Reaction of an Enantiomerically Pure Phosphaalkene-Oxazoline with MeM Nucleophiles (M = Li and MgBr): Stereoselectivity and Noninnocence of the P-Mesityl Substituent
Serin, Spencer C.; Patrick, Brian O.; Dake, Gregory R.; Gates, Derek P.; Organometallics  (2014) 141201152116001–; doi:10.1021/om501008m

data_4085005
_publ_section_title
;
 Reaction of an Enantiomerically Pure Phosphaalkene-Oxazoline with MeM
 Nucleophiles (M = Li and MgBr): Stereoselectivity and Noninnocence of the
 P-Mesityl Substituent
;
_journal_name_full               Organometallics
_journal_page_first              141201152116001
_journal_paper_doi               10.1021/om501008m
_journal_year                    2014
_chemical_absolute_configuration syn
_chemical_formula_moiety
'C26 H36 Cl1.8 N O P Pd0.9, C H2 Cl2, 0.1(Cl2 Pd)'
_chemical_formula_sum            'C27 H38 Cl4 N O P Pd'
_chemical_formula_weight         671.75
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_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
_audit_creation_date             2014-10-01
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.368(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.9103(19)
_cell_length_b                   12.603(3)
_cell_length_c                   12.636(3)
_cell_measurement_reflns_used    9945
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      28.314
_cell_measurement_theta_min      2.653
_cell_volume                     1541.6(6)
_computing_cell_refinement       'SAINT v8.27A (Bruker, 2012)'
_computing_data_reduction        'SAINT v8.27A (Bruker, 2012)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      90(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker-Nonius APEXII CCD area detector'
_diffrn_measured_fraction_theta_full 0.927
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device
'Bruker-Nonius APEXII CCD area detector and D8 diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0376
_diffrn_reflns_av_unetI/netI     0.0455
_diffrn_reflns_Laue_measured_fraction_full 0.927
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            13914
_diffrn_reflns_point_group_measured_fraction_full 0.913
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         25.416
_diffrn_reflns_theta_min         2.653
_diffrn_source                   'sealed X-ray tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.021
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.5937
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0769 before and 0.0605 after correction.
The Ratio of minimum to maximum transmission is 0.7962.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.447
_exptl_crystal_description       cut
_exptl_crystal_F_000             688
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.13
_refine_diff_density_max         1.779
_refine_diff_density_min         -1.492
_refine_diff_density_rms         0.170
_refine_ls_abs_structure_details
;
 Flack x determined using 2239 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.180
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     346
_refine_ls_number_reflns         5533
_refine_ls_number_restraints     290
_refine_ls_restrained_S_all      1.160
_refine_ls_R_factor_all          0.0748
_refine_ls_R_factor_gt           0.0632
_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^)+(0.0414P)^2^+13.8157P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1473
_refine_ls_wR_factor_ref         0.1624
_reflns_Friedel_coverage         0.879
_reflns_Friedel_fraction_full    0.897
_reflns_Friedel_fraction_max     0.960
_reflns_number_gt                5085
_reflns_number_total             5533
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om501008m_si_001.cif
_cod_data_source_block           dg242
_cod_depositor_comments
;
The following automatic conversions were performed:

'_diffrn_radiation_probe' value 'X-ray' changed to 'x-ray' according
to
/home/saulius/struct/COD-crude-data--automatic-downloads/rss-feeds/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 2935 2014-11-11 08:27:57Z andrius 
;
_cod_original_cell_volume        1541.7(6)
_cod_database_code               4085005
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.879
_shelx_estimated_absorpt_t_min   0.792
_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 C(H,H,H) groups
2. Restrained distances
 Cl1A-Pd1A
 2.35 with sigma of 0.02
 Pd1A-Cl2A
 2.35 with sigma of 0.02
 Pd1B-Cl2B
 2.35 with sigma of 0.02
 Pd1B-Cl1B
 2.35 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uiso(Cl1A) = Uiso(Cl2A)
Uiso(Cl1B) = Uiso(Cl2B)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: Pd1(0.9) Cl1(0.9) Cl2(0.9) Pd1A(0.05) Pd1B(0.05) Cl2A(0.05)
 Cl2B(0.05) Cl1B(0.05) Cl1A(0.05)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C13(H13), C15(H15)
6.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C27(H27A,H27B)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C20(H20), C8(H8), C22(H22), C7(H7), C5(H5), C6(H6)
6.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C2(H2A,H2B,H2C), C17(H17A,H17B,H17C), C10(H10A,H10B,
 H10C), C26(H26A,H26B,H26C), C11(H11A,H11B,H11C), C16(H16A,H16B,H16C), C25(H25A,
 H25B,H25C)
;
_olex2_submission_special_instructions 'No special instructions were received'