Decarboxylative Phosphine Synthesis: Insights into the Catalytic, Autocatalytic, and Inhibitory Roles of Additives and Intermediates
Jin, Shengfei; Haug, Graham C.; Nguyen, Vu T.; Flores-Hansen, Carsten; Arman, Hadi D.; Larionov, Oleg V.; ACS Catalysis  (2019) 9764–; doi:10.1021/acscatal.9b03366

data_4514896
_publ_section_title
;
 Decarboxylative Phosphine Synthesis: Insights into the Catalytic,
 Autocatalytic, and Inhibitory Roles of Additives and Intermediates
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              9764
_journal_paper_doi               10.1021/acscatal.9b03366
_journal_year                    2019
_chemical_formula_moiety         'C38 H46 Cl2 P2 Pd'
_chemical_formula_sum            'C38 H46 Cl2 P2 Pd'
_chemical_formula_weight         741.99
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-10-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                69.891(3)
_cell_angle_beta                 65.634(4)
_cell_angle_gamma                67.434(4)
_cell_formula_units_Z            1
_cell_length_a                   9.4779(5)
_cell_length_b                   9.5662(3)
_cell_length_c                   11.4380(4)
_cell_measurement_reflns_used    15392
_cell_measurement_temperature    98(2)
_cell_measurement_theta_max      29.5300
_cell_measurement_theta_min      2.4340
_cell_volume                     850.88(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28e (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28e (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28e (Rigaku OD, 2015)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      98(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -31.00  81.00   1.00   26.00    --   -7.50  38.00   0.00  112
  2  \w    -96.00  24.00   1.00   26.00    --   -7.50 -72.00 120.00  120
  3  \w    -96.00  21.00   1.00   26.00    --   -7.50 -57.00 -30.00  117
  4  \w    -36.00  81.00   1.00   26.00    --   -7.50  57.00 -90.00  117
  5  \w    -39.00  81.00   1.00   26.00    --   -7.50  72.00 150.00  120
  6  \w    -36.00  81.00   1.00   26.00    --   -7.50  57.00  60.00  117
  7  \w    -36.00  81.00   1.00   26.00    --   -7.50  57.00-120.00  117
  8  \w    -96.00  16.00   1.00   26.00    --   -7.50 -38.00-180.00  112
  9  \w    -36.00  20.00   1.00   26.00    --   -7.50  57.00 120.00   56
 10  \w    -31.00  81.00   1.00   26.00    --   -7.50  38.00  90.00  112
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RCD3): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0433238000
_diffrn_orient_matrix_UB_12      -0.0101339000
_diffrn_orient_matrix_UB_13      0.0683763000
_diffrn_orient_matrix_UB_21      -0.0623724000
_diffrn_orient_matrix_UB_22      -0.0122809000
_diffrn_orient_matrix_UB_23      -0.0109110000
_diffrn_orient_matrix_UB_31      0.0396082000
_diffrn_orient_matrix_UB_32      -0.0807655000
_diffrn_orient_matrix_UB_33      0.0087655000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0356
_diffrn_reflns_av_unetI/netI     0.0201
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            27761
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.998
_diffrn_reflns_theta_min         2.364
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.823
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94397
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28e (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.448
_exptl_crystal_description       plate
_exptl_crystal_F_000             384
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.369
_refine_diff_density_min         -0.273
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     200
_refine_ls_number_reflns         3331
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0240
_refine_ls_R_factor_gt           0.0229
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0220P)^2^+0.8130P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0529
_refine_ls_wR_factor_ref         0.0535
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3249
_reflns_number_total             3331
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b03366_si_005.cif
_cod_data_source_block           cd1757
_cod_database_code               4514896
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         Pd1P4Cl2C4
_shelx_estimated_absorpt_t_max   0.984
_shelx_estimated_absorpt_t_min   0.922
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.a Ternary CH refined with riding coordinates:
 C1(H1)
2.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C19(H19), C9(H9), C17(H17), C13(H13), C15(H15), C16(H16), C11(H11),
 C18(H18), C12(H12)
2.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C7(H7A,H7B,H7C), C6(H6A,H6B,H6C), C4(H4A,H4B,H4C)
;
_olex2_exptl_crystal_mounting_method 'nylon loop'
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.094
_oxdiff_exptl_absorpt_empirical_full_min 0.941