Probing the Mechanism of the PCl5-Initiated Living Cationic Polymerization of the Phosphoranimine Cl3P=NSiMe3 using Model Compound Chemistry
Vivienne Blackstone; Alan J. Lough; Martin Murray; Ian Manners; Journal of the American Chemical Society 131 (2009) 3658–3667; doi:10.1021/ja808517d

data_4104005
_publ_section_title
;
 Probing the Mechanism of the PCl5-Initiated Living Cationic
 Polymerization of the Phosphoranimine Cl3P=NSiMe3 using Model Compound
 Chemistry
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3658
_journal_page_last               3667
_journal_paper_doi               10.1021/ja808517d
_journal_volume                  131
_journal_year                    2009
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C36 H30 Cl4 N3 P4, Cl6 P, C H2 Cl2'
_chemical_formula_sum            'C37 H32 Cl12 N3 P5'
_chemical_formula_weight         1098.91
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 107.735(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   11.3728(4)
_cell_length_b                   17.6718(7)
_cell_length_c                   13.0181(3)
_cell_measurement_reflns_used    22025
_cell_measurement_temperature    150(1)
_cell_measurement_theta_max      27.5
_cell_measurement_theta_min      2.8
_cell_volume                     2492.01(15)
_computing_cell_refinement       'Denzo-SMN (Otwinowski & Minor, 1997)'
_computing_data_collection       'Collect (Nonius B.V., 1997-2002)'
_computing_data_reduction        Denzo-SMN
_computing_molecular_graphics    'SHELXTL V6.1'
_computing_publication_material  'SHELXTL V6.1'
_computing_structure_refinement  'SHELXTL V6.1(Sheldrick, 2001)'
_computing_structure_solution    'SIR-92 (Altomare et al., 1994)'
_diffrn_ambient_temperature      150(1)
_diffrn_detector_area_resol_mean 9
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_device_type  'Bruker-Nonius KappaCCD'
_diffrn_measurement_method       '\f scans and \w scans with \k offsets'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0611
_diffrn_reflns_av_sigmaI/netI    0.0833
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            22025
_diffrn_reflns_theta_full        27.51
_diffrn_reflns_theta_max         27.51
_diffrn_reflns_theta_min         2.83
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.858
_exptl_absorpt_correction_T_max  0.867
_exptl_absorpt_correction_T_min  0.731
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
multi-scan from symmetry-related measurements 
 Sortav (Blessing 1995)
;
_exptl_crystal_colour            white
_exptl_crystal_density_diffrn    1.465
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1108
_exptl_crystal_size_max          0.40
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.21
_refine_diff_density_max         1.902
_refine_diff_density_min         -0.752
_refine_diff_density_rms         0.128
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.05(11)
_refine_ls_extinction_coef       0.0065(15)
_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   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     536
_refine_ls_number_reflns         10176
_refine_ls_number_restraints     11
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.1052
_refine_ls_R_factor_gt           0.0723
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1331P)^2^+2.0613P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1921
_refine_ls_wR_factor_ref         0.2165
_reflns_number_gt                7430
_reflns_number_total             10176
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            ja808517d_si_002.cif
_cod_data_source_block           k06115
_cod_original_cell_volume        2492.01(14)
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4104005