Well-Defined Cobalt(I) Dihydrogen Catalyst: Experimental Evidence for a Co(I)/Co(III) Redox Process in Olefin Hydrogenation.
Tokmic, Kenan; Markus, Charles R.; Zhu, Lingyang; Fout, Alison R.; Journal of the American Chemical Society 138 (2016) 11907–11913; doi:10.1021/jacs.6b07066

data_4130807
_publ_contact_author
; 
Alison R. Fout 
University of Illinois 
School of Chemical Sciences 
A406 CLSL, Box 54-6 
600 South Mathews Avenue 
Urbana, Illinois  61801 
USA 
;
_publ_section_title
;
 Well-Defined Cobalt(I) Dihydrogen Catalyst: Experimental Evidence for a
 Co(I)/Co(III) Redox Process in Olefin Hydrogenation.
;
_journal_issue                   36
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11907
_journal_page_last               11913
_journal_paper_doi               10.1021/jacs.6b07066
_journal_volume                  138
_journal_year                    2016
_chemical_formula_sum            'C41 H42.18 Cl1.12 Co N4 P'
_chemical_formula_weight         720.66
_chemical_name_systematic
; 
C41 H42 Cl Co N4 P 
;
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-09-24
_audit_creation_method
; 
Olex2 1.2 
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998) 
;
_audit_update_record
; 
? 
;
_cell_angle_alpha                90.00
_cell_angle_beta                 94.5253(17)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   12.2774(5)
_cell_length_b                   18.0919(7)
_cell_length_c                   16.3936(7)
_cell_measurement_reflns_used    6649
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      22.62
_cell_measurement_theta_min      2.29
_cell_volume                     3630.0(3)
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2014.9-0 (Bruker, 2014)'
_computing_data_reduction
; 
SAINT V8.34A, XPREP v2014/2, SADABS V2014/4, TWINABS V2012/1 
(Bruker, 2012 & 2014) 
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'XCIF V2014-2 (Bruker, 2014)'
_computing_structure_refinement
; 
SHELX-2014-6 (Sheldrick, 2014) 
Olex2 1.2.6 (Dolomanov et. al., 2009) 
;
_computing_structure_solution    'SHELX-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'Bruker Kappa/ApexII CCD'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'profile data from \f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_wavelength_id  cm07w
_diffrn_reflns_av_R_equivalents  0.0664
_diffrn_reflns_av_unetI/netI     0.0515
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            6670
_diffrn_reflns_theta_full        25.42
_diffrn_reflns_theta_max         25.42
_diffrn_reflns_theta_min         2.16
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.634
_exptl_absorpt_correction_T_max  0.1362
_exptl_absorpt_correction_T_min  0.0291
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details   'SADABS V2014/4 (Bruker, 2014)'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.319
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             1509
_exptl_crystal_id                cm07w
_exptl_crystal_preparation
; 
The data crystal was mounted using oil (Parantone-N, Exxon) to a 
0.3 mm cryo-loop (Hampton Research) with the (-1 -4 2) scattering 
planes roughly normal to the spindle axis. 
;
_exptl_crystal_size_max          0.146
_exptl_crystal_size_mid          0.141
_exptl_crystal_size_min          0.049
_refine_diff_density_max         0.344
_refine_diff_density_min         -0.307
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     631
_refine_ls_number_reflns         6670
_refine_ls_number_restraints     524
_refine_ls_restrained_S_all      0.987
_refine_ls_R_factor_all          0.0720
_refine_ls_R_factor_gt           0.0443
_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^)+(0.0397P)^2^+2.7575P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0915
_refine_ls_wR_factor_ref         0.1006
_reflns_number_gt                4922
_reflns_number_total             6670
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja6b07066_si_001.cif
_cod_data_source_block           cm07w
_cod_database_code               4130807
_olex2_refinement_description
; 
1. Fixed Uiso 
 At 1.2 times of: 
  All C(H) groups 
 At 1.5 times of: 
  All C(H,H) groups, All C(H,H,H) groups 
2. Restrained distances 
 N1-C21 \\sim N1-C21A 
 with sigma of 0.01 
 N4-C30 \\sim N4-C30A 
 with sigma of 0.01 
3. Uiso/Uaniso restraints and constraints 
C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim 
C29 \\sim C21A \\sim C22A \\sim C23A \\sim C24A \\sim C25A \\sim C26A \\sim 
C27A \\sim C28A \\sim C29A: within 1.7A with sigma of 0.01 and sigma for 
terminal atoms of 0.02 
C30 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim 
C38 \\sim C30A \\sim C31A \\sim C32A \\sim C33A \\sim C34A \\sim C35A \\sim 
C36A \\sim C37A \\sim C38A: within 1.7A with sigma of 0.01 and sigma for 
terminal atoms of 0.02 
4. Same fragment restrains 
{C21, C22, C23, C24, C25, C26, C27, C28, C29} sigma for 1-2: 0.01, 1-3: 0.04 
as 
{C21A, C22A, C23A, C24A, C25A, C26A, C27A, C28A, C29A} 
{C30, C31, C32, C33, C34, C35, C36, C37, C38} sigma for 1-2: 0.01, 1-3: 0.04 
as 
{C30A, C31A, C32A, C33A, C34A, C35A, C36A, C37A, C38A} 
5. Others 
 Sof(C21A)=Sof(C22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(C25A)=Sof(H25A)= 
 Sof(C26A)=Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(C28A)=Sof(H28D)= 
 Sof(H28E)=Sof(H28F)=Sof(C29A)=Sof(H29D)=Sof(H29E)=1-FVAR(1) 
 Sof(C21)=Sof(C22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(C25)=Sof(H25)=Sof(C26)= 
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)= 
 Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=FVAR(1) 
 Sof(C30A)=Sof(C31A)=Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(C34A)=Sof(H34A)= 
 Sof(C35A)=Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=Sof(C37A)=Sof(H37D)= 
 Sof(H37E)=Sof(H37F)=Sof(C38A)=Sof(H38D)=Sof(H38E)=Sof(H38F)=1-FVAR(2) 
 Sof(C30)=Sof(C31)=Sof(C32)=Sof(H32)=Sof(C33)=Sof(C34)=Sof(H34)=Sof(C35)= 
 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)= 
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=FVAR(2) 
 Sof(Cl2)=1-FVAR(3) 
 Sof(H)=FVAR(3) 
6.a Aromatic/amide H refined with riding coordinates: 
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C15(H15), 
 C16(H16), C17(H17), C18(H18), C23(H23), C25(H25), C23A(H23A), C25A(H25A), 
 C32(H32), C34(H34), C32A(H32A), C34A(H34A) 
6.b Idealised Me refined as rotating group: 
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C27A(H27D,H27E, 
 H27F), C28A(H28D,H28E,H28F), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), 
 C38(H38A,H38B,H38C), C36A(H36D,H36E,H36F), C37A(H37D,H37E,H37F), C38A(H38D, 
 H38E,H38F), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C) 
;
_olex2_submission_special_instructions 'No special instructions were received'