Di-Palladium Complexes are Active Catalysts for Mono-N-Protected Amino Acid-Accelerated Enantioselective C‒H Functionalization
Gair, Joseph J.; Haines, Brandon E.; Filatov, Alexander S.; Musaev, Djamaladdin G.; Lewis, Jared C.; ACS Catalysis  (2019) 11386–; doi:10.1021/acscatal.9b03887

data_4516215
_publ_section_title
;
 Di-Palladium Complexes are Active Catalysts for Mono-N-Protected Amino
 Acid-Accelerated Enantioselective C--H Functionalization
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              11386
_journal_paper_doi               10.1021/acscatal.9b03887
_journal_year                    2019
_chemical_formula_moiety         'C34 H44 Fe2 N4 O6 Pd2, 0.5(C6 H6)'
_chemical_formula_sum            'C37 H47 Fe2 N4 O6 Pd2'
_chemical_formula_weight         968.28
_space_group_crystal_system      orthorhombic
_space_group_IT_number           52
_space_group_name_Hall           '-P 2a 2bc'
_space_group_name_H-M_alt        'P n n a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-03-16
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.4063(7)
_cell_length_b                   23.1323(11)
_cell_length_c                   21.3599(10)
_cell_measurement_reflns_used    9807
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.38
_cell_measurement_theta_min      2.40
_cell_volume                     7612.3(6)
_computing_cell_refinement       'SAINT V.8.35A (Bruker AXS Inc., 2013)'
_computing_data_collection       'APEX3 v.2015.9-0 (Bruker AXS Inc., 2015)'
_computing_data_reduction        'SAINT V.8.35A (Bruker AXS Inc., 2013)'
_computing_molecular_graphics
;
OLEX2: a complete structure solution, refinement and analysis program 
Dolomanov et al., 2009

Mercury: visualization and analysis of crystal structures
Macrae, et al., 2006

O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann.
J. Appl. Cryst. (2009). 42, 339-341;

C. F. Macrae, P. R. Edgington, P. McCabe, E. Pidcock, G. P. Shields, R. Taylor,
M. Towler and J. van de Streek, J. Appl. Cryst. (2006). 39, 453-457.
;
_computing_publication_material
;
 APEX3 v.2015.5-2 (Bruker AXS Inc., 2015)
 OLEX2 (Dolomanov et al., 2009)
;
_computing_structure_refinement  'XL-2018/3 (Sheldrick, 2015b)'
_computing_structure_solution    'XT 2018/2 (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker PHOTON 100'
_diffrn_detector_area_resol_mean 10.4167
_diffrn_detector_type            CMOS
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       'omega and phi scans'
_diffrn_radiation_monochromator  mirrors
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0649
_diffrn_reflns_av_unetI/netI     0.0246
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            196261
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.179
_diffrn_reflns_theta_min         2.399
_diffrn_source                   'micro-focus X-ray tube'
_diffrn_source_type              'INCOATEC ImuS'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.726
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6387
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0788 before and 0.0612 after correction.
The Ratio of minimum to maximum transmission is 0.8567.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.690
_exptl_crystal_description       block
_exptl_crystal_F_000             3912
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.128
_refine_diff_density_min         -0.666
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     550
_refine_ls_number_reflns         8460
_refine_ls_number_restraints     110
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0541
_refine_ls_R_factor_gt           0.0360
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0357P)^2^+19.4036P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0790
_refine_ls_wR_factor_ref         0.0869
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6827
_reflns_number_total             8460
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b03887_si_002.cif
_cod_data_source_block           02_FcGly
_cod_database_code               4516215
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.846
_shelx_estimated_absorpt_t_min   0.644
_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
 C31-C27 \\sim C28-C27 \\sim C29-C28 \\sim C30-C29 \\sim C31-C30
 with sigma of 0.01
 C29A-C28A \\sim C30A-C29A \\sim C31A-C30A \\sim C31A-C27A \\sim C28A-C27A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C29A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 C26, C32A, N4, C33A, C34A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C29A, C30A, C31A, C27A, C28A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C27, C29, C30, C31, C28
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(H29A)=Sof(C30A)=
 Sof(H30A)=Sof(C31A)=Sof(H31A)=1-FVAR(1)
 Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28)=Sof(C29)=Sof(H29)=Sof(C30)=Sof(H30)=
 Sof(C31)=Sof(H31)=FVAR(1)
 Sof(C32A)=Sof(H32A)=Sof(H32B)=Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=
 Sof(C34A)=Sof(H34D)=Sof(H34E)=Sof(H34F)=1-FVAR(2)
 Sof(C32)=Sof(H32C)=Sof(H32D)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C34)=
 Sof(H34A)=Sof(H34B)=Sof(H34C)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C31A(H31A)
6.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C11(H11A,H11B), C15(H15A,H15B), C32(H32C,H32D), C32A(H32A,H32B)
6.c Aromatic/amide H refined with riding coordinates:
 C23(H23), C24(H24), C25(H25), C1(H1), C2(H2A), C3(H3A), C4(H4), C5(H5),
 C6(H6), C7(H7), C8(H8), C35(H35), C36(H36), C37(H37), C27(H27), C28(H28),
 C29(H29), C30(H30), C31(H31), C27A(H27A), C28A(H28A), C29A(H29A), C30A(H30A)
6.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C17(H17A,H17B,
 H17C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C33A(H33D,H33E,H33F),
 C34A(H34D,H34E,H34F)
;
_shelx_res_checksum              161
_shelx_hkl_checksum              69703
_olex2_submission_special_instructions 'No special instructions were received'