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_1558980
_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         'C68 H55 Cl O Os P3, 2(C H Cl3), Cl'
_chemical_formula_sum            'C70 H57 Cl8 O Os P3'
_chemical_formula_weight         1480.86
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_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                106.991(5)
_cell_angle_beta                 103.843(4)
_cell_angle_gamma                105.956(4)
_cell_formula_units_Z            2
_cell_length_a                   12.0312(5)
_cell_length_b                   17.2019(10)
_cell_length_c                   19.2444(11)
_cell_measurement_reflns_used    17013
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      28.9555
_cell_measurement_theta_min      2.2717
_cell_volume                     3433.9(4)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      173(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type
'Goniometer Xcalibur, detector: Sapphire3 (Gemini ultra Mo)'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0351
_diffrn_reflns_av_unetI/netI     0.0587
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            29928
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.274
_exptl_absorpt_coefficient_mu    2.279
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64459
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.432
_exptl_crystal_description       block
_exptl_crystal_F_000             1484
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.531
_refine_diff_density_min         -0.846
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.962
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     796
_refine_ls_number_reflns         12097
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      0.962
_refine_ls_R_factor_all          0.0393
_refine_ls_R_factor_gt           0.0303
_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^)+(0.0323P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0639
_refine_ls_wR_factor_ref         0.0650
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10074
_reflns_number_total             12097
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc03215h2.cif
_cod_data_source_block           3b
_cod_original_cell_volume        3433.9(3)
_cod_database_code               1558980
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.659
_shelx_estimated_absorpt_t_min   0.342
_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 O(H) groups
2. Restrained distances
 H1a-Cl2
 2.52 with sigma of 0.02
 Cl6S-C2SA \\sim Cl4-C2SB
 with sigma of 0.02
 Cl5S-C2SA \\sim Cl3-C2SB
 with sigma of 0.02
 Cl4S-C2SA \\sim Cl5-C2SB
 with sigma of 0.02
 Cl6S-Cl5S \\sim Cl4-Cl3
 with sigma of 0.04
 Cl6S-Cl4S \\sim Cl4-Cl5
 with sigma of 0.04
 Cl5S-Cl4S \\sim Cl3-Cl5
 with sigma of 0.04
3. Others
 Sof(Cl3)=Sof(Cl4)=Sof(Cl5)=Sof(C2SB)=Sof(H2SB)=1-FVAR(1)
 Sof(Cl4S)=Sof(Cl5S)=Sof(Cl6S)=Sof(C2SA)=Sof(H2SA)=FVAR(1)
 Fixed Sof: H8a(0.667) H8b(0.333) O1(0.667) H1a(0.667) O1A(0.333) H1Aa(0.333)
4.a Ternary CH refined with riding coordinates:
 C8(H8a), C8(H8b), C1S(H1S), C2SA(H2SA), C2SB(H2SB)
4.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C5(H5), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14),
 C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C22(H22), C23(H23), C24(H24),
  C25(H25), C26(H26), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32),
 C34(H34), C35(H35), C36(H36), C37(H37), C38(H38), C40(H40), C41(H41), C42(H42),
  C43(H43), C44(H44), C46(H46), C47(H47), C48(H48), C49(H49), C50(H50),
 C52(H52), C53(H53), C54(H54), C55(H55), C56(H56), C58(H58), C59(H59), C60(H60),
  C61(H61), C62(H62), C64(H64), C65(H65), C66(H66), C67(H67), C68(H68)
4.c Idealised tetrahedral OH refined as rotating group:
 O1(H1a), O1A(H1Aa)
;
_shelx_res_checksum              27189
_shelx_fab_checksum              16501
_olex2_submission_special_instructions 'No special instructions were received'