Activator-free single-component Co(i)-catalysts for regio- and enantioselective heterodimerization and hydroacylation reactions of 1,3-dienes. New reduction procedures for synthesis of [L]Co(i)-complexes and comparison to in situ generated catalysts
Parsutkar, Mahesh M.; Moore, Curtis E.; RajanBabu, T. V.; Dalton Transactions  (2022) –; doi:10.1039/D2DT01484J

data_7710548
_publ_section_title
;
 Activator-free single-component Co(i)-catalysts for regio- and
 enantioselective heterodimerization and hydroacylation reactions of
 1,3-dienes. New reduction procedures for synthesis of [L]Co(i)-complexes
 and comparison to in situ generated catalysts
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT01484J
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C32 H54 Co P2, C32 H12 B F24'
_chemical_formula_sum            'C64 H66 B Co F24 P2'
_chemical_formula_weight         1422.84
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_block_doi                 10.5517/ccdc.csd.cc25nxpg
_audit_creation_date             2020-07-13
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.06.28 svn.raecde09e for OlexSys, GUI svn.r6132)
;
_audit_update_record
;
2020-07-13 deposited with the CCDC.	2022-06-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.252(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.2881(15)
_cell_length_b                   17.6461(13)
_cell_length_c                   38.074(3)
_cell_measurement_reflns_used    5019
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      25.295
_cell_measurement_theta_min      3.052
_cell_volume                     12938.0(17)
_computing_cell_refinement       'SAINT v8.40A (Bruker, 2019)'
_computing_data_collection       'APEX3 v2019.1-0 (Bruker, 2019)'
_computing_data_reduction        'SAINT v8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker Photon II area detector'
_diffrn_detector_area_resol_mean 10.5
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'Curved-Graphite, Bruker TRIUMPH'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0763
_diffrn_reflns_av_unetI/netI     0.0537
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            114095
_diffrn_reflns_point_group_measured_fraction_full 0.963
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.422
_diffrn_reflns_theta_min         3.051
_diffrn_source                   'sealed tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_type              fine-focus
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.424
_exptl_absorpt_correction_T_max  0.026491
_exptl_absorpt_correction_T_min  0.010092
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.

Final HKLF 4 output contains 114095 reflections, Rint = 0.0763
 (63862 with I > 3sig(I), Rint = 0.0637)
;
_exptl_crystal_colour            'Greenish Blue'
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.461
_exptl_crystal_description       Block
_exptl_crystal_F_000             5824
_exptl_crystal_size_max          0.271
_exptl_crystal_size_mid          0.172
_exptl_crystal_size_min          0.143
_refine_diff_density_max         0.320
_refine_diff_density_min         -0.873
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 8249 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.007(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1868
_refine_ls_number_reflns         23230
_refine_ls_number_restraints     253
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0573
_refine_ls_R_factor_gt           0.0492
_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^)+(0.0723P)^2^+6.5638P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1159
_refine_ls_wR_factor_ref         0.1200
_reflns_Friedel_coverage         0.870
_reflns_Friedel_fraction_full    0.931
_reflns_Friedel_fraction_max     0.921
_reflns_number_gt                20824
_reflns_number_total             23230
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01484j2.cif
_cod_data_source_block           RBabu_MP-05-158
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

data item '_exptl_crystal_colour_modifier' value 'Greenish' was
changed to 'greenish' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

data item '_exptl_crystal_colour_primary' value 'Blue' was changed to
'blue' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_original_cell_volume        12938.1(17)
_cod_database_code               7710548
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.942
_shelx_estimated_absorpt_t_min   0.894
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5647(12)
 0.4353(12)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(F17') = Uanis(F18C)
4. Rigid body (RIGU) restrains
 F22', F23', F24', F22C, F23C, F24C, C64'
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F4', F5', F6', F4C, F5C, F6C, C40'
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F10, F11, F12, F10B, F11B, F12B, C48
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F16', F17', F18', F16C, F17C, F18C, C56'
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F13, F14, F15, F13B, F14B, F15B, C55
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F22, F23, F24, F22B, F23B, F24B, C64
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F19, F20, F21, F19B, F20B, F21B, C63
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(F22C)=Sof(F23C)=Sof(F24C)=1-FVAR(1)
 Sof(F22')=Sof(F23')=Sof(F24')=FVAR(1)
 Sof(F4C)=Sof(F5C)=Sof(F6C)=1-FVAR(2)
 Sof(F4')=Sof(F5')=Sof(F6')=FVAR(2)
 Sof(F10B)=Sof(F11B)=Sof(F12B)=1-FVAR(3)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(3)
 Sof(F16C)=Sof(F17C)=Sof(F18C)=1-FVAR(4)
 Sof(F16')=Sof(F17')=Sof(F18')=FVAR(4)
 Sof(F13B)=Sof(F14B)=Sof(F15B)=1-FVAR(5)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(5)
 Sof(F22B)=Sof(F23B)=Sof(F24B)=1-FVAR(6)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(6)
 Sof(F19B)=Sof(F20B)=Sof(F21B)=1-FVAR(7)
 Sof(F19)=Sof(F20)=Sof(F21)=FVAR(7)
6.a Ternary CH refined with riding coordinates:
 C13(H13), C16(H16), C17(H17), C20(H20), C23(H23), C26(H26), C27(H27),
 C30(H30), C13'(H13'), C16'(H16'), C17'(H17'), C20'(H20'), C23'(H23'),
 C26'(H26'), C27'(H27'), C30'(H30')
6.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C4(H4A,H4B), C14(H14A,H14B), C15(H15A,H15B), C24(H24A,H24B),
 C25(H25A,H25B), C1'(H1'A,H1'B), C4'(H4'A,H4'B), C14'(H14C,H14D), C15'(H15C,
 H15D), C24'(H24C,H24D), C25'(H25C,H25D)
6.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C9'(H9'), C10'(H10'), C11'(H11'),
 C12'(H12'), C34(H34), C36(H36), C38(H38), C42(H42), C44(H44), C46(H46),
 C50(H50), C52(H52), C54(H54), C58(H58), C60(H60), C62(H62), C34'(H34'),
 C36'(H36'), C38'(H38'), C42'(H42'), C44'(H44'), C46'(H46'), C50'(H50'),
 C52'(H52'), C54'(H54'), C58'(H58'), C60'(H60'), C62'(H62')
6.d Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C),
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C5'(H5'A,H5'B,H5'C), C6'(H6'A,
 H6'B,H6'C), C18'(H18D,H18E,H18F), C19'(H19D,H19E,H19F), C21'(H21D,H21E,H21F),
 C22'(H22D,H22E,H22F), C28'(H28D,H28E,H28F), C29'(H29D,H29E,H29F), C31'(H31D,
 H31E,H31F), C32'(H32D,H32E,H32F)
;
_shelx_res_checksum              73766
_shelx_hkl_checksum              11449
_olex2_submission_special_instructions 'No special instructions were received'