Cobalt Phosphino-α-Iminopyridine-Catalyzed Hydrofunctionalization of Alkenes: Catalyst Development and Mechanistic Analysis
Chu, Wan-Yi; Gilbert-Wilson, Ryan; Rauchfuss, Thomas B.; van Gastel, Maurice; Neese, Frank; Organometallics 35 (2016) 2900–; doi:10.1021/acs.organomet.6b00457

data_4088810
_publ_section_title
;
 Cobalt Phosphino-\a-Iminopyridine-Catalyzed Hydrofunctionalization of
 Alkenes: Catalyst Development and Mechanistic Analysis
;
_journal_issue                   17
_journal_name_full               Organometallics
_journal_page_first              2900
_journal_paper_doi               10.1021/acs.organomet.6b00457
_journal_volume                  35
_journal_year                    2016
_chemical_formula_moiety         'C49 H41 Co N2 P2, C4 H8 O'
_chemical_formula_sum            'C53 H49 Co N2 O P2'
_chemical_formula_weight         850.81
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-01-15
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.828(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.3332(9)
_cell_length_b                   10.3192(5)
_cell_length_c                   25.6745(13)
_cell_measurement_reflns_used    9907
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.23
_cell_measurement_theta_min      2.52
_cell_volume                     4296.6(4)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_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  0.0575
_diffrn_reflns_av_unetI/netI     0.0247
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            122587
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.318
_diffrn_reflns_theta_min         2.129
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.516
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9178
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.1291 before and 0.0621 after correction.
The Ratio of minimum to maximum transmission is 0.9178.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.315
_exptl_crystal_description       block
_exptl_crystal_F_000             1784
_exptl_crystal_preparation
; 
The data crystal was mounted using oil (Parantone-N, Exxon) to a 
0.3 mm cryo-loop (Hampton Research) with the (0 -1 2) scattering 
planes roughly normal to the spindle axis.  
;
_exptl_crystal_size_max          0.445
_exptl_crystal_size_mid          0.397
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.872
_refine_diff_density_min         -0.511
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     579
_refine_ls_number_reflns         10673
_refine_ls_number_restraints     171
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0455
_refine_ls_R_factor_gt           0.0350
_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^)+(0.0330P)^2^+3.7880P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0808
_refine_ls_wR_factor_ref         0.0856
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9083
_reflns_number_total             10673
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00457_si_004.cif
_cod_data_source_block           CoMe(Ph2PC6H4NPhpy)(PPh3)
_cod_database_code               4088810
_shelx_estimated_absorpt_t_max   0.886
_shelx_estimated_absorpt_t_min   0.803
_olex2_refinement_description
;
1. 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
2. Restrained distances
 O1-C50 \\sim O1A-C50A \\sim O1-C53 \\sim O1A-C53A
 with sigma of 0.02
 C53-C52 \\sim C53A-C52A \\sim C51-C50 \\sim C51A-C50A
 with sigma of 0.02
 C52A-C51A \\sim C52-C51
 with sigma of 0.02
3. Rigid bond restraints
 O1, C50, C51, C52, C53, O1A, C50A, C51A, C52A, C53A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
O1 \\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim O1A \\sim C50A \\sim C51A
\\sim C52A \\sim C53A: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.02
5. Others
 Sof(O1A)=Sof(C50A)=Sof(H50D)=Sof(H50C)=Sof(C51A)=Sof(H51D)=Sof(H51C)=
 Sof(C52A)=Sof(H52C)=Sof(H52D)=Sof(C53A)=Sof(H53C)=Sof(H53D)=1-FVAR(1)
 Sof(O1)=Sof(C50)=Sof(H50B)=Sof(H50A)=Sof(C51)=Sof(H51B)=Sof(H51A)=Sof(C52)=
 Sof(H52B)=Sof(H52A)=Sof(C53)=Sof(H53A)=Sof(H53B)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C50(H50B,H50A), C51(H51B,H51A), C52(H52B,H52A), C53(H53A,H53B), C50A(H50D,
 H50C), C51A(H51D,H51C), C52A(H52C,H52D), C53A(H53C,H53D)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C15(H15), C16(H16), C17(H17), C18(H18), C21(H21), C22(H22), C23(H23),
  C24(H24), C25(H25), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31),
 C33(H33), C34(H34), C35(H35), C36(H36), C37(H37), C39(H39), C40(H40), C41(H41),
  C42(H42), C43(H43), C45(H45), C46(H46), C47(H47), C48(H48), C49(H49)
6.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_shelx_res_checksum              64360
_shelx_hkl_checksum              99321
_olex2_submission_special_instructions 'No special instructions were received'