Rapid Markovnikov addition of HCl to a pendant alkyne: evidence for a quinoidal cumulene
Samantha G. Eaves; Sam J. Hart; Adrian C. Whitwood; Dmitry S. Yufit; Paul J. Low; Jason M. Lynam; Chem.Commun. 51 (2015) 9362–; doi:10.1039/C4cc09696G

data_7117208
_publ_section_title
;
 Rapid Markovnikov addition of HCl to a pendant alkyne: evidence for a
 quinoidal cumulene
;
_journal_name_full               Chem.Commun.
_journal_page_first              9362
_journal_paper_doi               10.1039/C4cc09696G
_journal_volume                  51
_journal_year                    2015
_chemical_formula_moiety         'C62 H54 Cl2 P4 Ru, 1.5(C H2 Cl2)'
_chemical_formula_sum            'C63.5 H57 Cl5 P4 Ru'
_chemical_formula_weight         1222.29
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-10-14
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_audit_update_record
;
2014-10-14 deposited with the CCDC.
2014-12-22 downloaded from the CCDC.
;
_cell_angle_alpha                80.7264(18)
_cell_angle_beta                 74.684(2)
_cell_angle_gamma                83.7147(19)
_cell_formula_units_Z            2
_cell_length_a                   11.3506(3)
_cell_length_b                   12.3819(3)
_cell_length_c                   21.4222(5)
_cell_measurement_reflns_used    27948
_cell_measurement_temperature    110.05(10)
_cell_measurement_theta_max      31.9540
_cell_measurement_theta_min      3.0900
_cell_volume                     2858.75(13)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      110.05(10)
_diffrn_detector_area_resol_mean 16.1450
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.913
_diffrn_measurement_details
;
  1 omega    5.00   74.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       26.5735   77.0000  -30.0000 69

  2 omega    1.00   89.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       26.5735   77.0000 -120.0000 88

  3 omega  -13.00   66.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       26.5735  -99.0000   60.0000 79

  4 omega   -7.00   94.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       26.5735   19.0000 -120.0000 101

  5 omega  -43.00   57.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       26.5735  -77.0000  120.0000 100

  6 omega   -3.00   97.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       26.5735   77.0000   90.0000 100

  7 omega  -44.00   45.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       26.5735  -77.0000 -180.0000 89

  8 omega  -46.00   52.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       26.5735  -37.0000 -150.0000 98
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0231413000
_diffrn_orient_matrix_UB_12      0.0243368000
_diffrn_orient_matrix_UB_13      -0.0327203000
_diffrn_orient_matrix_UB_21      -0.0450705000
_diffrn_orient_matrix_UB_22      0.0443362000
_diffrn_orient_matrix_UB_23      0.0050178000
_diffrn_orient_matrix_UB_31      0.0406436000
_diffrn_orient_matrix_UB_32      0.0287719000
_diffrn_orient_matrix_UB_33      0.0102759000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0257
_diffrn_reflns_av_unetI/netI     0.0316
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.913
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            52246
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.913
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         32.215
_diffrn_reflns_theta_min         2.859
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.660
_exptl_absorpt_correction_T_max  0.972
_exptl_absorpt_correction_T_min  0.948
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
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)
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.420
_exptl_crystal_description       block
_exptl_crystal_F_000             1254
_exptl_crystal_size_max          0.2714
_exptl_crystal_size_mid          0.205
_exptl_crystal_size_min          0.1432
_refine_diff_density_max         1.261
_refine_diff_density_min         -1.207
_refine_diff_density_rms         0.087
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     678
_refine_ls_number_reflns         18443
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0479
_refine_ls_R_factor_gt           0.0384
_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^)+(0.0381P)^2^+3.6917P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0944
_refine_ls_wR_factor_ref         0.1011
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                15696
_reflns_number_total             18443
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4cc09696g2.cif
_cod_data_source_block           '[6b]_jml1380'
_cod_original_cell_volume        2858.75(12)
_cod_original_formula_sum        'C63.50 H57 Cl5 P4 Ru'
_cod_database_code               7117208
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C62 H54 Cl2 P4 Ru1'
_chemical_oxdiff_usercomment     'Samantha's sge1-12'
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.01
_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. Uiso/Uaniso restraints and constraints
Uanis(Cl6) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
3. Others
 Fixed Sof: Cl6(0.5) Cl5(0.5) C64(0.5) H64A(0.5) H64B(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C50(H50A,H50B), C63(H63A,H63B), C64(H64A,H64B)
4.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C10(H10), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C20(H20),
 C21(H21), C22(H22), C23(H23), C24(H24), C27(H27), C28(H28), C29(H29), C30(H30),
  C31(H31), C33(H33), C34(H34), C35(H35), C36(H36), C37(H37), C39(H39),
 C40(H40), C41(H41), C42(H42), C43(H43), C45(H45), C46(H46), C47(H47), C48(H48),
  C49(H49), C52(H52), C53(H53), C54(H54), C55(H55), C56(H56), C58(H58),
 C59(H59), C60(H60), C61(H61), C62(H62)
4.c X=CH2 refined with riding coordinates:
 C8(H8A,H8B)
4.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C)
;
_olex2_exptl_crystal_mounting_method 'oil on loop'
_olex2_submission_special_instructions 'No special instructions were received'