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_4088809
_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         'C46 H43 Co N2 P2, 2(C4 H8 O)'
_chemical_formula_sum            'C54 H59 Co N2 O2 P2'
_chemical_formula_weight         888.90
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-01-19
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.3260(5)
_cell_length_b                   18.1145(6)
_cell_length_c                   16.2045(6)
_cell_measurement_reflns_used    9974
_cell_measurement_temperature    103(2)
_cell_measurement_theta_max      26.05
_cell_measurement_theta_min      2.51
_cell_volume                     4498.7(3)
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      102.78
_diffrn_detector                 'Bruker APEXII CCD area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II 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  0.0332
_diffrn_reflns_av_unetI/netI     0.0316
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            43118
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.084
_diffrn_reflns_theta_min         2.147
_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    0.497
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9115
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0821 before and 0.0667 after correction.
The Ratio of minimum to maximum transmission is 0.9115.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.312
_exptl_crystal_description       prism
_exptl_crystal_F_000             1880
_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 -2 1) scattering 
planes roughly normal to the spindle axis.  
;
_exptl_crystal_size_max          0.228
_exptl_crystal_size_mid          0.156
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.534
_refine_diff_density_min         -0.322
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 3965 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.027(4)
_refine_ls_extinction_coef       0.0092(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     644
_refine_ls_number_reflns         8849
_refine_ls_number_restraints     280
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0315
_refine_ls_R_factor_gt           0.0299
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0478P)^2^+1.2458P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0793
_refine_ls_wR_factor_ref         0.0804
_reflns_Friedel_coverage         0.919
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                8557
_reflns_number_total             8849
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00457_si_004.cif
_cod_data_source_block           CoMe(Ph2PC3NPhpy)(PPh3)
_cod_database_code               4088809
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.895
_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-C47 \\sim O1-C50
 with sigma of 0.02
 C52-C51 \\sim C54-C53
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O1 \\sim O1A \\sim C47 \\sim C47A \\sim C48 \\sim C48A \\sim C49 \\sim C49A
\\sim C50 \\sim C50A: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O2 \\sim O2A \\sim C51 \\sim C51A \\sim C52 \\sim C52A \\sim C53 \\sim C53A
\\sim C54A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C53A) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
4. Rigid body (RIGU) restrains
 O2, C51, C52, C53
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{O2, C51, C52, C53, C54} sigma for 1-2: 0.1, 1-3: 0.04
as
{O2A, C51A, C52A, C53A, C54A}
6. Others
 Sof(O1A)=Sof(C47A)=Sof(H47C)=Sof(H47D)=Sof(C48A)=Sof(H48C)=Sof(H48D)=
 Sof(C49A)=Sof(H49C)=Sof(H49D)=Sof(C50A)=Sof(H50C)=Sof(H50D)=1-FVAR(1)
 Sof(O1)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(C49)=
 Sof(H49A)=Sof(H49B)=Sof(C50)=Sof(H50A)=Sof(H50B)=FVAR(1)
 Sof(O2A)=Sof(C51A)=Sof(H51C)=Sof(H51D)=Sof(C52A)=Sof(H52C)=Sof(H52D)=
 Sof(C53A)=Sof(H53C)=Sof(H53D)=Sof(C54A)=Sof(H54C)=Sof(H54D)=1-FVAR(2)
 Sof(O2)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(C53)=
 Sof(H53A)=Sof(H53B)=Sof(C54)=Sof(H54A)=Sof(H54B)=FVAR(2)
7.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C51(H51A,H51B), C52(H52A,
 H52B), C53(H53A,H53B), C54(H54A,H54B), C51A(H51C,H51D), C52A(H52C,H52D),
 C53A(H53C,H53D), C54A(H54C,H54D), C47(H47A,H47B), C47A(H47C,H47D), C48(H48A,
 H48B), C48A(H48C,H48D), C49(H49A,H49B), C49A(H49C,H49D), C50(H50A,H50B),
 C50A(H50C,H50D)
7.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), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C24(H24), C25(H25),
  C26(H26), C27(H27), C28(H28), C30(H30), C31(H31), C32(H32), C33(H33),
 C34(H34), C36(H36), C37(H37), C38(H38), C39(H39), C40(H40), C42(H42), C43(H43),
  C44(H44), C45(H45), C46(H46)
7.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_shelx_res_checksum              66280
_shelx_hkl_checksum              22842
_olex2_submission_special_instructions 'No special instructions were received'