Probing Catalyst Speciation in Pd-MPAAM-Catalyzed Enantioselective C(sp3)‒H Arylation: Catalyst Improvement via Destabilization of Off-Cycle Species
Hao, Wei; Bay, Katherine L.; Harris, Caleb F.; King, Daniel S.; Guzei, Ilia A.; Aristov, Michael M.; Zhuang, Zhe; Plata, R. Erik; Hill, David E.; Houk, K. N.; Berry, John F.; Yu, Jin-Quan; Blackmond, Donna G.; ACS Catalysis  (2021) 11040–11048; doi:10.1021/acscatal.1c02805

data_4518969
_publ_section_title
;
 Probing Catalyst Speciation in Pd-MPAAM-Catalyzed Enantioselective
 C(sp3)--H Arylation: Catalyst Improvement via Destabilization of
 Off-Cycle Species
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              11040
_journal_page_last               11048
_journal_paper_doi               10.1021/acscatal.1c02805
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C52 H76 Li N8 O4 Pd2, Cl'
_chemical_formula_sum            'C52 H76 Cl Li N8 O4 Pd2'
_chemical_formula_weight         1132.39
_space_group_crystal_system      trigonal
_space_group_IT_number           152
_space_group_name_Hall           'P 31 2"'
_space_group_name_H-M_alt        'P 31 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-20
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   22.416(7)
_cell_length_b                   22.416(7)
_cell_length_c                   24.448(10)
_cell_measurement_reflns_used    9832
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.664
_cell_measurement_theta_min      2.257
_cell_volume                     10639(6)
_computing_cell_refinement       'SAINT+ Ver. 2018.1-0. (Bruker-AXS, 2018)'
_computing_data_collection       'APEX3 Ver. 2018.1-0. (Bruker-AXS, 2018)'
_computing_data_reduction        'SAINT+ Ver. 2018.1-0. (Bruker-AXS, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2015b)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100.01
_diffrn_detector                 'charge-coupled device (CCD) area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker APEX II'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II Quazar'
_diffrn_measurement_method       '0.5\% \w and 0.5\% \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_detector       'Bruker APEX II'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0807
_diffrn_reflns_av_unetI/netI     0.0382
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            142563
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.735
_diffrn_reflns_theta_min         1.049
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.583
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.6731
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Krause et al., 2015) was used for absorption correction.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.060
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             3528
_exptl_crystal_size_max          0.106
_exptl_crystal_size_mid          0.075
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.307
_refine_diff_density_min         -0.681
_refine_diff_density_rms         0.085
_refine_ls_abs_structure_details
;
 Flack x determined using 5222 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.024(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     556
_refine_ls_number_reflns         13559
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0509
_refine_ls_R_factor_gt           0.0419
_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^)+(0.0683P)^2^+5.5768P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1048
_refine_ls_wR_factor_ref         0.1103
_reflns_Friedel_coverage         0.851
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                12375
_reflns_number_total             13559
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c02805_si_002.cif
_cod_data_source_block           berry862i_sq
_cod_original_cell_volume        10639(8)
_cod_database_code               4518969
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.994
_shelx_estimated_absorpt_t_min   0.941
_olex2_refinement_description
;
1. Others
 Fixed Uiso: H1A(0.053) H1B(0.053) H1C(0.053) H3(0.039) H4A(0.043) H4B(0.043)
 H6(0.065) H7(0.086) H8(0.085) H9(0.07) H10(0.052) H11A(0.034) H11B(0.034)
 H12A(0.057) H12B(0.057) H12C(0.057) H13A(0.06) H13B(0.06) H13C(0.06)
 H14A(0.057) H14B(0.057) H14C(0.057) H15A(0.061) H15B(0.061) H15C(0.061)
 H16A(0.036) H16B(0.036) H17(0.033) H18A(0.052) H18B(0.052) H24(0.057)
 H23(0.068) H22(0.076) H21(0.071) H20(0.055) H26A(0.068) H26B(0.068)
 H26C(0.068) H27A(0.071) H27B(0.071) H27C(0.071) H29(0.046) H30A(0.07)
 H30B(0.07) H30C(0.07) H30D(0.07) H32(0.096) H33(0.096) H34(0.096) H35(0.096)
 H36(0.096) H32A(0.096) H33A(0.096) H34A(0.096) H35A(0.096) H36A(0.096)
 H37A(0.07) H37B(0.07) H38A(0.071) H38B(0.071) H38C(0.071) H39A(0.106)
 H39B(0.106) H39C(0.106) H40A(0.059) H40B(0.059) H40C(0.059) H42(0.036)
 H43A(0.049) H43B(0.049) H49(0.067) H48(0.087) H47(0.1) H46(0.082) H45(0.07)
 H50A(0.039) H50B(0.039) H51A(0.051) H51B(0.051) H51C(0.051) H52A(0.064)
 H52B(0.064) H52C(0.064)
 Fixed X: H1A(0.659078) H1B(0.678492) H1C(0.617358) H3(0.78396) H4A(0.816664)
 H4B(0.888648) H6(0.78973) H7(0.833006) H8(0.947746) H9(1.019212) H10(0.975937)
 H11A(0.885749) H11B(0.91461) H12A(0.783973) H12B(0.810664) H12C(0.754601)
 H13A(0.946616) H13B(0.926836) H13C(0.896065) H14A(0.844014) H14B(0.805383)
 H14C(0.762083) H15A(0.715228) H15B(0.766957) H15C(0.768384) H16A(0.886513)
 H16B(0.917747) H17(0.882961) H18A(0.99747) H18B(0.987751) H24(1.04041)
 H23(1.091794) H22(1.095882) H21(1.048586) H20(0.997201) H26A(0.83223)
 H26B(0.897247) H26C(0.902324) H27A(0.76768) H27B(0.78065) H27C(0.844435)
 H29(0.794937) H30A(0.939302) H30B(0.910878) H30C(0.939233) H30D(0.908713)
 H32(0.82913) H33(0.843471) H34(0.930787) H35(1.003762) H36(0.989422)
 H32A(0.847007) H33A(0.870372) H34A(0.950335) H35A(1.006933) H36A(0.983569)
 H37A(0.81398) H37B(0.868538) H38A(0.665115) H38B(0.69098) H38C(0.700051)
 H39A(0.812161) H39B(0.754751) H39C(0.732225) H40A(0.64805) H40B(0.674952)
 H40C(0.634502) H42(0.836631) H43A(0.843151) H43B(0.91518) H49(0.937381)
 H48(0.989759) H47(0.999578) H46(0.957019) H45(0.904641) H50A(0.93888)
 H50B(0.934263) H51A(0.814555) H51B(0.873945) H51C(0.807142) H52A(0.94331)
 H52B(0.969894) H52C(0.913015) Cl1(1) Cl2(1)
 Fixed Y: H1A(0.392704) H1B(0.384667) H1C(0.320089) H3(0.285957) H4A(0.361729)
 H4B(0.410708) H6(0.243478) H7(0.172047) H8(0.20463) H9(0.308645) H10(0.380077)
 H11A(0.319113) H11B(0.399406) H12A(0.304756) H12B(0.264296) H12C(0.282035)
 H13A(0.434073) H13B(0.356651) H13C(0.39477) H14A(0.524078) H14B(0.566943)
 H14C(0.484607) H15A(0.495578) H15B(0.576993) H15C(0.532839) H16A(0.622068)
 H16B(0.574414) H17(0.596703) H18A(0.585758) H18B(0.60183) H24(0.677478)
 H23(0.795113) H22(0.871771) H21(0.830795) H20(0.71316) H26A(0.517704)
 H26B(0.5722) H26C(0.515193) H27A(0.233353) H27B(0.187106) H27C(0.249285)
 H29(0.175862) H30A(0.269325) H30B(0.242752) H30C(0.272435) H30D(0.23835)
 H32(0.104001) H33(0.007589) H34(0.009794) H35(0.108411) H36(0.204823)
 H32A(0.097228) H33A(0.009694) H34A(0.028078) H35A(0.133996) H36A(0.22153)
 H37A(0.167005) H37B(0.247824) H38A(0.184513) H38B(0.129673) H38C(0.175613)
 H39A(0.260147) H39B(0.180212) H39C(0.237623) H40A(0.274958) H40B(0.285847)
 H40C(0.323219) H42(0.481596) H43A(0.423652) H43B(0.438423) H49(0.58275)
 H48(0.69166) H47(0.701638) H46(0.602707) H45(0.493797) H50A(0.508373)
 H50B(0.437552) H51A(0.436179) H51B(0.50862) H51C(0.462015) H52A(0.399122)
 H52B(0.479526) H52C(0.424761)
 Fixed Z: H1A(0.160997) H1B(0.222499) H1C(0.191582) H3(0.166061) H4A(0.083342)
 H4B(0.112962) H6(0.053696) H7(0.027272) H8(0.045805) H9(0.090761)
 H10(0.117186) H11A(0.209363) H11B(0.197853) H12A(0.32225) H12B(0.28481)
 H12C(0.261532) H13A(0.287993) H13B(0.302282) H13C(0.338075) H14A(0.144259)
 H14B(0.153922) H14C(0.15136) H15A(0.243338) H15B(0.2415) H15C(0.292403)
 H16A(0.232036) H16B(0.214531) H17(0.32182) H18A(0.283595) H18B(0.345704)
 H24(0.215573) H23(0.19584) H22(0.262698) H21(0.34929) H20(0.369024)
 H26A(0.432835) H26B(0.398006) H26C(0.433891) H27A(0.419627) H27B(0.462535)
 H27C(0.431737) H29(0.543266) H30A(0.564746) H30B(0.504267) H30C(0.561849)
 H30D(0.503564) H32(0.50208) H33(0.50544) H34(0.559378) H35(0.609956)
 H36(0.606597) H32A(0.503648) H33A(0.526909) H34A(0.595737) H35A(0.641304)
 H36A(0.618043) H37A(0.63516) H37B(0.640519) H38A(0.634154) H38B(0.632854)
 H38C(0.580017) H39A(0.715057) H39B(0.714456) H39C(0.714788) H40A(0.700994)
 H40B(0.639164) H40C(0.660711) H42(0.672092) H43A(0.762512) H43B(0.737667)
 H49(0.690181) H48(0.731152) H47(0.826434) H46(0.880745) H45(0.839775)
 H50A(0.631479) H50B(0.650102) H51A(0.526104) H51B(0.549011) H51C(0.585404)
 H52A(0.556704) H52B(0.549438) H52C(0.508666) Cl1(0.166667) Cl2(0.666667)
;
_shelx_res_checksum              49023
_shelx_hkl_checksum              91607
_shelx_fab_checksum              99352
_olex2_submission_special_instructions 'No special instructions were received'