Triaryl-Like MONO-, BIS-, and TRISKITPHOS Phosphines: Synthesis, Solution NMR Studies, and a Comparison in Gold-Catalyzed Carbon‒Heteroatom Bond Forming 5-exo-dig and 6-endo-dig Cyclizations
Doherty, Simon; Knight, Julian G.; Perry, Daniel O.; Ward, Nicholas A. B.; Bittner, Dror M.; McFarlane, William; Wills, Corinne; Probert, Michael R.; Organometallics 35 (2016) 1265–; doi:10.1021/acs.organomet.6b00146

data_4088518
_publ_section_title
;
 Triaryl-Like MONO-, BIS-, and TRISKITPHOS Phosphines: Synthesis, Solution
 NMR Studies, and a Comparison in Gold-Catalyzed Carbon--Heteroatom Bond
 Forming 5-exo-dig and 6-endo-dig Cyclizations
;
_journal_issue                   9
_journal_name_full               Organometallics
_journal_page_first              1265
_journal_paper_doi               10.1021/acs.organomet.6b00146
_journal_volume                  35
_journal_year                    2016
_chemical_formula_moiety         'C50 H35 Au Cl P, C H Cl3'
_chemical_formula_sum            'C51 H36 Au Cl4 P'
_chemical_formula_weight         1018.53
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-07-16
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3151 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 105.083(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.6875(3)
_cell_length_b                   18.8693(3)
_cell_length_c                   17.1115(4)
_cell_measurement_reflns_used    15172
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      28.5354
_cell_measurement_theta_min      3.0014
_cell_volume                     4267.20(16)
_computing_cell_refinement
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET)
(compiled Apr 28 2010,14:27:37)
;
_computing_data_collection
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET)
(compiled Apr 28 2010,14:27:37)
;
_computing_data_reduction
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET)
(compiled Apr 28 2010,14:27:37)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      150.0
_diffrn_detector_area_resol_mean 10.3968
_diffrn_measured_fraction_theta_full 0.982
_diffrn_measured_fraction_theta_max 0.842
_diffrn_measurement_details
;
  1 omega  -64.00   28.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -        9.8257  -38.0000 -150.0000 92

  2 omega  -19.00   28.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -        9.8257  -38.0000   60.0000 47

  3 omega   18.00   43.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -        9.8257   77.0000   90.0000 25

  4 omega  -11.00   71.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -        9.8257   38.0000   30.0000 82
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0501216000
_diffrn_orient_matrix_UB_12      0.0102103000
_diffrn_orient_matrix_UB_13      0.0201104000
_diffrn_orient_matrix_UB_21      -0.0064780000
_diffrn_orient_matrix_UB_22      0.0319436000
_diffrn_orient_matrix_UB_23      -0.0225850000
_diffrn_orient_matrix_UB_31      -0.0181005000
_diffrn_orient_matrix_UB_32      0.0169522000
_diffrn_orient_matrix_UB_33      0.0304971000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0302
_diffrn_reflns_av_unetI/netI     0.0349
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.842
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            26772
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.842
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.598
_diffrn_reflns_theta_min         3.090
_diffrn_source                   'Enhance (Mo) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.771
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69257
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET)
(compiled Apr 28 2010,14:27:37)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.585
_exptl_crystal_description       block
_exptl_crystal_F_000             2016
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.4
_refine_diff_density_max         1.361
_refine_diff_density_min         -1.318
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     527
_refine_ls_number_reflns         9187
_refine_ls_number_restraints     42
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0414
_refine_ls_R_factor_gt           0.0315
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0347P)^2^+10.4584P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0752
_refine_ls_wR_factor_ref         0.0812
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7829
_reflns_number_total             9187
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00146_si_002.cif
_cod_data_source_block           sd299
_cod_original_cell_volume        4267.16(15)
_cod_database_code               4088518
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C50 H35 Au Cl P'
_shelx_estimated_absorpt_t_max   0.314
_shelx_estimated_absorpt_t_min   0.300
_reflns_odcompleteness_completeness 99.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 Cl2P-C1P \\sim Cl1S-C1S \\sim Cl1P-C1P \\sim Cl2S-C1S \\sim Cl3S-C1S \\sim
Cl3P-C1P
 with sigma of 0.02
 Cl1P-Cl2P \\sim Cl1S-Cl2S \\sim Cl1P-Cl3P \\sim Cl1S-Cl3S \\sim Cl3S-Cl2S
\\sim Cl3P-Cl2P
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl1P \\sim Cl1S \\sim Cl2P \\sim Cl2S \\sim Cl3P \\sim Cl3S: within 1.7A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(Cl3S) = Uanis(Cl3P)
Uanis(C1S) = Uanis(C1P)
Uanis(Cl1S) = Uanis(Cl1P)
Uanis(Cl2S) = Uanis(Cl2P)
4. Others
 Sof(Cl1P)=Sof(Cl2P)=Sof(Cl3P)=Sof(C1P)=Sof(H1P)=1-FVAR(1)
 Sof(Cl1S)=Sof(Cl2S)=Sof(Cl3S)=Sof(C1S)=Sof(H1S)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C1P(H1P), C1S(H1S), C2(H2), C9(H9), C24(H24), C31(H31)
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C11(H11), C12(H12), C13(H13), C14(H14),
 C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C26(H26), C27(H27), C28(H28),
  C29(H29), C33(H33), C34(H34), C35(H35), C36(H36), C40(H40), C41(H41),
 C42(H42), C43(H43), C44(H44), C46(H46), C47(H47), C48(H48), C49(H49), C50(H50)
;
_shelx_res_checksum              24138
_shelx_hkl_checksum              87
_olex2_submission_special_instructions 'No special instructions were received'