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_7117207
_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         'C60 H50 Cl2 P4 Ru, 2(C H2 Cl2)'
_chemical_formula_sum            'C62 H54 Cl6 P4 Ru'
_chemical_formula_weight         1236.70
_chemical_name_systematic
;
 ? 
;
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-03-19
_audit_creation_method
;
  Olex2 1.2-beta
  (compiled Mar 13 2013 19:31:35, GUI svn.r4414)
;
_audit_update_record
;
2014-10-14 deposited with the CCDC.
2014-12-22 downloaded from the CCDC.
;
_cell_angle_alpha                67.588(5)
_cell_angle_beta                 85.054(5)
_cell_angle_gamma                78.028(5)
_cell_formula_units_Z            2
_cell_length_a                   12.3129(7)
_cell_length_b                   14.9215(8)
_cell_length_c                   18.0053(11)
_cell_measurement_reflns_used    2586
_cell_measurement_temperature    120
_cell_measurement_theta_max      20.7020
_cell_measurement_theta_min      2.9550
_cell_volume                     2991.6(3)
_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
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
XL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      120
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 16.1511
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.9992
_diffrn_measured_fraction_theta_max 0.9017
_diffrn_measurement_details
;
  1 omega  -85.00  -34.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -26.1867 -179.0000 -150.0000 51

  2 omega  -95.00  -66.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -26.1867  -57.0000  120.0000 29

  3 omega  -95.00  -11.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -26.1867  -57.0000  150.0000 84

  4 omega  -47.00   43.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -26.1867   57.0000  -90.0000 90

  5 omega   62.00  102.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       26.9679  179.0000 -150.0000 40

  6 omega   14.00   39.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       26.9679 -118.0000 -138.0000 25

  7 omega   32.00   80.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       26.9679 -118.0000   52.0000 48

  8 omega   50.00   77.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       26.9679 -118.0000 -138.0000 27

  9 omega   15.00   69.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       26.9679 -100.0000  -90.0000 54

 10 omega   -6.00   96.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       26.9679   19.0000   90.0000 102

 11 omega  -48.00   43.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -26.1867   57.0000   60.0000 91

 12 omega  -96.00  -71.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -26.1867  -77.0000   30.0000 25

 13 omega  -95.00   -5.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -26.1867  -57.0000  -90.0000 90
;
_diffrn_measurement_device       '3-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Gemini ultra'
_diffrn_measurement_method       \w-scan
_diffrn_orient_matrix_UB_11      -0.0300902000
_diffrn_orient_matrix_UB_12      0.0476244000
_diffrn_orient_matrix_UB_13      -0.0041144000
_diffrn_orient_matrix_UB_21      0.0106995000
_diffrn_orient_matrix_UB_22      0.0171366000
_diffrn_orient_matrix_UB_23      -0.0419635000
_diffrn_orient_matrix_UB_31      -0.0494773000
_diffrn_orient_matrix_UB_32      -0.0134439000
_diffrn_orient_matrix_UB_33      -0.0061727000
_diffrn_radiation_collimation    monochromator
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_radiation_xray_symbol    Mo
_diffrn_reflns_av_R_equivalents  0.1584
_diffrn_reflns_av_unetI/netI     0.1937
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            37868
_diffrn_reflns_theta_full        26.00
_diffrn_reflns_theta_max         26.00
_diffrn_reflns_theta_min         2.66
_diffrn_source                   'Enhance (Mo) X-ray Source'
_diffrn_source_type              'sealed tube'
_exptl_absorpt_coefficient_mu    0.675
_exptl_absorpt_correction_T_max  0.965
_exptl_absorpt_correction_T_min  0.906
_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            'dull brownish yellow'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.373
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1264
_exptl_crystal_size_max          0.1711
_exptl_crystal_size_mid          0.1442
_exptl_crystal_size_min          0.0487
_refine_diff_density_max         1.856
_refine_diff_density_min         -0.784
_refine_diff_density_rms         0.159
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     579
_refine_ls_number_reflns         11752
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.1876
_refine_ls_R_factor_gt           0.0999
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1300P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2459
_refine_ls_wR_factor_ref         0.3129
_reflns_number_gt                5633
_reflns_number_total             11752
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c4cc09696g2.cif
_cod_data_source_block           '[6a]_13srv100'
_cod_database_code               7117207
_chemical_oxdiff_formula         'C63 H52 Cl8 P4 Ru1'
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.05
3. Others
 Fixed Sof: Cl5A(0.25) Cl6A(0.25) C2SA(0.25) H2SC(0.25) H2SD(0.25) Cl5B(0.25)
 Cl6B(0.25) C2SB(0.25) H2SA(0.25) H2SB(0.25) Cl7A(0.25) Cl7B(0.25) Cl8A(0.25)
 Cl8B(0.25) C3S(0.5) H3SA(0.5) H3SB(0.5)
4.a Riding coordinates:
 C3S(H3SA,H3SB)
4.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C1S(H1SA,H1SB), C2SA(H2SC,H2SD), C2SB(H2SA,
 H2SB)
4.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C7(H7), C8(H8), C22(H22), C23(H23), C24(H24), C25(H25),
 C26(H26), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C42(H42), C43(H43),
  C44(H44), C45(H45), C46(H46), C52(H52), C53(H53), C54(H54), C55(H55),
 C56(H56), C62(H62), C63(H63), C64(H64), C65(H65), C66(H66), C72(H72), C73(H73),
  C74(H74), C75(H75), C76(H76), C82(H82), C83(H83), C84(H84), C85(H85),
 C86(H86), C92(H92), C93(H93), C94(H94), C95(H95), C96(H96)
4.d Fitted hexagon refined as free rotating group:
 C21(C22,C23,C24,C25,C26), C31(C32,C33,C34,C35,C36), C41(C42,C43,C44,C45,C46),
 C51(C52,C53,C54,C55,C56), C61(C62,C63,C64,C65,C66), C71(C72,C73,C74,C75,C76),
 C81(C82,C83,C84,C85,C86), C91(C92,C93,C94,C95,C96)
4.e X=CH2 refined with riding coordinates:
 C10(H10A,H10B)
;