Exploring efficient and air-stable d<sup>2</sup> Re(v) alkylidyne catalysts: toward room temperature alkyne metathesis.
Cui, Mingxu; Huang, Jie; Tsang, Long Yiu; Sung, Herman H. Y.; Williams, Ian D.; Jia, Guochen; Chemical science 15 (2024) 18318–18326; doi:10.1039/d4sc05369a

data_1572838
_publ_section_title
;
 Exploring efficient and air-stable d<sup>2</sup> Re(v) alkylidyne
 catalysts: toward room temperature alkyne metathesis.
;
_journal_issue                   44
_journal_name_full               'Chemical science'
_journal_page_first              18318
_journal_page_last               18326
_journal_paper_doi               10.1039/d4sc05369a
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C104 H54 Cl2 F48 O4 P4 Re2 Zn, 1.5(C H Cl3)'
_chemical_formula_sum            'C105.5 H55.5 Cl6.5 F48 O4 P4 Re2 Zn'
_chemical_formula_weight         3091.07
_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     iterative
_audit_creation_date             2024-05-21
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-06-05 deposited with the CCDC.	2024-10-02 downloaded from the CCDC.
;
_cell_angle_alpha                107.093(2)
_cell_angle_beta                 92.870(2)
_cell_angle_gamma                113.868(2)
_cell_formula_units_Z            2
_cell_length_a                   17.1380(3)
_cell_length_b                   18.3645(4)
_cell_length_c                   21.0670(5)
_cell_measurement_reflns_used    18497
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      72.5800
_cell_measurement_theta_min      2.7960
_cell_volume                     5686.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5-alpha (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1788
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.950
_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     35.00 134.00   1.00    4.00    --  104.18 -61.00  90.00   99
  2  \w    -66.00  30.00   1.00    1.00    --  -40.20  37.00-180.00   96
  3  \w   -113.00 -14.00   1.00    1.00    --  -40.20 -37.00   0.00   99
  4  \w    -86.00  -6.00   1.00    1.00    --  -40.20 125.00-120.00   80
  5  \w     77.00 173.00   1.00    4.00    --  104.18  30.00 -90.00   96
  6  \w     48.00 109.00   1.00    4.00    --  104.18-111.00 -90.00   61
  7  \w     70.00 146.00   1.00    4.00    --  104.18 178.00-180.00   76
  8  \w     26.00  64.00   1.00    4.00    --  104.18-111.00-180.00   38
  9  \w     75.00 109.00   1.00    4.00    --  104.18-111.00-180.00   34
 10  \w    103.00 178.00   1.00    4.00    --  104.18  77.00-180.00   75
 11  \w     99.00 178.00   1.00    4.00    --  104.18  30.00 -30.00   79
 12  \w     49.00 120.00   1.00    4.00    --  104.18 -45.00-150.00   71
 13  \w     67.00 146.00   1.00    4.00    --  104.18 178.00  90.00   79
;
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0170087000
_diffrn_orient_matrix_UB_12      -0.0914559000
_diffrn_orient_matrix_UB_13      -0.0407056000
_diffrn_orient_matrix_UB_21      -0.0111543000
_diffrn_orient_matrix_UB_22      -0.0232030000
_diffrn_orient_matrix_UB_23      0.0646327000
_diffrn_orient_matrix_UB_31      -0.0981019000
_diffrn_orient_matrix_UB_32      -0.0253330000
_diffrn_orient_matrix_UB_33      -0.0156881000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0368
_diffrn_reflns_av_unetI/netI     0.0568
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.950
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            34705
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.950
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.711
_diffrn_reflns_theta_min         2.236
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           0.80
_diffrn_source_power             0.040
_diffrn_source_target            Cu
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    7.436
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60022
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.69a (Rigaku Oxford Diffraction, 2020)
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    1.805
_exptl_crystal_description       plate
_exptl_crystal_F_000             3006
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.06
_refine_diff_density_max         2.963
_refine_diff_density_min         -1.621
_refine_diff_density_rms         0.146
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1916
_refine_ls_number_reflns         21495
_refine_ls_number_restraints     953
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0632
_refine_ls_R_factor_gt           0.0537
_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^)+(0.0948P)^2^+10.2798P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1450
_refine_ls_wR_factor_ref         0.1564
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18132
_reflns_number_total             21495
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05369a2.cif
_cod_data_source_block           cui42_173k
_cod_depositor_comments
'Adding full bibliography for 1572837--1572839.cif.'
_cod_original_cell_volume        5686.2(2)
_cod_original_formula_sum        'C105.50 H55.50 Cl6.50 F48 O4 P4 Re2 Zn'
_cod_database_code               1572838
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.664
_shelx_estimated_absorpt_t_min   0.292
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 Cl7-C2S \\sim Cl7-C2SA
 with sigma of 0.02
 Cl6-C2S \\sim Cl6-C2SA
 with sigma of 0.02
 Cl8A-C2S \\sim Cl8A-C2SA
 with sigma of 0.02
 Cl8-C2S \\sim Cl8-C2SA
 with sigma of 0.02
 F34-C118 \\sim F34A-C9
 with sigma of 0.02
 F35-C118 \\sim F35A-C9
 with sigma of 0.02
 F36-C118 \\sim F36A-C9
 with sigma of 0.02
 C115-C118 \\sim C115-C9
 with sigma of 0.02
 F34-F35 \\sim F34A-F35A
 with sigma of 0.04
 F34-F36 \\sim F34A-F36A
 with sigma of 0.04
 F34-C115 \\sim F34A-C115
 with sigma of 0.04
 F35-F36 \\sim F35A-F36A
 with sigma of 0.04
 F35-C115 \\sim F35A-C115
 with sigma of 0.04
 F36-C115 \\sim F36A-C115
 with sigma of 0.04
 F31-C117 \\sim F31A-C117
 with sigma of 0.02
 F32-C117 \\sim F32A-C117
 with sigma of 0.02
 F33-C117 \\sim F33A-C117
 with sigma of 0.02
 F40-C128 \\sim F40A-C128
 with sigma of 0.02
 F41-C128 \\sim F41A-C128
 with sigma of 0.02
 F42-C128 \\sim F42A-C128
 with sigma of 0.02
 F37-C127 \\sim F37A-C127
 with sigma of 0.02
 F38-C127 \\sim F38A-C127
 with sigma of 0.02
 F39-C127 \\sim F39A-C127
 with sigma of 0.02
 F43-C137 \\sim F43A-C137
 with sigma of 0.02
 F44-C137 \\sim F44A-C137
 with sigma of 0.02
 F45-C137 \\sim F45A-C137
 with sigma of 0.02
 F1-C67 \\sim F1A-C67
 with sigma of 0.02
 F2-C67 \\sim F2A-C67
 with sigma of 0.02
 F3-C67 \\sim F3A-C67
 with sigma of 0.02
 F19-C97 \\sim F19A-C97
 with sigma of 0.02
 F20-C97 \\sim F20A-C97
 with sigma of 0.02
 F21-C97 \\sim F21A-C97
 with sigma of 0.02
 F22-C98 \\sim F22A-C98
 with sigma of 0.02
 F23-C98 \\sim F23A-C98
 with sigma of 0.02
 F24-C98 \\sim F24A-C98
 with sigma of 0.02
 F7-C77 \\sim F7A-C77
 with sigma of 0.02
 F8-C77 \\sim F8A-C77
 with sigma of 0.02
 F9-C77 \\sim F9A-C77
 with sigma of 0.02
 F4-C68 \\sim F4A-C68
 with sigma of 0.02
 F5-C68 \\sim F5A-C68
 with sigma of 0.02
 F6-C68 \\sim F6A-C68
 with sigma of 0.02
 F13-C87 \\sim F13A-C87
 with sigma of 0.02
 F14-C87 \\sim F14A-C87
 with sigma of 0.02
 F15-C87 \\sim F15A-C87
 with sigma of 0.02
 F46-C138 \\sim F46A-C138
 with sigma of 0.02
 F47-C138 \\sim F47A-C138
 with sigma of 0.02
 F48-C138 \\sim F48A-C138
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C2S) \\sim Ueq, Uanis(C2SA) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.006
Uanis(F34) \\sim Ueq, Uanis(F35) \\sim Ueq, Uanis(F36) \\sim Ueq, Uanis(C118)
\\sim Ueq, Uanis(F34A) \\sim Ueq, Uanis(F36A) \\sim Ueq, Uanis(F35A) \\sim Ueq,
Uanis(C9) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(F31) \\sim Ueq, Uanis(F32) \\sim Ueq, Uanis(F33) \\sim Ueq, Uanis(C117)
\\sim Ueq, Uanis(F31A) \\sim Ueq, Uanis(F32A) \\sim Ueq, Uanis(F33A) \\sim Ueq:
with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(F40) \\sim Ueq, Uanis(F41) \\sim Ueq, Uanis(F42) \\sim Ueq, Uanis(C128)
\\sim Ueq, Uanis(F40A) \\sim Ueq, Uanis(F41A) \\sim Ueq, Uanis(F42A) \\sim Ueq:
with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(F37) \\sim Ueq, Uanis(F38) \\sim Ueq, Uanis(F39) \\sim Ueq, Uanis(C127)
\\sim Ueq, Uanis(F37A) \\sim Ueq, Uanis(F38A) \\sim Ueq, Uanis(F39A) \\sim Ueq:
with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(F43) \\sim Ueq, Uanis(F44) \\sim Ueq, Uanis(F45) \\sim Ueq, Uanis(C137)
\\sim Ueq, Uanis(F43A) \\sim Ueq, Uanis(F44A) \\sim Ueq, Uanis(F45A) \\sim Ueq:
with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(F1) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(C67) \\sim
Ueq, Uanis(F1A) \\sim Ueq, Uanis(F2A) \\sim Ueq, Uanis(F3A) \\sim Ueq: with
sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(F19) \\sim Ueq, Uanis(F20) \\sim Ueq, Uanis(F21) \\sim Ueq, Uanis(C97)
\\sim Ueq, Uanis(F19A) \\sim Ueq, Uanis(F20A) \\sim Ueq, Uanis(F21A) \\sim Ueq:
with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(F9) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F8) \\sim Ueq, Uanis(F7A) \\sim
Ueq, Uanis(F8A) \\sim Ueq, Uanis(F9A) \\sim Ueq: with sigma of 0.003 and sigma
for terminal atoms of 0.006
Uanis(F4) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F4A) \\sim
Ueq, Uanis(F5A) \\sim Ueq, Uanis(F6A) \\sim Ueq: with sigma of 0.003 and sigma
for terminal atoms of 0.006
Uanis(F13) \\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(F15) \\sim Ueq, Uanis(C87)
\\sim Ueq, Uanis(F13A) \\sim Ueq, Uanis(F14A) \\sim Ueq, Uanis(F15A) \\sim Ueq:
with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(F16) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(F46) \\sim Ueq, Uanis(F47) \\sim Ueq, Uanis(F48) \\sim Ueq, Uanis(C138)
\\sim Ueq, Uanis(F46A) \\sim Ueq, Uanis(F47A) \\sim Ueq, Uanis(F48A) \\sim Ueq:
with sigma of 0.003 and sigma for terminal atoms of 0.006
4. Rigid body (RIGU) restrains
 F34, F35, F36, C118
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Cl8, F35A, C2SA, F36A, H2SA, C9, F34A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F32A, F33A, F31A, C117
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C117, F31, F32, F33
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F42, F40, F41, C128
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F42A, C128, F40A, F41A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C127, F37, F38, F39
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C127, F38A, F39A, F37A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C137, F45A, F43A, F44A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C137, F43, F44, F45
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C67, F3A, F1A, F2A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F3, F2, F1, C67
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C97, F20A, F21A, F19A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F20, C97, F21, F19
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F23, F22, F24, C98
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C98, F22A, F24A, F23A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C77, F9, F8, F7
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F8A, F9A, F7A, C77
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F5, F6, F4, C68
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F5A, C68, F6A, F4A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F13A, F14A, F15A, C87
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F13, F14, C87, F15
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C138, F47A, F46A, F48A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F48, F47, F46, C138
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(F31A)=Sof(F32A)=Sof(F33A)=1-FVAR(1)
 Sof(F31)=Sof(F32)=Sof(F33)=FVAR(1)
 Sof(F40A)=Sof(F41A)=Sof(F42A)=1-FVAR(2)
 Sof(F40)=Sof(F41)=Sof(F42)=FVAR(2)
 Sof(F37A)=Sof(F38A)=Sof(F39A)=1-FVAR(3)
 Sof(F37)=Sof(F38)=Sof(F39)=FVAR(3)
 Sof(F43A)=Sof(F44A)=Sof(F45A)=1-FVAR(4)
 Sof(F43)=Sof(F44)=Sof(F45)=FVAR(4)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(5)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(5)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=1-FVAR(6)
 Sof(F19)=Sof(F20)=Sof(F21)=FVAR(6)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=1-FVAR(7)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(7)
 Fixed Sof: F4(0.5) F5(0.5) F6(0.5) F7(0.5) F8(0.5) F9(0.5) F22(0.5) F23(0.5)
 F24(0.5) F34(0.6) F35(0.6) F36(0.6) F46(0.5) F47(0.5) F48(0.5) C118(0.6)
 Cl3(0.5) Cl4(0.5) Cl5(0.5) C1S(0.5) H1S(0.5) Cl8(0.5) Cl8A(0.5) C2S(0.5)
 H2S(0.5) C2SA(0.5) H2SA(0.5) F34A(0.4) F36A(0.4) F35A(0.4) C9(0.4) F23A(0.5)
 F24A(0.5) F22A(0.5) F7A(0.5) F8A(0.5) F9A(0.5) F4A(0.5) F5A(0.5) F6A(0.5)
 F46A(0.5) F47A(0.5) F48A(0.5)
6.a Ternary CH refined with riding coordinates:
 C1S(H1S), C2S(H2S), C2SA(H2SA)
6.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C12(H12A,H12B)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C14(H14), C15(H15), C16(H16),
 C17(H17), C18(H18), C23(H23), C24(H24), C25(H25), C26(H26), C33(H33), C34(H34),
  C35(H35), C36(H36), C43(H43), C44(H44), C45(H45), C46(H46), C53(H53),
 C54(H54), C55(H55), C56(H56), C62(H62), C64(H64), C66(H66), C72(H72), C74(H74),
  C76(H76), C82(H82), C84(H84), C86(H86), C92(H92), C94(H94), C96(H96),
 C102(H102), C104(H104), C106(H106), C112(H112), C114(H114), C116(H116),
 C122(H122), C124(H124), C126(H126), C132(H132), C134(H134), C136(H136)
;
_shelx_res_checksum              9866
_shelx_hkl_checksum              57784
_olex2_date_sample_data_collection 2020-11-12
_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 1.548
_oxdiff_exptl_absorpt_empirical_full_min 0.751