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_7712134
_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 H30 N2 O P2 Rh, F6 P, C6 H6'
_chemical_formula_sum            'C44 H36 F6 N2 O P3 Rh'
_chemical_formula_weight         918.57
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-10-20
_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                90
_cell_angle_beta                 105.181(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.2904(3)
_cell_length_b                   16.1205(5)
_cell_length_c                   19.0392(6)
_cell_measurement_reflns_used    5445
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      72.1270
_cell_measurement_theta_min      4.0410
_cell_volume                     4529.2(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1297
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.974
_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     20.00 104.00   1.00   14.00    --   36.65  57.00-120.00   84
  2  \w    -33.00  66.00   1.00   14.00    --   36.65 -19.00 -90.00   99
  3  \w     34.00  90.00   1.00   14.00    --   36.65-125.00 -30.00   56
  4  \w    -21.00  62.00   1.00   14.00    --   36.65 -77.00  90.00   83
  5  \w     43.00  70.00   1.00   57.50    --  109.99-111.00 120.00   27
  6  \w    115.00 178.00   1.00   57.50    --  109.99 111.00-180.00   63
  7  \w     43.00 127.00   1.00   57.50    --  109.99 -45.00-180.00   84
  8  \w    141.00 168.00   1.00   57.50    --  109.99  45.00 -30.00   27
  9  \w     76.00 176.00   1.00   57.50    --  109.99  15.00  30.00  100
 10  \w     63.00 109.00   1.00   57.50    --  109.99-111.00-120.00   46
 11  \w     93.00 121.00   1.00   57.50    --  109.99  45.00 -30.00   28
 12  \w     77.00 109.00   1.00   57.50    --  109.99-111.00 120.00   32
 13  \w     46.00 121.00   1.00   57.50    --  109.99 -45.00 -90.00   75
 14  \w     54.00 137.00   1.00   57.50    --  109.99 -77.00  90.00   83
;
_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      0.0137810000
_diffrn_orient_matrix_UB_12      0.0788793000
_diffrn_orient_matrix_UB_13      0.0473110000
_diffrn_orient_matrix_UB_21      0.0289607000
_diffrn_orient_matrix_UB_22      -0.0534965000
_diffrn_orient_matrix_UB_23      0.0692834000
_diffrn_orient_matrix_UB_31      0.0993224000
_diffrn_orient_matrix_UB_32      0.0047588000
_diffrn_orient_matrix_UB_33      -0.0036761000
_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  0.0365
_diffrn_reflns_av_unetI/netI     0.0595
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            17713
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.937
_diffrn_reflns_theta_min         4.303
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.553
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.95033
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
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    1.347
_exptl_crystal_description       needle
_exptl_crystal_F_000             1864
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.788
_refine_diff_density_min         -0.388
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     564
_refine_ls_number_reflns         8798
_refine_ls_number_restraints     310
_refine_ls_restrained_S_all      1.000
_refine_ls_R_factor_all          0.0740
_refine_ls_R_factor_gt           0.0450
_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^)+(0.0512P)^2^+3.1770P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1048
_refine_ls_wR_factor_ref         0.1163
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6124
_reflns_number_total             8798
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03984b4.cif
_cod_data_source_block           ljw-test-51_scale
_cod_depositor_comments
'Adding full bibliography for 7712131--7712137.cif.'
_cod_database_code               7712134
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C50H42F6OP3Rh
_shelx_estimated_absorpt_t_max   0.772
_shelx_estimated_absorpt_t_min   0.634
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C1G-C1L
 1.38 with sigma of 0.02
 C1B-C1C = C1C-C1D
 1.36 with sigma of 0.02
 C1H-C1I = C1I-C1J
 1.36 with sigma of 0.02
 C1G-C1H = C1J-C1K = C1K-C1L
 1.37 with sigma of 0.02
 C1A-C1B = C1D-C1E = C1E-C1F
 1.37 with sigma of 0.02
 C1A-C1F
 1.38 with sigma of 0.02
 C1H-C1J
 2.36 with sigma of 0.04
 C1A-C1C = C1C-C1E = C1D-C1F
 2.37 with sigma of 0.04
 C1A-C1E
 2.38 with sigma of 0.04
 C1G-C1I = C1I-C1K = C1J-C1L
 2.37 with sigma of 0.04
 C1G-C1K
 2.38 with sigma of 0.04
 C1B-C1D
 2.36 with sigma of 0.04
 C1A-C1B \\sim C1B-C1C \\sim C1C-C1D \\sim C1D-C1E \\sim C1E-C1F \\sim C1F-C1A
 with sigma of 0.02
 C1A-C1E \\sim C1A-C1C \\sim C1E-C1C \\sim C1D-C1B \\sim C1D-C1F \\sim C1F-C1B
 with sigma of 0.04
 C1G-C1H \\sim C1H-C1I \\sim C1I-C1J \\sim C1J-C1K \\sim C1K-C1L \\sim C1L-C1G
 with sigma of 0.02
 C1G-C1K \\sim C1G-C1I \\sim C1K-C1I \\sim C1J-C1H \\sim C1J-C1L \\sim C1L-C1H
 with sigma of 0.04
 C24-C22 \\sim C24A-C22A
 with sigma of 0.04
 C24-H24 \\sim C24A-H24A
 with sigma of 0.02
 C22-H23 \\sim C22A-H23A
 with sigma of 0.04
 C24-C23 \\sim C24A-C23A
 with sigma of 0.02
 H25-C26 \\sim H25A-C26A
 with sigma of 0.04
 C25-C26 \\sim C25A-C26A
 with sigma of 0.02
 C22-H22 \\sim C22A-H22A
 with sigma of 0.02
 H22-C23 \\sim H22A-C23A
 with sigma of 0.04
 C25-H25 \\sim C25A-H25A
 with sigma of 0.02
 C25-C24 \\sim C25A-C24A
 with sigma of 0.02
 C26-H26 \\sim C26A-H26A
 with sigma of 0.02
 C23-H23 \\sim C23A-H23A
 with sigma of 0.02
 H25-C24 \\sim H25A-C24A
 with sigma of 0.04
 C24-C26 \\sim C24A-C26A
 with sigma of 0.04
 C24-H23 \\sim C24A-H23A
 with sigma of 0.04
 C21-C25 \\sim C21A-C25A
 with sigma of 0.04
 H24-C23 \\sim H24A-C23A
 with sigma of 0.04
 C26-C22 \\sim C26A-C22A
 with sigma of 0.04
 C21-H26 \\sim C21A-H26A
 with sigma of 0.04
 C21-H22 \\sim C21A-H22A
 with sigma of 0.04
 C21-C23 \\sim C21A-C23A
 with sigma of 0.04
 C21-C22 \\sim C21A-C22A
 with sigma of 0.02
 H21-C26 \\sim H21A-C26A
 with sigma of 0.04
 H21-C22 \\sim H21A-C22A
 with sigma of 0.04
 C21-H21 \\sim C21A-H21A
 with sigma of 0.02
 C21-C26 \\sim C21A-C26A
 with sigma of 0.02
 C22-C23 \\sim C22A-C23A
 with sigma of 0.02
 C25-C23 \\sim C25A-C23A
 with sigma of 0.04
 C25-H24 \\sim C25A-H24A
 with sigma of 0.04
 C25-H26 \\sim C25A-H26A
 with sigma of 0.04
3. Restrained planarity
 C1A, C1B, C1C, C1D, C1E, C1F
 with sigma of 0.1
 C1G, C1H, C1I, C1J, C1K, C1L
 with sigma of 0.1
4. Rigid bond restraints
 C24, C23, C22, C21, C26, C25
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
5. Uiso/Uaniso restraints and constraints
C24 \\sim C25 \\sim C23 \\sim C22 \\sim C21 \\sim C26: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.04 within 1.7A
C1G \\sim C1H \\sim C1I \\sim C1J \\sim C1K \\sim C1L: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C1A \\sim C1B \\sim C1C \\sim C1D \\sim C1E \\sim C1F: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C21) = Uanis(C22) = Uanis(C24) = Uanis(C23) = Uanis(C25) = Uanis(C26)
Uanis(C21) = Uanis(C22A) = Uanis(C22) = Uanis(C23) = Uanis(C23A) = Uanis(C24) =
Uanis(C24A) = Uanis(C25) = Uanis(C25A) = Uanis(C26) = Uanis(C26A) = Uanis(C21A)
6. Rigid body (RIGU) restrains
 C1G, C1H, C1I, C1J, C1K, C1L
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, C1B, C1C, C1D, C1E, C1F
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(C1A)=Sof(H1A)=Sof(C1B)=Sof(H1B)=Sof(C1C)=Sof(H1C)=Sof(C1D)=Sof(H1D)=
 Sof(C1E)=Sof(H1E)=Sof(C1F)=1-FVAR(1)
 Sof(C1G)=Sof(H1G)=Sof(C1H)=Sof(H1H)=Sof(C1I)=Sof(H1I)=Sof(C1J)=Sof(H1J)=
 Sof(C1K)=Sof(H1K)=Sof(C1L)=FVAR(1)
 Sof(C26A)=Sof(H26A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(H22A)=Sof(C25A)=
 Sof(H25A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=1-FVAR(2)
 Sof(C21)=Sof(H21)=Sof(C25)=Sof(H25)=Sof(C24)=Sof(H24)=Sof(C26)=Sof(H26)=
 Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=FVAR(2)
8.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B)
8.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C10(H10), C6(H6), C7(H7), C28(H28), C34(H34), C32(H32), C16(H16),
 C11(H11), C8(H8), C20(H20), C29(H29), C38(H38), C18(H18), C17(H17), C37(H37),
 C36(H36), C31(H31), C30(H30), C35(H35), C19(H19), C1A(H1A), C1B(H1B), C1C(H1C),
  C1D(H1D), C1E(H1E), C1G(H1G), C1H(H1H), C1I(H1I), C1J(H1J), C1K(H1K),
 C21(H21), C25(H25), C24(H24), C26(H26), C22(H22), C23(H23), C26A(H26A),
 C21A(H21A), C22A(H22A), C25A(H25A), C23A(H23A), C24A(H24A)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              19440
_shelx_hkl_checksum              13193
_shelx_fab_checksum              29318
_ins_header
;
TITL LJW-test-51_scale in P2(1)/n 
REM P2(1)/n (#14 in standard setting)
CELL 1.54184  15.290426  16.120485  19.039241  90.0000 105.1813  90.0000
ZERR    4.00   0.000342   0.000460   0.000649   0.0000   0.0028   0.0000
LATT  1
SYMM -x+1/2, y+1/2,-z+1/2 
SFAC C H O F P Rh
UNIT 200.00 168.00 4.00 24.00 12.00 4.00
REM  CrysAlisPro recorded range (K): Min=150.0; max=150.0; aver:150.0
TEMP -123
SIZE 0.06 0.07 0.11
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 1.257
_oxdiff_exptl_absorpt_empirical_full_min 0.838
_publcif_funding_html
;
;