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_4088803
_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         'C25 H21 Cl2 Co N2 P'
_chemical_formula_sum            'C25 H21 Cl2 Co N2 P'
_chemical_formula_weight         510.24
_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             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                 95.112(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.5905(16)
_cell_length_b                   18.320(4)
_cell_length_c                   15.217(3)
_cell_measurement_reflns_used    5697
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      25.54
_cell_measurement_theta_min      2.22
_cell_volume                     2385.3(8)
_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    'XT (Sheldrick, 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 0.987
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'Bruker Kappa/ApexII CCD'
_diffrn_measurement_method       'profile data from \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  0.0597
_diffrn_reflns_av_unetI/netI     0.0393
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            37848
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.374
_diffrn_reflns_theta_min         1.744
_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    1.026
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6161
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0713 before and 0.0340 after correction.
The Ratio of minimum to maximum transmission is 0.8262.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.421
_exptl_crystal_description       prism
_exptl_crystal_F_000             1044
_exptl_crystal_preparation
; 
The data crystal was mounted using oil (Parantone-N, Exxon) to a 
0.3 mm cryo-loop (Hampton Research) with the (4 0 -1) scattering 
planes roughly normal to the spindle axis.  
;
_exptl_crystal_size_max          0.266
_exptl_crystal_size_mid          0.164
_exptl_crystal_size_min          0.076
_refine_diff_density_max         0.317
_refine_diff_density_min         -0.291
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     391
_refine_ls_number_reflns         5909
_refine_ls_number_restraints     521
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0514
_refine_ls_R_factor_gt           0.0324
_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^)+(0.0274P)^2^+1.1152P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0686
_refine_ls_wR_factor_ref         0.0771
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4520
_reflns_number_total             5909
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00457_si_004.cif
_cod_data_source_block           CoCl2(Ph2PC6H4NMepy)
_cod_original_cell_volume        2385.4(8)
_cod_database_code               4088803
_shelx_estimated_absorpt_t_max   0.926
_shelx_estimated_absorpt_t_min   0.772
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 P1-C20A \\sim P1-C20
 with sigma of 0.02
 P1-C14A \\sim P1-C14
 with sigma of 0.02
3. Restrained planarity
 C20, C21, C22, C23, C24, C25
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C20 \\sim C20A \\sim C21 \\sim C21A \\sim C22 \\sim C22A \\sim C23 \\sim C23A
\\sim C24 \\sim C24A \\sim C25 \\sim C25A: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C14 \\sim C14A \\sim C15 \\sim C15A \\sim C16 \\sim C16A \\sim C17 \\sim C17A
\\sim C18 \\sim C18A \\sim C19 \\sim C19A: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C20, C20A, C21, C21A, C22, C22A, C23, C23A, C24, C24A, C25, C25A
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 C14, C14A, C15, C15A, C16, C16A, C17, C17A, C18, C18A, C19, C19A
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
6. Same fragment restrains
{C14, C15, C16, C17, C18, C19} sigma for 1-2: 0.01, 1-3: 0.04
as
{C14A, C15A, C16A, C17A, C18A, C19A}
{C20, C21, C22, C23, C24, C25} sigma for 1-2: 0.01, 1-3: 0.04
as
{C20A, C21A, C22A, C23A, C24A, C25A}
7. Others
 Sof(C20A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(H22A)=Sof(C23A)=Sof(H23A)=
 Sof(C24A)=Sof(H24A)=Sof(C25A)=Sof(H25A)=1-FVAR(1)
 Sof(C20)=Sof(C21)=Sof(H21)=Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=Sof(C24)=
 Sof(H24)=Sof(C25)=Sof(H25)=FVAR(1)
 Sof(C14A)=Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(H17A)=
 Sof(C18A)=Sof(H18A)=Sof(C19A)=Sof(H19A)=1-FVAR(2)
 Sof(C14)=Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17)=Sof(C18)=
 Sof(H18)=Sof(C19)=Sof(H19)=FVAR(2)
8.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C9(H9), C10(H10), C11(H11), C12(H12),
 C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C15A(H15A), C16A(H16A),
 C17A(H17A), C18A(H18A), C19A(H19A), C21(H21), C22(H22), C23(H23), C24(H24),
 C25(H25), C21A(H21A), C22A(H22A), C23A(H23A), C24A(H24A), C25A(H25A)
8.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_shelx_res_checksum              2377
_shelx_hkl_checksum              35650
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'