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_1558976
_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         'C65 H55 I O2 Os P3, I'
_chemical_formula_sum            'C65 H55 I2 O2 Os P3'
_chemical_formula_weight         1405.00
_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                 96.8380(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.57170(10)
_cell_length_b                   12.22040(10)
_cell_length_c                   38.2280(4)
_cell_measurement_reflns_used    48514
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.8710
_cell_measurement_theta_min      3.3110
_cell_volume                     6295.08(10)
_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 0.999
_diffrn_measured_fraction_theta_max 0.989
_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    -24.00   3.00   0.50    0.50    --  -43.10  19.00   0.00   54
  2  \w    -46.00 -17.00   0.50    1.60    --  -90.25  45.00  30.00   58
  3  \w    -23.00  37.00   0.50    0.50    --  -43.10  19.00 120.00  120
  4  \w     -1.00  25.00   0.50    0.50    --   43.10 -19.00 -60.00   52
  5  \w     35.00  64.00   0.50    1.60    --  109.34 -61.00  30.00   58
  6  \w     50.00  98.00   0.50    1.60    --  109.34 -77.00   0.00   96
  7  \w     88.00 116.00   0.50    1.60    --  109.34-125.00  60.00   56
  8  \w     59.00 126.00   0.50    1.60    --  109.34-137.00 158.67  134
  9  \w     55.00  97.00   0.50    0.50    --   43.10-125.00   0.00   84
 10  \w     35.00  69.00   0.50    1.60    --  109.34 -61.00  60.00   68
 11  \w     41.00  67.00   0.50    1.60    --  109.34 -61.00 120.00   52
 12  \w     94.00 178.00   0.50    1.60    --  109.34  15.00  60.00  168
 13  \w    111.00 175.00   0.50    1.60    --  109.34  61.00  90.00  128
 14  \w    142.00 169.00   0.50    1.60    --  109.34 125.00  60.00   54
 15  \w    116.00 177.00   0.50    1.60    --  109.34  45.00 150.00  122
 16  \w     95.00 170.00   0.50    1.60    --  109.34 125.00   0.00  150
 17  \w    150.00 178.00   0.50    1.60    --  109.34 125.00 -90.00   56
 18  \w    128.00 174.00   0.50    1.60    --  109.34 125.00-120.00   92
 19  \w    141.00 178.00   0.50    1.60    --  109.34  30.00-120.00   74
 20  \w     98.00 127.00   0.50    1.60    --  109.34 125.00 -90.00   58
 21  \w     83.00 126.00   0.50    1.60    --  109.34  30.00-120.00   86
 22  \w     39.00 105.00   0.50    1.60    --  109.34 -94.00 -30.00  132
 23  \w     73.00 110.00   0.50    1.60    --  109.34-125.00 -60.00   74
 24  \w     83.00 117.00   0.50    1.60    --  109.34-125.00-150.00   68
 25  \w     35.00 116.00   0.50    1.60    --  109.34-125.00-120.00  162
 26  \w     46.00  77.00   0.50    1.60    --  109.34 -94.00   0.00   62
 27  \w     37.00  63.00   0.50    1.60    --  109.34-125.00 -60.00   52
 28  \w     35.00 110.00   0.50    1.60    --  109.34-125.00 -30.00  150
 29  \w     45.00  72.00   0.50    1.60    --  109.34-125.00-150.00   54
 30  \w     37.00  62.00   0.50    1.60    --  109.34 -77.00 -90.00   50
 31  \w     52.00  91.00   0.50    1.60    --  109.34  15.00  60.00   78
 32  \w     85.00 112.00   0.50    1.60    --  109.34  45.00 150.00   54
 33  \w    105.00 132.00   0.50    1.60    --  109.34 125.00  60.00   54
 34  \w    -24.00  14.00   0.50    0.50    --  -43.10  19.00-150.00   76
 35  \w    -42.00 -13.00   0.50    1.60    --  -90.25  45.00-150.00   58
 36  \w    -43.00 -18.00   0.50    1.60    --  -90.25  45.00 -60.00   50
 37  \w    -74.00  14.00   0.50    0.50    --  -43.10  77.00-120.00  176
 38  \w    -70.00 -41.00   0.50    1.60    --  -90.25  61.00-150.00   58
 39  \w    -88.00 -10.00   0.50    0.50    --  -43.10 125.00 -60.00  156
 40  \w    -71.00 -16.00   0.50    1.60    --  -90.25  61.00  90.00  110
 41  \w   -111.00 -71.00   0.50    0.50    --  -43.10-125.00 -90.00   80
 42  \w    -99.00 -70.00   0.50    0.50    --  -43.10-125.00 120.00   58
 43  \w    -97.00 -72.00   0.50    0.50    --  -43.10-125.00  30.00   50
 44  \w   -126.00 -71.00   0.50    1.60    --  -90.25-125.00  90.00  110
 45  \w   -156.00-131.00   0.50    1.60    --  -90.25-125.00  90.00   50
 46  \w   -165.00 -85.00   0.50    1.60    --  -90.25 -61.00 -30.00  160
;
_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      0.0856658000
_diffrn_orient_matrix_UB_12      0.0547392000
_diffrn_orient_matrix_UB_13      0.0237834000
_diffrn_orient_matrix_UB_21      0.0335717000
_diffrn_orient_matrix_UB_22      0.0577055000
_diffrn_orient_matrix_UB_23      -0.0323916000
_diffrn_orient_matrix_UB_31      -0.0678026000
_diffrn_orient_matrix_UB_32      0.0978032000
_diffrn_orient_matrix_UB_33      0.0058144000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0339
_diffrn_reflns_av_unetI/netI     0.0199
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            71539
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.154
_diffrn_reflns_theta_min         3.347
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.551
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71639
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.482
_exptl_crystal_description       block
_exptl_crystal_F_000             2752
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.900
_refine_diff_density_min         -2.980
_refine_diff_density_rms         0.123
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     659
_refine_ls_number_reflns         12830
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0350
_refine_ls_R_factor_gt           0.0347
_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^)+(0.0361P)^2^+32.8935P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0880
_refine_ls_wR_factor_ref         0.0883
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12676
_reflns_number_total             12830
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc03215h2.cif
_cod_data_source_block           hfp-2020-0810-2_sq
_cod_database_code               1558976
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Os C P Cl'
_shelx_estimated_absorpt_t_max   0.188
_shelx_estimated_absorpt_t_min   0.117
_diffrn_oxdiff_digest_frames
;
010cf23617b2e2b85d01806731109b34eb000381198
;
_diffrn_oxdiff_digest_hkl
;
01b8c06493e05f136e662cde6cdbea00f2c869
;
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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), C10(H10A,H10B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C5(H5), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17),
 C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C25(H25), C26(H26), C27(H27),
  C28(H28), C29(H29), C31(H31), C32(H32), C33(H33), C34(H34), C35(H35),
 C37(H37), C38(H38), C39(H39), C40(H40), C41(H41), C43(H43), C44(H44), C45(H45),
  C46(H46), C47(H47), C49(H49), C50(H50), C51(H51), C52(H52), C53(H53),
 C55(H55), C56(H56), C57(H57), C58(H58), C59(H59), C61(H61), C62(H62), C63(H63),
  C64(H64), C65(H65)
2.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C)
;
_shelx_res_checksum              27408
_shelx_fab_checksum              75762
_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 1.678
_oxdiff_exptl_absorpt_empirical_full_min 0.696