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_1558977
_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         'C69 H59 Cl O4 P3 Ru, Cl'
_chemical_formula_sum            'C69 H59 Cl2 O4 P3 Ru'
_chemical_formula_weight         1217.04
_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
_audit_creation_date             2020-08-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-08-29 deposited with the CCDC.	2020-09-01 downloaded from the CCDC.
;
_cell_angle_alpha                95.726(3)
_cell_angle_beta                 110.761(3)
_cell_angle_gamma                102.104(3)
_cell_formula_units_Z            4
_cell_length_a                   18.0079(6)
_cell_length_b                   18.6935(7)
_cell_length_c                   24.9721(9)
_cell_measurement_reflns_used    12931
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      28.02880
_cell_measurement_theta_min      1.8950
_cell_volume                     7545.1(5)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      173.00(10)
_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  0.0446
_diffrn_reflns_av_unetI/netI     0.0687
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            66266
_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         1.569
_exptl_absorpt_coefficient_mu    0.381
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92220
_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            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.071
_exptl_crystal_description       block
_exptl_crystal_F_000             2512
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.956
_refine_diff_density_min         -0.772
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1427
_refine_ls_number_reflns         26546
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0831
_refine_ls_R_factor_gt           0.0601
_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^)+(0.0386P)^2^+19.0424P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1263
_refine_ls_wR_factor_ref         0.1355
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20267
_reflns_number_total             26546
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc03215h2.cif
_cod_data_source_block           7
_cod_depositor_comments
;

2022-04-19
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C138 H118 Cl4 O8 P6 Ru2'
_cod_original_formula_weight         2434.08
_cod_original_formula_moiety         '2(C69 H59 Cl O4 P3 Ru), 2(Cl)'
_cod_original_formula_units_Z            2
_cod_database_code               1558977
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.894
_shelx_estimated_absorpt_t_min   0.863
_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), C9(H9a,H9b), C11(H11a,H11b), C77(H77a,H77b), C78(H78a,H78b),
 C80(H80a,H80b)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C23(H23),
 C24(H24), C25(H25), C26(H26), C27(H27), C29(H29), C30(H30), C31(H31), C32(H32),
  C33(H33), C35(H35), C36(H36), C37(H37), C38(H38), C39(H39), C41(H41),
 C42(H42), C43(H43), C44(H44), C45(H45), C47(H47), C48(H48), C49(H49), C50(H50),
  C51(H51), C53(H53), C54(H54), C55(H55), C56(H56), C57(H57), C59(H59),
 C60(H60), C61(H61), C62(H62), C63(H63), C65(H65), C66(H66), C67(H67), C68(H68),
  C69(H69), C70(H70), C72(H72), C86(H86), C87(H87), C88(H88), C89(H89),
 C90(H90), C92(H92), C93(H93), C94(H94), C95(H95), C96(H96), C98(H98), C99(H99),
  C100(H100), C101(H101), C102(H102), C104(H104), C105(H105), C106(H106),
 C107(H107), C108(H108), C110(H110), C111(H111), C112(H112), C113(H113),
 C114(H114), C116(H116), C117(H117), C118(H118), C119(H119), C120(H120),
 C122(H122), C123(H123), C124(H124), C125(H125), C126(H126), C128(H128),
 C129(H129), C130(H130), C131(H131), C132(H132), C134(H134), C135(H135),
 C136(H136), C137(H137), C138(H138)
2.c Idealised Me refined as rotating group:
 C13(H13a,H13b,H13c), C15(H15a,H15b,H15c), C82(H82a,H82b,H82c), C84(H84a,H84b,
 H84c)
;
_shelx_res_checksum              95956
_shelx_fab_checksum              71346
_olex2_submission_special_instructions 'No special instructions were received'