Catalytic activity of cyclobutadiene rhodium complexes in hydrosilylation and other transformations of alkynes
Petrushina, Tatiana N.; Nelyubina, Yulia V.; Perekalin, Dmitry S.; Shvydkiy, Nikita V.; New Journal of Chemistry 48 (2024) 3952–3956; doi:10.1039/D3NJ05426H

data_7063011
_publ_section_title
;
 Catalytic activity of cyclobutadiene rhodium complexes in hydrosilylation
 and other transformations of alkynes
;
_journal_issue                   9
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              3952
_journal_page_last               3956
_journal_paper_doi               10.1039/D3NJ05426H
_journal_volume                  48
_journal_year                    2024
_chemical_formula_moiety         'C22 H28 Rh, F6 P'
_chemical_formula_sum            'C22 H28 F6 P Rh'
_chemical_formula_weight         540.32
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-19
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-10-19 deposited with the CCDC.	2024-02-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.557(6)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.9090(14)
_cell_length_b                   17.5486(17)
_cell_length_c                   15.8848(16)
_cell_measurement_reflns_used    9838
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.69
_cell_measurement_theta_min      2.56
_cell_volume                     4434.5(7)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_device_type  'Bruker Quest D8'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0697
_diffrn_reflns_av_unetI/netI     0.0666
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            30655
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.821
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.898
_exptl_absorpt_correction_T_max  0.4330
_exptl_absorpt_correction_T_min  0.3388
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1074 before and 0.0696 after correction.
The Ratio of minimum to maximum transmission is 0.7824.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.619
_exptl_crystal_description       plate
_exptl_crystal_F_000             2192
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.965
_refine_diff_density_min         -1.959
_refine_diff_density_rms         0.168
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     617
_refine_ls_number_reflns         7725
_refine_ls_number_restraints     126
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0978
_refine_ls_R_factor_gt           0.0840
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1678P)^2^+49.5686P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2455
_refine_ls_wR_factor_ref         0.2683
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6571
_reflns_number_total             7725
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3nj05426h2.cif
_cod_data_source_block           C4Et4RhC10H8
_cod_depositor_comments
'Adding full bibliography for 7063011--7063012.cif.'
_cod_database_code               7063011
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.956
_shelx_estimated_absorpt_t_min   0.744
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.649(2)
 0.351(2)
2. 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
3. Restrained distances
 C32'-C31' \\sim C31-C32
 with sigma of 0.02
 C31-C25 \\sim C25-C31'
 with sigma of 0.02
 C23-C27 \\sim C23-C27'
 with sigma of 0.02
 C11'-C12' \\sim C12-C11
 with sigma of 0.02
 C6-C5 \\sim C5'-C6'
 with sigma of 0.02
 C1-C5 \\sim C1-C5'
 with sigma of 0.02
 C26-C33' \\sim C33-C26
 with sigma of 0.02
 C33-C34 \\sim C34'-C33'
 with sigma of 0.02
 C30'-C29' \\sim C30-C29
 with sigma of 0.02
 C24-C29' \\sim C24-C29
 with sigma of 0.02
 P2-F12 \\sim P2-F12'
 with sigma of 0.02
 P2-F8' \\sim P2-F8
 with sigma of 0.02
 P2-F10 \\sim P2-F10'
 with sigma of 0.02
 P2-F7 \\sim P2-F7'
 with sigma of 0.02
 P2-F9 \\sim P2-F9'
 with sigma of 0.02
 P2-F11 \\sim P2-F11'
 with sigma of 0.02
 C6'-C5' \\sim C6-C5
 with sigma of 0.02
 C5'-C1 \\sim C5-C1
 with sigma of 0.02
 C27'-C23 \\sim C27-C23
 with sigma of 0.02
 C12'-C11' \\sim C12-C11
 with sigma of 0.02
 C34'-C33' \\sim C34-C33
 with sigma of 0.02
 C30-C29 \\sim C30'-C29'
 with sigma of 0.02
 C33'-C26 \\sim C33-C26
 with sigma of 0.02
 C32'-C31' \\sim C32-C31
 with sigma of 0.02
 C29'-C24 \\sim C29-C24
 with sigma of 0.02
 C4-C11' \\sim C4-C11
 with sigma of 0.02
 C31'-C25 \\sim C31-C25
 with sigma of 0.02
 C28-C27 \\sim C28'-C27'
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C21) \\sim Ueq, Uanis(C20) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C12') \\sim Ueq, Uanis(C12) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C31) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C27) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C11') \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C34) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C29') \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C30') \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F10') \\sim Ueq, Uanis(F12) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F12) \\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F8') \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(F12) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(F9') \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(F11') \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C11) = Uanis(C11')
Uanis(C12') = Uanis(C12)
Uanis(C31') = Uanis(C31)
Uanis(C32') = Uanis(C32)
Uanis(C27') = Uanis(C27)
Uanis(C28') = Uanis(C28)
Uanis(C6) = Uanis(C6')
Uanis(C5') = Uanis(C5)
Uanis(C33') = Uanis(C33)
Uanis(C34) = Uanis(C34')
Uanis(C30') = Uanis(C30)
Uanis(C29) = Uanis(C29')
Uanis(F9) = Uanis(F9')
Uanis(F10') = Uanis(F10)
Uanis(F8) = Uanis(F8')
Uanis(F12') = Uanis(F12)
Uanis(F7) = Uanis(F7')
Uanis(F11') = Uanis(F11)
5. Others
 Sof(C31')=Sof(H31C)=Sof(H31D)=Sof(C32')=Sof(H32D)=Sof(H32E)=Sof(H32F)=1-FVAR(1)
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(1)
 Sof(C27')=Sof(H27C)=Sof(H27D)=Sof(C28')=Sof(H28D)=Sof(H28E)=Sof(H28F)=1-FVAR(2)
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=FVAR(2)
 Sof(C11)=Sof(H11C)=Sof(H11D)=Sof(C12)=Sof(H12D)=Sof(H12E)=Sof(H12F)=1-FVAR(3)
 Sof(C11')=Sof(H11A)=Sof(H11B)=Sof(C12')=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(3)
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=1-FVAR(4)
 Sof(C5')=Sof(H5'A)=Sof(H5'B)=Sof(C6')=Sof(H6'A)=Sof(H6'B)=Sof(H6'C)=FVAR(4)
 Sof(C33')=Sof(H33C)=Sof(H33D)=Sof(C34')=Sof(H34D)=Sof(H34E)=Sof(H34F)=1-FVAR(5)
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=FVAR(5)
 Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=1-FVAR(6)
 Sof(C29')=Sof(H29C)=Sof(H29D)=Sof(C30')=Sof(H30D)=Sof(H30E)=Sof(H30F)=FVAR(6)
 Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=1-FVAR(7)
 Sof(F7')=Sof(F8')=Sof(F9')=Sof(F10')=Sof(F11')=Sof(F12')=FVAR(7)
6.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C9(H9A,H9B), C5'(H5'A,H5'B), C11'(H11A,H11B), C5(H5A,H5B),
 C11(H11C,H11D), C27(H27A,H27B), C29(H29A,H29B), C31(H31A,H31B), C33(H33A,H33B),
  C27'(H27C,H27D), C29'(H29C,H29D), C31'(H31C,H31D), C33'(H33C,H33D)
6.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C16(H16), C17(H17), C19(H19), C20(H20), C21(H21),
 C22(H22), C36(H36), C37(H37), C38(H38), C39(H39), C41(H41), C42(H42), C43(H43),
  C44(H44)
6.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C10(H10A,H10B,H10C), C6'(H6'A,H6'B,H6'C), C12'(H12A,H12B,
 H12C), C6(H6A,H6B,H6C), C12(H12D,H12E,H12F), C28(H28A,H28B,H28C), C30(H30A,
 H30B,H30C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C28'(H28D,H28E,H28F),
 C30'(H30D,H30E,H30F), C32'(H32D,H32E,H32F), C34'(H34D,H34E,H34F)
;
_shelx_res_checksum              37036
_olex2_submission_special_instructions 'No special instructions were received'