Extension of Simmons‒Smith Reaction to Metal-Carbynes: Efficient Synthesis of Metallacyclopropenes with σ-Aromaticity
Huang, Fanping; Zheng, Xuejuan; Lin, Xinlei; Ding, Lin-Ting; Zhuo, Qingde; Wen, Ting-Bin; Zhang, Hong; Xia, Haiping; Chemical Science  (2020) –; doi:10.1039/D0SC03215H

data_1558979
_publ_section_title
;
 Extension of Simmons--Smith Reaction to Metal-Carbynes: Efficient
 Synthesis of Metallacyclopropenes with \s-Aromaticity
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC03215H
_journal_year                    2020
_chemical_formula_moiety         'C67 H59 I O2 Os P3, I'
_chemical_formula_sum            'C67 H59 I2 O2 Os P3'
_chemical_formula_weight         1433.05
_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     iterative
_audit_creation_date             2020-08-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-08-28 deposited with the CCDC.	2020-09-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.2220(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.5224(2)
_cell_length_b                   12.6665(2)
_cell_length_c                   29.5255(4)
_cell_measurement_reflns_used    28570
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      67.6030
_cell_measurement_theta_min      3.0530
_cell_volume                     6770.09(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    104.00 166.00   0.50    0.20    --   93.75 100.00-158.00  124
  2  \w     61.00 110.00   0.50    0.20    --   93.75-100.00  96.00   98
  3  \w     20.00  55.00   0.50    0.11    --   43.22-100.00  96.00   70
  4  \w     67.00  97.00   0.50    0.20    --   93.75  30.00 150.00   60
  5  \w    117.00 174.00   0.50    0.20    --   93.75  30.00 150.00  114
  6  \w     12.00  37.00   0.50    0.11    --  -43.22  19.00-120.00   50
  7  \w    -31.00  36.00   0.50    0.11    --  -43.22  38.00 -60.00  134
  8  \w    -69.00 -31.00   0.50    0.20    --  -90.25  61.00 -30.00   76
  9  \w    -40.00 -15.00   0.50    0.20    --  -90.25  61.00-150.00   50
 10  \w    -67.00 -26.00   0.50    0.20    --  -90.25  61.00  30.00   82
 11  \w    -51.00 -13.00   0.50    0.20    --  -90.25  45.00 150.00   76
 12  \w    -61.00 -20.00   0.50    0.20    --  -90.25  61.00  60.00   82
 13  \w    -43.00 -17.00   0.50    0.20    --  -90.25  45.00  30.00   52
 14  \w    -39.00 -13.00   0.50    0.20    --  -90.25  45.00-120.00   52
 15  \w    -50.00 -14.00   0.50    0.20    --  -90.25  45.00-150.00   72
 16  \w    -49.00 -23.00   0.50    0.20    --  -90.25 100.00-158.00   52
 17  \w    -72.00 -46.00   0.50    0.11    --  -43.22 100.00-158.00   52
 18  \w    -21.00  25.00   0.50    0.11    --  -43.22 100.00-158.00   92
 19  \w   -114.00 -72.00   0.50    0.11    --  -43.22-125.00-120.00   84
 20  \w   -117.00 -71.00   0.50    0.11    --  -43.22-125.00 -90.00   92
 21  \w   -125.00-100.00   0.50    0.20    --  -90.25-100.00  96.00   50
 22  \w   -111.00 -86.00   0.50    0.11    --  -43.22-125.00 150.00   50
 23  \w   -150.00-112.00   0.50    0.20    --  -90.25 -61.00 120.00   76
 24  \w    -95.00 -66.00   0.50    0.20    --  -90.25 -61.00 120.00   58
 25  \w     32.00  57.00   0.50    0.20    --   93.75 -61.00  90.00   50
 26  \w     24.00  50.00   0.50    0.20    --   93.75 -45.00  30.00   52
 27  \w     22.00  48.00   0.50    0.20    --   93.75 -45.00 -30.00   52
 28  \w     24.00  50.00   0.50    0.20    --   93.75 -45.00 -90.00   52
 29  \w     34.00  71.00   0.50    0.20    --   93.75 -61.00-120.00   74
 30  \w     17.00  49.00   0.50    0.20    --   93.75 -45.00-180.00   64
 31  \w     20.00  50.00   0.50    0.20    --   93.75 -45.00-150.00   60
 32  \w     17.00  42.00   0.50    0.20    --   93.75 -45.00-120.00   50
 33  \w     18.00  51.00   0.50    0.20    --   93.75 -45.00 -60.00   66
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0333075000
_diffrn_orient_matrix_UB_12      0.0074495000
_diffrn_orient_matrix_UB_13      -0.0435141000
_diffrn_orient_matrix_UB_21      0.0705246000
_diffrn_orient_matrix_UB_22      -0.0556002000
_diffrn_orient_matrix_UB_23      0.0261577000
_diffrn_orient_matrix_UB_31      -0.0340509000
_diffrn_orient_matrix_UB_32      -0.1078806000
_diffrn_orient_matrix_UB_33      -0.0165142000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0375
_diffrn_reflns_av_unetI/netI     0.0308
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            46265
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        64.998
_diffrn_reflns_theta_max         64.998
_diffrn_reflns_theta_min         2.592
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.681
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.07275
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.80a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.406
_exptl_crystal_description       block
_exptl_crystal_F_000             2816
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.286
_refine_diff_density_min         -1.589
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     667
_refine_ls_number_reflns         11456
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0328
_refine_ls_R_factor_gt           0.0316
_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^)+(0.0341P)^2^+29.0993P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0774
_refine_ls_wR_factor_ref         0.0781
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11055
_reflns_number_total             11456
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc03215h2.cif
_cod_data_source_block           hfp-200702-2_sq
_cod_database_code               1558979
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C94 O94 P94 Os94 Cl1 I1 '
_shelx_estimated_absorpt_t_max   0.203
_shelx_estimated_absorpt_t_min   0.105
_diffrn_oxdiff_digest_frames
;
016a0d1304551607e6e1600bc35d56333f02318e272
;
_diffrn_oxdiff_digest_hkl
;
010f3257b85f1ee9454f53223366cb256e64d5
;
_reflns_odcompleteness_completeness 99.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     62.30
_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.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C5(H5), C15(H15), C16(H16), C17(H17), C18(H18), C19(H19),
 C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), 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), C51(H51), C52(H52), C53(H53), C54(H54), C55(H55),
 C57(H57), C58(H58), C59(H59), C60(H60), C61(H61), C64(H64), C65(H65), C66(H66),
  C67(H67), C63(H63)
2.c Fitted hexagon refined as free rotating group:
 C64(C65,C66,C67,C62,C63)
2.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C)
;
_shelx_res_checksum              6652
_shelx_fab_checksum              78174
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 7.972
_oxdiff_exptl_absorpt_empirical_full_min 0.735