Isolation of N-Heterocyclic Alkyl Intermediates en Route to Transition Metal N-Heterocyclic Carbene Complexes: Insight into a C‒H Activation Mechanism
Pan, Baofei; Pierre, Sadrach; Bezpalko, Mark W.; Napoline, J. Wesley; Foxman, Bruce M.; Thomas, Christine M.; Organometallics 32 (2013) 704–; doi:10.1021/om301230f

data_4080048
_publ_section_title
;
 Isolation of N-Heterocyclic Alkyl Intermediates en Route to Transition
 Metal N-Heterocyclic Carbene Complexes: Insight into a C--H Activation
 Mechanism
;
_journal_issue                   2
_journal_name_full               Organometallics
_journal_page_first              704
_journal_paper_doi               10.1021/om301230f
_journal_volume                  32
_journal_year                    2013
_chemical_formula_moiety         'C39 H33 F6 N2 P3 Pt1'
_chemical_formula_sum            'C39 H33 F6 N2 P3 Pt'
_chemical_formula_weight         931.70
_space_group_IT_number           15
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     other
_audit_creation_date             2012-06-25
_audit_creation_method           CRYSTALS_ver_14.43
_cell_angle_alpha                90
_cell_angle_beta                 101.3590(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.074(2)
_cell_length_b                   33.689(4)
_cell_length_c                   13.5753(16)
_cell_measurement_reflns_used    2942
_cell_measurement_temperature    120
_cell_measurement_theta_max      25
_cell_measurement_theta_min      8
_cell_volume                     7655.6(16)
_computing_cell_refinement       'Apex2 (Bruker AXS, 2006)'
_computing_data_collection       'Apex2 (Bruker AXS, 2006)'
_computing_data_reduction        'Apex2 (Bruker AXS, 2006)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'Superflip (Palatinus & Chapuis, 2007)'
_diffrn_ambient_temperature      120
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Bruker Kappa Apex2'
_diffrn_measurement_method       '\f & \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.067
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       47
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            11148
_diffrn_reflns_theta_full        29.986
_diffrn_reflns_theta_max         29.986
_diffrn_reflns_theta_min         1.358
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.850
_exptl_absorpt_correction_T_max  0.71
_exptl_absorpt_correction_T_min  0.65
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
; 
 Analytical Absorption (De Meulenaer & Tompa, 1965) 
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.617
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             3664
_exptl_crystal_size_max          0.330
_exptl_crystal_size_mid          0.110
_exptl_crystal_size_min          0.090
_platon_squeeze_details
;
During the structure solution, electron density difference 
maps revealed that there were considerable disordered solvent 
molecules which could not be successfully modeled.  From 
history, the remaining solvate was likely diethyl ether 
in a volume of 956.9 \%A3 per unit cell (12.5%).  It appeared 
that the cavity area contained about four ether molecules, 
located near the twofold axes at (1/2, 0, 1/4), 
(0, 1/2, 1/4), ( 1/2, 0, 3/4 ) and ( 0, 1/2, 3/4). Modeling with 
or without restraints 
was unsuccessful, as was step by step acquisition of peaks 
using successive electron density difference maps.  
Thus, the structure factors were modified using the 
PLATON SQUEEZE technique, in order to produce a "solvate-free" 
structure factor set.  PLATON reported a total electron 
density of 200 e- per unit cell, likely representing 
four ether molecules, consistent with our earlier observations.  
Use of the SQUEEZE technique resulted in a decrease of 
ca. 1.3 % in R.   
;
_refine_diff_density_max         2.46
_refine_diff_density_min         -1.87
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   1.0017
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     481
_refine_ls_number_reflns         11148
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0416
_refine_ls_R_factor_gt           0.0276
_refine_ls_shift/su_max          0.0046660
_refine_ls_shift/su_mean         0.0000658
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.02P)^2^ +25.27P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0579
_refine_ls_wR_factor_gt          0.0545
_refine_ls_wR_factor_ref         0.0579
_reflns_limit_h_max              23
_reflns_limit_h_min              -24
_reflns_limit_k_max              47
_reflns_limit_k_min              0
_reflns_limit_l_max              19
_reflns_limit_l_min              0
_reflns_number_gt                8680
_reflns_number_total             11148
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   1.47
_oxford_diffrn_Wilson_scale      1115.65
_oxford_refine_ls_r_factor_ref   0.0416
_oxford_refine_ls_scale          0.0308773(10)
_oxford_reflns_number_all        11148
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title 'bfpan_816_0m in C2/c'
_cod_data_source_file            om301230f_si_002.cif
_cod_data_source_block           5[PF6]
_cod_depositor_comments
;
The following automatic conversions were performed:

'_atom_sites_solution_primary' value 'Other' changed to 'other'
according to /home/saulius/struct/CIF-dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 1891 2012-01-12 08:04:46Z andrius 
;
_cod_original_sg_symbol_Hall     '-C 2yc '
_cod_original_sg_symbol_H-M      'C 1 2/c 1 '
_cod_original_formula_sum        'C39 H33 F6 N2 P3 Pt1'
_cod_database_code               4080048
_iucr_refine_instructions_details_constraints
;
BLOCK 
CONT SCALE 
CONT H(1, X'S,U[ISO]) 
CONT PT   (    1 ,X'S,U'S)  UNTIL F    (    1 ) 
CONT F    (    2 ,X'S,U[ISO]) 
CONT F    (    3 ,X'S,U'S) 
CONT F    (    4 ,X'S,U[ISO]) 
CONT F    (    5 ,X'S,U'S) 
CONT F    (    6 ,X'S,U[ISO]) 
CONT F    (    7 ,X'S,U'S) 
CONT F    (    8 ,X'S,U[ISO]) 
CONT F    (    9 ,X'S,U'S)  UNTIL C    (   39 ) 
SUMFIX PART(1001,OCC) AND PART(1002,OCC) 
RIDE C   (   2,X'S) H   (  21,X'S) 
RIDE C   (   3,X'S) H   (  31,X'S) 
RIDE C   (   4,X'S) H   (  41,X'S) 
RIDE C   (   5,X'S) H   (  51,X'S) 
RIDE C   (   6,X'S) H   (  61,X'S) 
RIDE C   (   8,X'S) H   (  81,X'S) 
RIDE C   (   9,X'S) H   (  91,X'S) 
RIDE C   (  10,X'S) H   ( 101,X'S) 
RIDE C   (  11,X'S) H   ( 111,X'S) 
RIDE C   (  12,X'S) H   ( 121,X'S) 
RIDE C   (  14,X'S) H   ( 141,X'S) 
RIDE C   (  15,X'S) H   ( 151,X'S) 
RIDE C   (  16,X'S) H   ( 161,X'S) 
RIDE C   (  17,X'S) H   ( 171,X'S) 
RIDE C   (  19,X'S) H   ( 191,X'S) H   ( 192,X'S) 
RIDE C   (  20,X'S) H   ( 201,X'S) H   ( 202,X'S) 
RIDE C   (  22,X'S) H   ( 221,X'S) 
RIDE C   (  23,X'S) H   ( 231,X'S) 
RIDE C   (  24,X'S) H   ( 241,X'S) 
RIDE C   (  25,X'S) H   ( 251,X'S) 
RIDE C   (  28,X'S) H   ( 281,X'S) 
RIDE C   (  29,X'S) H   ( 291,X'S) 
RIDE C   (  30,X'S) H   ( 301,X'S) 
RIDE C   (  31,X'S) H   ( 311,X'S) 
RIDE C   (  32,X'S) H   ( 321,X'S) 
RIDE C   (  34,X'S) H   ( 341,X'S) 
RIDE C   (  35,X'S) H   ( 351,X'S) 
RIDE C   (  36,X'S) H   ( 361,X'S) 
RIDE C   (  37,X'S) H   ( 371,X'S) 
RIDE C   (  38,X'S) H   ( 381,X'S) 
END                                                                             
;
_iucr_refine_instructions_details_restraints
;
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
END                                                                             
;