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_4514898
_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         'C21 H22 B P'
_chemical_formula_sum            'C21 H22 B P'
_chemical_formula_weight         316.16
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-08-23
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.659(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.01980(10)
_cell_length_b                   15.1635(3)
_cell_length_c                   14.6975(3)
_cell_measurement_reflns_used    11058
_cell_measurement_temperature    98(2)
_cell_measurement_theta_max      29.3230
_cell_measurement_theta_min      3.0560
_cell_volume                     1778.63(6)
_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    -40.00  82.00   1.00    5.00    --   -7.70  72.00  60.00  122
  2  \w    -97.00  17.00   1.00    5.00    --   -7.70 -38.00-120.00  114
  3  \w    -97.00  22.00   1.00    5.00    --   -7.70 -57.00-150.00  119
  4  \w    -32.00  69.00   1.00    5.00    --   -7.70  38.00-150.00  101
  5  \w    -37.00  82.00   1.00    5.00    --   -7.70  57.00 -60.00  119
;
_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      -0.0581483000
_diffrn_orient_matrix_UB_12      -0.0352997000
_diffrn_orient_matrix_UB_13      -0.0054048000
_diffrn_orient_matrix_UB_21      -0.0671569000
_diffrn_orient_matrix_UB_22      0.0306320000
_diffrn_orient_matrix_UB_23      -0.0033015000
_diffrn_orient_matrix_UB_31      0.0023129000
_diffrn_orient_matrix_UB_32      0.0018884000
_diffrn_orient_matrix_UB_33      -0.0480895000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0307
_diffrn_reflns_av_unetI/netI     0.0158
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            28542
_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         25.500
_diffrn_reflns_theta_min         2.552
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.151
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97234
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.181
_exptl_crystal_description       plate
_exptl_crystal_F_000             672
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.383
_refine_diff_density_min         -0.295
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         3303
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0406
_refine_ls_R_factor_gt           0.0403
_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^)+(0.0400P)^2^+1.9000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0957
_refine_ls_wR_factor_ref         0.0960
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3291
_reflns_number_total             3303
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b03366_si_002.cif
_cod_data_source_block           cd1732
_cod_database_code               4514898
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         PC15H17
_chemical_oxdiff_usercomment     R-P-(Ph)2
_shelx_estimated_absorpt_t_max   0.975
_shelx_estimated_absorpt_t_min   0.942
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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 B(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C2(H2A,H2B)
2.b Aromatic/amide H refined with riding coordinates:
 C17(H17), C11(H11), C15(H15), C9(H9), C18(H18), C21(H21), C5(H5), C13(H13),
 C19(H19), C14(H14), C20(H20), C12(H12), C8(H8), C7(H7), C6(H6)
2.c Idealised Me refined as rotating group:
 B1(H1A,H1B,H1C)
;
_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 1.068
_oxdiff_exptl_absorpt_empirical_full_min 0.957