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_4088807
_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         'C42 H44 Co2 N4 P2, 2(C4 H8 O)'
_chemical_formula_sum            'C50 H60 Co2 N4 O2 P2'
_chemical_formula_weight         928.82
_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
_audit_creation_date             2015-11-24
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.677(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.3404(10)
_cell_length_b                   14.6679(16)
_cell_length_c                   18.312(2)
_cell_measurement_reflns_used    9900
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      26.220
_cell_measurement_theta_min      2.256
_cell_volume                     2208.3(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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      173.15
_diffrn_detector                 'Bruker APEXII CCD area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1030
_diffrn_reflns_av_unetI/netI     0.0464
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            53087
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.692
_diffrn_reflns_theta_min         1.789
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Siemens fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.869
_exptl_absorpt_correction_T_max  0.8555
_exptl_absorpt_correction_T_min  0.7173
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1503 before and 0.1126 after correction.
The Ratio of minimum to maximum transmission is 0.8385.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.397
_exptl_crystal_description       block
_exptl_crystal_F_000             976
_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 -3) scattering 
planes roughly normal to the spindle axis.  
;
_exptl_crystal_size_max          0.397
_exptl_crystal_size_mid          0.298
_exptl_crystal_size_min          0.156
_refine_diff_density_max         0.398
_refine_diff_density_min         -0.441
_refine_diff_density_rms         0.064
_refine_ls_extinction_coef       0.0014(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     319
_refine_ls_number_reflns         4597
_refine_ls_number_restraints     204
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0455
_refine_ls_R_factor_gt           0.0342
_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^)+(0.0361P)^2^+1.1797P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0859
_refine_ls_wR_factor_ref         0.0934
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3808
_reflns_number_total             4597
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00457_si_004.cif
_cod_data_source_block           '[CoMe(Ph2PC2NHpy)]2'
_cod_original_cell_volume        2208.4(4)
_cod_database_code               4088807
_shelx_estimated_absorpt_t_max   0.876
_shelx_estimated_absorpt_t_min   0.724
_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. Uiso/Uaniso restraints and constraints
C23A \\sim O1A \\sim C22A \\sim C25A \\sim C24A \\sim C22B \\sim C23B \\sim O1B
\\sim C24B \\sim C25B: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
3. Rigid body (RIGU) restrains
 C24A, O1A, C22A, C25A, C23A, C24B, C22B, C23B, O1B, C25B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Same fragment restrains
{O1A, C22A, C23A, C24A, C25A} sigma for 1-2: 0.01, 1-3: 0.04
as
{C22B, C23B, C24B, C25B, Co1}
5. Others
 Sof(O1B)=Sof(C22B)=Sof(H22C)=Sof(H22D)=Sof(C23B)=Sof(H23C)=Sof(H23D)=
 Sof(C24B)=Sof(H24C)=Sof(H24D)=Sof(C25B)=Sof(H25C)=Sof(H25D)=1-FVAR(1)
 Sof(O1A)=Sof(C22A)=Sof(H22A)=Sof(H22B)=Sof(C23A)=Sof(H23A)=Sof(H23B)=
 Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(C25A)=Sof(H25A)=Sof(H25B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C2(H2)
6.b Secondary CH2 refined with riding coordinates:
 C22A(H22A,H22B), C23A(H23A,H23B), C24A(H24A,H24B), C25A(H25A,H25B), C22B(H22C,
 H22D), C23B(H23C,H23D), C24B(H24C,H24D), C25B(H25C,H25D), C8(H8A,H8B), C9(H9A,
 H9B)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C11(H11), C12(H12), C13(H13), C14(H14),
 C15(H15), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21)
6.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_shelx_res_checksum              59575
_shelx_hkl_checksum              46429
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'