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_4514649
_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 H32 Li O4, C4 H8 O'
_chemical_formula_sum            'C92 H123 Co2 Li N4 O5'
_chemical_formula_weight         1489.74
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-07
_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                 101.0860(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.4917(16)
_cell_length_b                   13.0279(10)
_cell_length_c                   29.987(2)
_cell_measurement_reflns_used    9783
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.995
_cell_measurement_theta_min      2.186
_cell_volume                     8239.4(10)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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      100
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.945
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0433
_diffrn_reflns_av_unetI/netI     0.0344
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            125720
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.906
_diffrn_reflns_theta_min         1.291
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.456
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6478
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.1342 before and 0.0439 after correction. The Ratio of minimum to maximum transmission is 0.8686. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            'metallic dark green'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.201
_exptl_crystal_description       block
_exptl_crystal_F_000             3200
_exptl_crystal_size_max          0.235
_exptl_crystal_size_mid          0.156
_exptl_crystal_size_min          0.069
_refine_diff_density_max         0.604
_refine_diff_density_min         -0.469
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1478
_refine_ls_number_reflns         20508
_refine_ls_number_restraints     1020
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0650
_refine_ls_R_factor_gt           0.0432
_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^)+(0.0470P)^2^+5.8845P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0994
_refine_ls_wR_factor_ref         0.1100
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15724
_reflns_number_total             20508
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b01584_si_002.cif
_cod_data_source_block           ssc22e
_cod_original_cell_volume        8239.5(11)
_cod_database_code               4514649
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.969
_shelx_estimated_absorpt_t_min   0.900
_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
 C4EA-C2AA \\sim C2AA-C022 \\sim C022-C01M \\sim C1AA-C0AA \\sim C0AA-C022
 with sigma of 0.1
 O007-C4EA \\sim O007-C1AA \\sim O007-C01M
 with sigma of 0.1
 O2-C02O \\sim O2-C021
 with sigma of 0.1
 C3AA-C023 \\sim C4AA-C02O \\sim C4AA-C01N \\sim C023-C01N \\sim C021-C01N
 with sigma of 0.1
 O00N-C7EA \\sim O00M-C1EA \\sim O00N-C6DA \\sim O00M-C2EA
 with sigma of 0.1
 C3EA-C2EA \\sim C3EA-C0FA \\sim C02E-C02C \\sim C1EA-C0FA \\sim C7EA-C02C
\\sim C6DA-C02E
 with sigma of 0.1
 C8CA-C3CA \\sim C4CA-C0DA \\sim C5CA-C4CA \\sim C8CA-C7CA \\sim C9CA-C7CA
\\sim C6CA-C5CA
 with sigma of 0.1
 C70B-C69B \\sim C69A-C70A \\sim C69A-C71A \\sim C71B-C69B
 with sigma of 0.1
 C60A-C61A \\sim C65A-C60A \\sim C60B-C61B \\sim C65B-C60B \\sim C65B-C64B
\\sim C64A-C65A \\sim C61A-
 C62A \\sim C62B-C61B \\sim C63B-C62B \\sim C62A-C63A \\sim C64A-C63A \\sim
C64B-C63B
 with sigma of 0.1
 C57B-C59A \\sim C59B-C57A \\sim C58B-C57A \\sim C57B-C58A
 with sigma of 0.1
 C52B-C53B \\sim C53A-C52A \\sim C51A-C52A \\sim C52B-C51B \\sim C51A-C50A
\\sim C51B-C50B \\sim C50B-
 C49B \\sim C49A-C50A \\sim C49B-C48 \\sim C49A-C48 \\sim C53B-C48 \\sim
C53A-C48
 with sigma of 0.1
 C67A-C66A \\sim C67B-C66B \\sim C68A-C66A \\sim C68B-C66B
 with sigma of 0.1
 C54B-C56B \\sim C54A-C56A \\sim C54A-C55A \\sim C54B-C55B
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
C4EA \\sim C1AA \\sim C0AA \\sim C2AA \\sim C022 \\sim C01M: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.01
C3AA \\sim C4AA \\sim C02O \\sim C023 \\sim C01N \\sim C021: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.01
C2EA \\sim C02E \\sim C3EA \\sim C6DA \\sim C02C \\sim C0FA \\sim C1EA \\sim
C7EA: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.01
C7CA \\sim C4CA \\sim C5CA \\sim C6CA \\sim C9CA \\sim C8CA \\sim C3CA \\sim
C0DA: within 1.7A with sigma of 0.005 and sigma for terminal atoms of 0.005
C70B \\sim C69B \\sim C69A \\sim C70A \\sim C71A \\sim C71B: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.01
C60A \\sim C61A \\sim C62A \\sim C61B \\sim C62B \\sim C63A \\sim C63B \\sim
C64A \\sim C64B \\sim C65B \\sim C65A \\sim C60B: within 1.7A with sigma of
0.01 and sigma for terminal atoms of 0.01
C59A \\sim C59B \\sim C57B \\sim C57A \\sim C58B \\sim C58A: within 1.7A with
sigma of 0.005 and sigma for terminal atoms of 0.005
C53B \\sim C53A \\sim C52B \\sim C52A \\sim C51B \\sim C51A \\sim C50B \\sim
C50A \\sim C49B \\sim C49A \\sim C48: within 1.7A with sigma of 0.005 and sigma
for terminal atoms of 0.005
C67B \\sim C68B \\sim C68A \\sim C67A \\sim C66A \\sim C66B: within 1.7A with
sigma of 0.1 and sigma for terminal atoms of 0.1
C55B \\sim C55A \\sim C54A \\sim C54B \\sim C56B \\sim C56A: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.01
4. Others
 Sof(H02E)=Sof(H02F)=Sof(C2AA)=Sof(H2AA)=Sof(H2AB)=Sof(C4EA)=Sof(H4EA)=
 Sof(H4EB)=1-FVAR(1)
 Sof(H02C)=Sof(H02D)=Sof(C1AA)=Sof(H1AA)=Sof(H1AB)=Sof(C0AA)=Sof(H0AA)=
 Sof(H0AB)=FVAR(1)
 Sof(H01I)=Sof(H01J)=Sof(C02O)=Sof(H02M)=Sof(H02N)=Sof(C4AA)=Sof(H4AA)=
 Sof(H4AB)=1-FVAR(2)
 Sof(H01G)=Sof(H01H)=Sof(C023)=Sof(H02G)=Sof(H02H)=Sof(C3AA)=Sof(H3AA)=
 Sof(H3AB)=FVAR(2)
 Sof(C52A)=Sof(H52A)=Sof(C50A)=Sof(H50A)=Sof(C51A)=Sof(H51A)=Sof(C58A)=
 Sof(H58A)=Sof(H58B)=Sof(H58C)=Sof(C59A)=Sof(H59A)=Sof(H59B)=Sof(H59C)=
 Sof(C57B)=Sof(H57B)=Sof(C49A)=Sof(C56A)=Sof(H56D)=Sof(H56E)=Sof(H56F)=
 Sof(C55A)=Sof(H55D)=Sof(H55E)=Sof(H55F)=Sof(C54A)=Sof(H54A)=Sof(C53A)=1-FVAR(3)
 Sof(C49B)=Sof(C53B)=Sof(C57A)=Sof(H57A)=Sof(C55B)=Sof(H55A)=Sof(H55B)=
 Sof(H55C)=Sof(C56B)=Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(C59B)=Sof(H59D)=
 Sof(H59E)=Sof(H59F)=Sof(C58B)=Sof(H58D)=Sof(H58E)=Sof(H58F)=Sof(C51B)=
 Sof(H51B)=Sof(C50B)=Sof(H50B)=Sof(C52B)=Sof(H52B)=Sof(C54B)=Sof(H54B)=FVAR(3)
 Sof(C61B)=Sof(C62B)=Sof(H62B)=Sof(C63B)=Sof(H63B)=Sof(C70B)=Sof(H70D)=
 Sof(H70E)=Sof(H70F)=Sof(C71B)=Sof(H71D)=Sof(H71E)=Sof(H71F)=Sof(C69B)=
 Sof(H69B)=Sof(C67B)=Sof(H67D)=Sof(H67E)=Sof(H67F)=Sof(C68B)=Sof(H68D)=
 Sof(H68E)=Sof(H68F)=Sof(C66B)=Sof(H66B)=Sof(C64B)=Sof(H64B)=Sof(C65B)=
 Sof(C60B)=1-FVAR(4)
 Sof(C70A)=Sof(H70A)=Sof(H70B)=Sof(H70C)=Sof(C69A)=Sof(H69A)=Sof(C71A)=
 Sof(H71A)=Sof(H71B)=Sof(H71C)=Sof(C67A)=Sof(H67A)=Sof(H67B)=Sof(H67C)=
 Sof(C68A)=Sof(H68A)=Sof(H68B)=Sof(H68C)=Sof(C66A)=Sof(H66A)=Sof(C62A)=
 Sof(H62A)=Sof(C63A)=Sof(H63A)=Sof(C65A)=Sof(C64A)=Sof(H64A)=Sof(C61A)=
 Sof(C60A)=FVAR(4)
 Sof(C3CA)=Sof(H3CA)=Sof(H3CB)=Sof(C7CA)=Sof(H7CA)=Sof(H7CB)=Sof(O0AA)=
 Sof(C8CA)=Sof(H8CA)=Sof(H8CB)=Sof(C9CA)=Sof(H9CA)=Sof(H9CB)=1-FVAR(5)
 Sof(O1)=Sof(C6CA)=Sof(H6CA)=Sof(H6CB)=Sof(C5CA)=Sof(H5CA)=Sof(H5CB)=Sof(C4CA)=
 Sof(H4CA)=Sof(H4CB)=Sof(C0DA)=Sof(H0DA)=Sof(H0DB)=FVAR(5)
 Fixed Sof: O00M(0.5) C02C(0.5) H02I(0.5) H02J(0.5) C02E(0.5) H02K(0.5)
 H02L(0.5) C2EA(0.5) H2EA(0.5) H2EB(0.5) C7EA(0.5) H7EA(0.5) H7EB(0.5)
 C6DA(0.5) H6DA(0.5) H6DB(0.5) C1EA(0.5) H1EA(0.5) H1EB(0.5) C3EA(0.5)
 H3EA(0.5) H3EB(0.5) C0FA(0.5) H0FA(0.5) H0FB(0.5) O00N(0.5)
5.a Ternary CH refined with riding coordinates:
 C57A(H57A), C69A(H69A), C69B(H69B), C66A(H66A), C66B(H66B), C57B(H57B),
 C54B(H54B), C54A(H54A)
5.b Secondary CH2 refined with riding coordinates:
 C01M(H01E,H01F), C01N(H01I,H01J), C01N(H01G,H01H), C01X(H01M,H01N), C021(H02A,
 H02B), C022(H02E,H02F), C022(H02C,H02D), C023(H02G,H02H), C02C(H02I,H02J),
 C02E(H02K,H02L), C02O(H02M,H02N), C2EA(H2EA,H2EB), C7EA(H7EA,H7EB), C6DA(H6DA,
 H6DB), C1EA(H1EA,H1EB), C3EA(H3EA,H3EB), C0FA(H0FA,H0FB), C2AA(H2AA,H2AB),
 C1AA(H1AA,H1AB), C0AA(H0AA,H0AB), C4EA(H4EA,H4EB), C3AA(H3AA,H3AB), C4AA(H4AA,
 H4AB), C3CA(H3CA,H3CB), C6CA(H6CA,H6CB), C5CA(H5CA,H5CB), C4CA(H4CA,H4CB),
 C7CA(H7CA,H7CB), C8CA(H8CA,H8CB), C9CA(H9CA,H9CB), C0DA(H0DA,H0DB)
5.c Aromatic/amide H refined with riding coordinates:
 C52A(H52A), C50A(H50A), C51A(H51A), C62B(H62B), C63B(H63B), C62A(H62A),
 C63A(H63A), C64A(H64A), C64B(H64B), C51B(H51B), C50B(H50B), C52B(H52B)
5.d Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C46(H46A,H46B,H46C), C55B(H55A,H55B,
 H55C), C58A(H58A,H58B,H58C), C56B(H56A,H56B,H56C), C59A(H59A,H59B,H59C),
 C59B(H59D,H59E,H59F), C58B(H58D,H58E,H58F), C70A(H70A,H70B,H70C), C70B(H70D,
 H70E,H70F), C71A(H71A,H71B,H71C), C71B(H71D,H71E,H71F), C67A(H67A,H67B,H67C),
 C68A(H68A,H68B,H68C), C67B(H67D,H67E,H67F), C68B(H68D,H68E,H68F), C56A(H56D,
 H56E,H56F), C55A(H55D,H55E,H55F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method 'The crystal was mounted on a None'
_olex2_submission_special_instructions 'No special instructions were received'