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_1558975
_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         'C62 H51 Cl O1.3 Os P3, Cl, H2 O, 2(C H Cl3)'
_chemical_formula_sum            'C64 H55 Cl8 O2.3 Os P3'
_chemical_formula_weight         1427.59
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2020-08-28
_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                80.333(3)
_cell_angle_beta                 80.005(4)
_cell_angle_gamma                72.223(4)
_cell_formula_units_Z            2
_cell_length_a                   12.5033(6)
_cell_length_b                   14.0801(5)
_cell_length_c                   18.7137(8)
_cell_measurement_reflns_used    7920
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      28.9719
_cell_measurement_theta_min      2.8064
_cell_volume                     3066.3(2)
_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_temperature      173(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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  0.0528
_diffrn_reflns_av_unetI/netI     0.1194
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            25229
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.825
_exptl_absorpt_coefficient_mu    2.550
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.95482
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.46 (release 27-08-2009 CrysAlis171 .NET)
(compiled Aug 27 2009,17:19:36)
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    1.546
_exptl_crystal_description       block
_exptl_crystal_F_000             1429
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.710
_refine_diff_density_min         -0.563
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.757
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     753
_refine_ls_number_reflns         10777
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      0.757
_refine_ls_R_factor_all          0.0609
_refine_ls_R_factor_gt           0.0369
_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^)] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0411
_refine_ls_wR_factor_ref         0.0434
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7690
_reflns_number_total             10777
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc03215h2.cif
_cod_data_source_block           3a
_cod_original_formula_sum        'C64 H55 Cl8 O2.30 Os P3'
_cod_database_code               1558975
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.883
_shelx_estimated_absorpt_t_min   0.629
_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, All O(H,H) groups
2. Restrained distances
 Cl5S-C2SB \\sim Cl5-C2SA
 with sigma of 0.02
 Cl6S-C2SB \\sim Cl4-C2SA
 with sigma of 0.02
 Cl4S-C2SB \\sim Cl3-C2SA
 with sigma of 0.02
 Cl5S-Cl6S \\sim Cl5-Cl4
 with sigma of 0.04
 Cl5S-Cl4S \\sim Cl5-Cl3
 with sigma of 0.04
 Cl6S-Cl4S \\sim Cl4-Cl3
 with sigma of 0.04
3. Others
 Sof(Cl3)=Sof(Cl4)=Sof(Cl5)=Sof(C2SA)=Sof(H2SA)=1-FVAR(1)
 Sof(Cl5S)=Sof(Cl4S)=Sof(Cl6S)=Sof(C2SB)=Sof(H2SB)=FVAR(1)
 Fixed Sof: O2(0.3)
4.a Free rotating group:
 O1W(H1Wa,H1Wb)
4.b Ternary CH refined with riding coordinates:
 C1S(H1S), C2SB(H2SB), C2SA(H2SA)
4.c Secondary CH2 refined with riding coordinates:
 C8(H8a,H8b)
4.d Aromatic/amide H refined with riding coordinates:
 C1(H1a), 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)
4.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              81268
_olex2_submission_special_instructions 'No special instructions were received'