B)=Sof(H72D)=Sof(H72E)=
 Sof(H72F)=FVAR(2)
 Sof(H73C)=Sof(H73D)=Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(C74)=Sof(H74A)=Sof(H74B)=
 Sof(C84)=Sof(H84A)=Sof(H84B)=Sof(C83)=Sof(H83A)=Sof(H83B)=Sof(C81)=Sof(H81A)=
 Sof(H81B)=Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(C9AA)=Sof(H9AA)=Sof(H9AB)=Sof(C1BA)=
 Sof(H1BA)=Sof(H1BB)=Sof(C0BA)=Sof(H0BA)=Sof(H0BB)=Sof(C8AA)=Sof(H8AA)=
 Sof(H8AB)=Sof(C4BA)=Sof(H4BA)=Sof(H4BB)=1-FVAR(3)
 Sof(H73A)=Sof(H73B)=Sof(C81A)=Sof(H81C)=Sof(H81D)=Sof(C82A)=Sof(H82C)=
 Sof(H82D)=Sof(C83A)=Sof(H83C)=Sof(H83D)=Sof(C84A)=Sof(H84C)=Sof(H84D)=
 Sof(C0AA)=Sof(H0AA)=Sof(H0AB)=Sof(C2AA)=Sof(H2AA)=Sof(H2AB)=Sof(C1AA)=
 Sof(H1AA)=Sof(H1AB)=Sof(C5AA)=Sof(H5AA)=Sof(H5AB)=Sof(C6AA)=Sof(H6AA)=
 Sof(H6AB)=Sof(C7AA)=Sof(H7AA)=Sof(H7AB)=Sof(C4AA)=Sof(H4AA)=Sof(H4AB)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C55(H55), C58(H58), C58(H58A), C34(H34), C22(H22), C22(H22A), C19(H19A),
 C19(H19), C31(H31), C67A(H67A), C70A(H70A), C67B(H67B), C70B(H70B)
5.b Secondary CH2 refined with riding coordinates:
 C73(H73C,H73D), C73(H73A,H73B), C75(H75A,H75B), C74(H74A,H74B), C84(H84A,
 H84B), C83(H83A,H83B), C81(H81A,H81B), C82(H82A,H82B), C81A(H81C,H81D),
 C82A(H82C,H82D), C83A(H83C,H83D), C84A(H84C,H84D), C0AA(H0AA,H0AB), C2AA(H2AA,
 H2AB), C1AA(H1AA,H1AB), C5AA(H5AA,H5AB), C6AA(H6AA,H6AB), C7AA(H7AA,H7AB),
 C4AA(H4AA,H4AB), C9AA(H9AA,H9AB), C1BA(H1BA,H1BB), C0BA(H0BA,H0BB), C8AA(H8AA,
 H8AB), C3BA(H3BA,H3BB), C6BA(H6BA,H6BB), C4BA(H4BA,H4BB)
5.c Aromatic/amide H refined with riding coordinates:
 C48(H48), C12(H12), C42(H42), C43(H43), C41(H41), C6(H6), C10(H10), C15(H15),
 C17(H17), C16(H16), C11(H11), C46(H46), C7(H7), C47(H47), C8(H8), C27(H27),
 C29(H29), C28(H28), C65(H65), C64(H64), C63(H63), C51(H51), C53(H53), C52(H52),
  C65A(H65A), C64A(H64A), C63A(H63A)
5.d Fitted hexagon refined as free rotating group:
 C66(C65,C64,C63,C62,C61)
5.e Idealised Me refined as rotating group:
 C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C35(H35A,H35B,H35C), C20(H20A,H20B,
 H20C), C56(H56A,H56B,H56C), C36(H36A,H36B,H36C), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C), C23(H23A,H23B,H23C), C57(H57A,H57B,H57C), C21(H21A,H21B,H21C),
 C24(H24A,H24B,H24C), C24A(H24D,H24E,H24F), C23A(H23D,H23E,H23F), C21A(H21D,
 H21E,H21F), C20A(H20D,H20E,H20F), C59A(H59D,H59E,H59F), C60A(H60D,H60E,H60F),
 C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C72A(H72A,H72B,H72C), C71A(H71A,H71B,
 H71C), C2BA(H2BA,H2BB,H2BC), C7BA(H7BA,H7BB,H7BC), C69A(H69D,H69E,H69F),
 C68A(H68D,H68E,H68F), C71B(H71D,H71E,H71F), C72B(H72D,H72E,H72F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 152 electrons were 
found in a volume of 804\%A^3 in 2 voids. 
This is consistent with the presence of 
0.5[C4H8O] per formula unit 
which account for 160.0 electrons.
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;