C-H activation in bimetallic rhodium complexes to afford N-heterocyclic carbene pincer complexes.
Watson, Lachlan J.; Hill, Anthony F.; Dalton transactions (Cambridge, England : 2003) 52 (2023) 2164–2174; doi:10.1039/d2dt03984b

data_7712133
_publ_section_title
;
 C-H activation in bimetallic rhodium complexes to afford N-heterocyclic
 carbene pincer complexes.
;
_journal_issue                   7
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              2164
_journal_page_last               2174
_journal_paper_doi               10.1039/d2dt03984b
_journal_volume                  52
_journal_year                    2023
_chemical_formula_moiety         'C38 H32 Cl N2 P2 Rh S, C H Cl3'
_chemical_formula_sum            'C39 H33 Cl4 N2 P2 Rh S'
_chemical_formula_weight         868.38
_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             2022-10-18
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-11-25 deposited with the CCDC.	2023-01-16 downloaded from the CCDC.
;
_cell_angle_alpha                70.396(5)
_cell_angle_beta                 77.844(4)
_cell_angle_gamma                84.928(4)
_cell_formula_units_Z            2
_cell_length_a                   12.1459(6)
_cell_length_b                   12.7759(8)
_cell_length_c                   13.1675(7)
_cell_measurement_reflns_used    5490
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      72.9440
_cell_measurement_theta_min      4.6840
_cell_volume                     1881.32(19)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1297
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.975
_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     23.00 108.00   1.00    4.50    --   37.17  19.00  90.00   85
  2  \w    -21.00  57.00   1.00    4.50    --   37.17 -77.00   0.00   78
  3  \w     21.00 101.00   1.00    4.50    --   37.17  57.00-150.00   80
  4  \w    -26.00  52.00   1.00    4.50    --   37.17 -57.00 -90.00   78
  5  \w     20.00 104.00   1.00    4.50    --   37.17  57.00 150.00   84
  6  \w     30.00  91.00   1.00    4.50    --   37.17-125.00 -90.00   61
  7  \w      6.00  73.00   1.00    4.50    --   37.17 -99.00  60.00   67
  8  \w    151.00 178.00   1.00   22.50    --  111.00  50.00   0.00   27
  9  \w     94.00 148.00   1.00   22.50    --  111.00  50.00   0.00   54
 10  \w     41.00 109.00   1.00   22.50    --  111.00-111.00 -90.00   68
 11  \w     69.00 109.00   1.00   22.50    --  111.00-111.00 120.00   40
 12  \w    116.00 178.00   1.00   22.50    --  111.00  77.00  30.00   62
 13  \w    112.00 174.00   1.00   22.50    --  111.00 111.00  60.00   62
 14  \w     46.00 128.00   1.00   22.50    --  111.00 -50.00  30.00   82
 15  \w     56.00 103.00   1.00   22.50    --  111.00 -92.00 -90.00   47
 16  \w     92.00 177.00   1.00   22.50    --  111.00  38.00 120.00   85
 17  \w     62.00 109.00   1.00   22.50    --  111.00-111.00  60.00   47
 18  \w    105.00 173.00   1.00   22.50    --  111.00 111.00 -60.00   68
 19  \w     59.00 104.00   1.00   22.50    --  111.00 -92.00 150.00   45
 20  \w     68.00 106.00   1.00   22.50    --  111.00 -92.00 -30.00   38
 21  \w     47.00 114.00   1.00   22.50    --  111.00 -38.00 -30.00   67
 22  \w    107.00 175.00   1.00   22.50    --  111.00 111.00 -30.00   68
 23  \w     46.00 114.00   1.00   22.50    --  111.00 -50.00 -90.00   68
 24  \w    105.00 178.00   1.00   22.50    --  111.00  25.00  60.00   73
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0762164000
_diffrn_orient_matrix_UB_12      0.0828348000
_diffrn_orient_matrix_UB_13      -0.0707560000
_diffrn_orient_matrix_UB_21      0.1040814000
_diffrn_orient_matrix_UB_22      0.0459119000
_diffrn_orient_matrix_UB_23      -0.0896336000
_diffrn_orient_matrix_UB_31      -0.0140993000
_diffrn_orient_matrix_UB_32      -0.0861476000
_diffrn_orient_matrix_UB_33      -0.0545863000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0342
_diffrn_reflns_av_unetI/netI     0.0466
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            13600
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.702
_diffrn_reflns_theta_min         3.673
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.852
_exptl_absorpt_correction_T_max  0.834
_exptl_absorpt_correction_T_min  0.569
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
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    1.533
_exptl_crystal_description       block
_exptl_crystal_F_000             880
_exptl_crystal_size_max          0.164
_exptl_crystal_size_mid          0.074
_exptl_crystal_size_min          0.07
_refine_diff_density_max         1.247
_refine_diff_density_min         -0.767
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     733
_refine_ls_number_reflns         7420
_refine_ls_number_restraints     625
_refine_ls_restrained_S_all      0.989
_refine_ls_R_factor_all          0.0641
_refine_ls_R_factor_gt           0.0506
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0807P)^2^+1.9679P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1294
_refine_ls_wR_factor_ref         0.1418
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5998
_reflns_number_total             7420
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03984b4.cif
_cod_data_source_block           ljw-340
_cod_depositor_comments
'Adding full bibliography for 7712131--7712137.cif.'
_cod_database_code               7712133
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C25 H25 Cl N2 P2 Rh S'
_chemical_oxdiff_usercomment     'CDCl3/EtOH liquid diff 5C'
_shelx_estimated_absorpt_t_max   0.609
_shelx_estimated_absorpt_t_min   0.359
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 C5A-C6A = C10A-C11A
 1.37 with sigma of 0.02
 C5A-C14A = C6A-C7A = C8A-C9A = C9A-C14A = C9A-C10A = C11A-C12A = C13A-C14A
 1.42 with sigma of 0.02
 C7A-C8A = C12A-C13A
 1.38 with sigma of 0.02
 C36A-C35A = C35A-C34A
 1.36 with sigma of 0.02
 C37A-C38A
 1.38 with sigma of 0.02
 C37A-C36A = C34A-C33A = C33A-C38A
 1.37 with sigma of 0.02
 C16A-C17A = C19A-C20A = C20A-C15A
 1.37 with sigma of 0.02
 C16A-C15A
 1.38 with sigma of 0.02
 C17A-C18A = C18A-C19A
 1.36 with sigma of 0.02
 C24A-C25A = C21A-C22A = C22A-C23A
 1.37 with sigma of 0.02
 C24A-C23A
 1.38 with sigma of 0.02
 C25A-C26A = C26A-C21A
 1.36 with sigma of 0.02
 C5A-C9A = C8A-C14A = C9A-C13A
 2.45 with sigma of 0.04
 C7A-C9A = C9A-C11A = C12A-C14A
 2.43 with sigma of 0.04
 C5A-C7A = C6A-C8A = C10A-C12A = C11A-C13A
 2.42 with sigma of 0.04
 C5A-C13A = C8A-C10A
 2.48 with sigma of 0.04
 C36A-C34A
 2.36 with sigma of 0.04
 C37A-C35A = C35A-C33A = C34A-C38A
 2.37 with sigma of 0.04
 C37A-C33A
 2.38 with sigma of 0.04
 C16A-C20A
 2.38 with sigma of 0.04
 C16A-C18A = C18A-C20A = C19A-C15A
 2.37 with sigma of 0.04
 C17A-C19A
 2.36 with sigma of 0.04
 C24A-C26A = C26A-C22A = C21A-C23A
 2.37 with sigma of 0.04
 C24A-C22A
 2.38 with sigma of 0.04
 C25A-C21A
 2.36 with sigma of 0.04
 C5A-C6A \\sim C6A-C7A \\sim C7A-C8A \\sim C8A-C9A \\sim C5A-C14A \\sim
C9A-C10A \\sim C10A-C11A ~
 C11A-C12A \\sim C13A-C14A \\sim C12A-C13A \\sim C9A-C14A
 with sigma of 0.02
 C10A-C12A \\sim C9A-C11A \\sim C11A-C13A \\sim C8A-C10A \\sim C12A-C14A \\sim
C7A-C9A \\sim C6A-C8A ~
 C5A-C13A \\sim C5A-C7A \\sim C6A-C14A
 with sigma of 0.04
 C5A-C9A \\sim C8A-C14A \\sim C10A-C14A \\sim C9A-C13A
 with sigma of 0.04
 C37A-C36A \\sim C36A-C35A \\sim C35A-C34A \\sim C34A-C33A \\sim C33A-C38A
\\sim C38A-C37A
 with sigma of 0.02
 C37A-C33A \\sim C37A-C35A \\sim C33A-C35A \\sim C34A-C36A \\sim C34A-C38A
\\sim C38A-C36A
 with sigma of 0.04
 C16A-C17A \\sim C17A-C18A \\sim C18A-C19A \\sim C19A-C20A \\sim C20A-C15A
\\sim C15A-C16A
 with sigma of 0.02
 C16A-C20A \\sim C16A-C18A \\sim C20A-C18A \\sim C19A-C17A \\sim C19A-C15A
\\sim C15A-C17A
 with sigma of 0.04
 C24A-C22A \\sim C24A-C26A \\sim C22A-C26A \\sim C21A-C25A \\sim C21A-C23A
\\sim C23A-C25A
 with sigma of 0.04
 C24A-C25A \\sim C25A-C26A \\sim C26A-C21A \\sim C21A-C22A \\sim C22A-C23A
\\sim C23A-C24A
 with sigma of 0.02
3. Restrained planarity
 C5A, C6A, C7A, C8A, C9A, C10A, C11A, C12A, C13A, C14A
 with sigma of 0.1
 C37A, C36A, C35A, C34A, C33A, C38A
 with sigma of 0.1
 C16A, C17A, C18A, C19A, C20A, C15A
 with sigma of 0.1
 C24A, C25A, C26A, C21A, C22A, C23A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C5A \\sim C6A \\sim C7A \\sim C8A \\sim C9A \\sim C10A \\sim C11A \\sim C12A
\\sim C13A \\sim C14A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C37A \\sim C36A \\sim C35A \\sim C34A \\sim C33A \\sim C38A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C16A \\sim C17A \\sim C18A \\sim C19A \\sim C20A \\sim C15A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C24A \\sim C25A \\sim C26A \\sim C21A \\sim C22A \\sim C23A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C14B) = Uanis(C14A)
5. Rigid body (RIGU) restrains
 C5A, C6A, C7A, C8A, C9A, C10A, C11A, C12A, C13A, C14A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C37A, C36A, C35A, C34A, C33A, C38A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C16A, C17A, C18A, C19A, C20A, C15A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C24A, C25A, C26A, C21A, C22A, C23A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: N1B(0.5) Cl3A(0.5) N2A(0.5) Cl4B(0.5) H3AA(0.5) H3AB(0.5)
 H3BC(0.5) H3BD(0.5) H2BC(0.5) H2BD(0.5) H2AA(0.5) H2AB(0.5) Cl4A(0.5)
 Cl3B(0.5) H39(0.5) H39A(0.5) C4B(0.5) H4BA(0.5) H4BB(0.5) C19B(0.5) H19B(0.5)
 C18B(0.5) H18B(0.5) C17B(0.5) H17B(0.5) C16B(0.5) H16B(0.5) C15B(0.5)
 C20B(0.5) H20B(0.5) C16A(0.5) H16A(0.5) C17A(0.5) H17A(0.5) C18A(0.5)
 H18A(0.5) C19A(0.5) H19A(0.5) C20A(0.5) H20A(0.5) C15A(0.5) C5A(0.5) C6A(0.5)
 H6A(0.5) C7A(0.5) H7A(0.5) C8A(0.5) H8A(0.5) C9A(0.5) C10A(0.5) H10A(0.5)
 C11A(0.5) H11A(0.5) C12A(0.5) H12A(0.5) C13A(0.5) C14A(0.5) C5B(0.5) C6B(0.5)
 H6B(0.5) C7B(0.5) H7B(0.5) C8B(0.5) H8B(0.5) C9B(0.5) C10B(0.5) H10B(0.5)
 C11B(0.5) H11B(0.5) C12B(0.5) H12B(0.5) C13B(0.5) C14B(0.5) C4A(0.5) H4AA(0.5)
 H4AB(0.5) C24A(0.5) H24A(0.5) C25A(0.5) H25A(0.5) C26A(0.5) H26A(0.5)
 C21A(0.5) C22A(0.5) H22A(0.5) C23A(0.5) H23A(0.5) C24B(0.5) H24B(0.5)
 C25B(0.5) H25B(0.5) C26B(0.5) H26B(0.5) C21B(0.5) C22B(0.5) H22B(0.5)
 C23B(0.5) H23B(0.5) C35B(0.5) H35B(0.5) C36B(0.5) H36B(0.5) C37B(0.5)
 H37B(0.5) C38B(0.5) H38B(0.5) C33B(0.5) C34B(0.5) H34B(0.5) C37A(0.5)
 H37A(0.5) C36A(0.5) H36A(0.5) C35A(0.5) H35A(0.5) C34A(0.5) H34A(0.5)
 C33A(0.5) C38A(0.5) H38A(0.5) N2B(0.5) N1A(0.5)
7.a Ternary CH refined with riding coordinates:
 C39(H39), C39(H39A)
7.b Secondary CH2 refined with riding coordinates:
 C3(H3AA,H3AB), C3(H3BC,H3BD), C2(H2BC,H2BD), C2(H2AA,H2AB), C4B(H4BA,H4BB),
 C4A(H4AA,H4AB)
7.c Aromatic/amide H refined with riding coordinates:
 C30(H30), C28(H28), C29(H29), C32(H32), C31(H31), C19B(H19B), C18B(H18B),
 C17B(H17B), C16B(H16B), C20B(H20B), C16A(H16A), C17A(H17A), C18A(H18A),
 C19A(H19A), C20A(H20A), C6A(H6A), C7A(H7A), C8A(H8A), C10A(H10A), C11A(H11A),
 C12A(H12A), C6B(H6B), C7B(H7B), C8B(H8B), C10B(H10B), C11B(H11B), C12B(H12B),
 C24A(H24A), C25A(H25A), C26A(H26A), C22A(H22A), C23A(H23A), C24B(H24B),
 C25B(H25B), C26B(H26B), C22B(H22B), C23B(H23B), C35B(H35B), C36B(H36B),
 C37B(H37B), C38B(H38B), C34B(H34B), C37A(H37A), C36A(H36A), C35A(H35A),
 C34A(H34A), C38A(H38A)
;
_shelx_res_checksum              62378
_shelx_hkl_checksum              63105
_ins_header
;
TITL LJW-340_scale2 in P1 
REM P1 (#1 in standard setting)
CELL 1.54184  12.145872  12.775942  13.167544  70.3955  77.8441  84.9285
ZERR    3.00   0.000569   0.000753   0.000723   0.0052   0.0043   0.0043
LATT -1
SFAC C H N P S Cl Rh
UNIT 75.00 75.00 6.00 6.00 3.00 3.00 3.00
TREF
HKLF 4
END
;
_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 1.286
_oxdiff_exptl_absorpt_empirical_full_min 0.817
_publcif_funding_html
;
;