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_4088519
_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         '2(C H2 Cl2), C66 H45 O P'
_chemical_formula_sum            'C68 H49 Cl4 O P'
_chemical_formula_weight         1054.84
_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
_atom_sites_solution_primary     direct
_audit_creation_date             2015-07-17
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3151 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.508(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.1207(11)
_cell_length_b                   21.9524(17)
_cell_length_c                   18.5508(15)
_cell_measurement_reflns_used    10764
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      28.6321
_cell_measurement_theta_min      2.9938
_cell_volume                     5326.7(7)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.0
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3968
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.882
_diffrn_measurement_details
;
  1 omega   -5.00   24.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.1850   38.0000  -90.0000 29

  2 omega  -48.00   26.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.1850   98.0000  145.0000 74

  3 omega  -66.00  -10.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -        9.9038  -38.0000  120.0000 56

  4 omega   48.00   75.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -        9.9038   77.0000  -30.0000 27

  5 omega   12.00   39.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -        9.9038   77.0000   60.0000 27

  6 omega   64.00   89.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -        9.9038   77.0000   60.0000 25

  7 omega  -17.00   89.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -        9.9038   77.0000   30.0000 106

  8 omega  -22.00   26.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -        9.9038   77.0000  -30.0000 48

  9 omega  -11.00   26.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -        9.9038   98.0000  141.0000 37
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0230759000
_diffrn_orient_matrix_UB_12      -0.0001795000
_diffrn_orient_matrix_UB_13      -0.0359140000
_diffrn_orient_matrix_UB_21      -0.0163818000
_diffrn_orient_matrix_UB_22      0.0304344000
_diffrn_orient_matrix_UB_23      0.0043478000
_diffrn_orient_matrix_UB_31      0.0463527000
_diffrn_orient_matrix_UB_32      0.0106524000
_diffrn_orient_matrix_UB_33      -0.0128035000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0466
_diffrn_reflns_av_unetI/netI     0.0374
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.882
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            57411
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.882
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.632
_diffrn_reflns_theta_min         2.994
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.298
_exptl_absorpt_correction_T_max  0.939
_exptl_absorpt_correction_T_min  0.868
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
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    1.315
_exptl_crystal_description
;
;
_exptl_crystal_F_000             2192
_exptl_crystal_size_max          0.7011
_exptl_crystal_size_mid          0.3149
_exptl_crystal_size_min          0.2659
_refine_diff_density_max         0.607
_refine_diff_density_min         -0.633
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     687
_refine_ls_number_reflns         12068
_refine_ls_number_restraints     674
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0712
_refine_ls_R_factor_gt           0.0503
_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^)+(0.0538P)^2^+3.9200P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1169
_refine_ls_wR_factor_ref         0.1331
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9283
_reflns_number_total             12068
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00146_si_002.cif
_cod_data_source_block           sd306
_cod_original_cell_volume        5326.7(8)
_cod_database_code               4088519
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C68 H49 P1 Cl4 O1'
_reflns_odcompleteness_completeness 98.39
_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
2. Restrained distances
 Cl3T-C2T \\sim Cl3S-C2S \\sim Cl4S-C2S \\sim Cl4T-C2T
 with sigma of 0.02
 Cl3S-Cl4S \\sim Cl4T-Cl3T
 with sigma of 0.02
 Cl2S-C1S \\sim Cl2T-C1T \\sim Cl1T-C1T \\sim Cl1S-C1S
 with sigma of 0.02
 Cl1T-Cl2T \\sim Cl2S-Cl1S
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Cl3T) = Uanis(Cl3S)
Uanis(C2T) = Uanis(C2S)
Uanis(Cl4T) = Uanis(Cl4S)
Uanis(Cl1T) = Uanis(Cl1S)
Uanis(C1T) = Uanis(C1S)
Uanis(Cl2T) = Uanis(Cl2S)
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
 Sof(Cl3S)=Sof(Cl4S)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=1-FVAR(1)
 Sof(Cl3T)=Sof(Cl4T)=Sof(C2T)=Sof(H2TA)=Sof(H2TB)=FVAR(1)
 Sof(Cl1S)=Sof(Cl2S)=Sof(C1S)=Sof(H1SA)=Sof(H1SB)=1-FVAR(2)
 Sof(Cl1T)=Sof(Cl2T)=Sof(C1T)=Sof(H1TA)=Sof(H1TB)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C2(H2), C9(H9), C24(H24), C31(H31), C46(H46), C53(H53)
6.b Secondary CH2 refined with riding coordinates:
 C1S(H1SA,H1SB), C1T(H1TA,H1TB), C2S(H2SA,H2SB), C2T(H2TA,H2TB)
6.c 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), C48(H48), C49(H49), C50(H50), C51(H51), C55(H55),
  C56(H56), C57(H57), C58(H58), C62(H62), C63(H63), C64(H64), C65(H65), C66(H66)
;
_shelx_res_checksum              43993
_shelx_hkl_checksum              99042
_olex2_submission_special_instructions 'No special instructions were received'