Arene displacement, C-H activation and acetonitrile insertion reactions enabled by coordination of a functionalized iminophosphorane to a Ru<sup>II</sup>-<i>p</i>-cymene scaffold.
Gourkhede, Rani; Kaur, Bhupinder; Kote, Basvaraj S.; Balakrishna, Maravanji S.; Dalton transactions (Cambridge, England : 2003) 53 (2024) 10693–10703; doi:10.1039/d4dt00940a

data_7716295
_publ_section_title
;
 Arene displacement, C-H activation and acetonitrile insertion reactions
 enabled by coordination of a functionalized iminophosphorane to a
 Ru<sup>II</sup>-<i>p</i>-cymene scaffold.
;
_journal_issue                   25
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10693
_journal_page_last               10703
_journal_paper_doi               10.1039/d4dt00940a
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety
'C58 H48 Cl N O P2 Ru, 0.9(C H2 Cl2), 1.6(C4 H10 O)'
_chemical_formula_sum            'C65.3 H65.8 Cl2.8 N O2.6 P2 Ru'
_chemical_formula_weight         1168.46
_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             2024-05-24
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-05-24 deposited with the CCDC.	2024-05-29 downloaded from the CCDC.
;
_cell_angle_alpha                74.144(2)
_cell_angle_beta                 70.026(2)
_cell_angle_gamma                67.700(2)
_cell_formula_units_Z            2
_cell_length_a                   13.1607(2)
_cell_length_b                   13.4638(3)
_cell_length_c                   18.5572(3)
_cell_measurement_reflns_used    50198
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      31.6410
_cell_measurement_theta_min      1.8490
_cell_volume                     2820.02(10)
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      150.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \f    -10.27 349.73   0.50    4.00  81.02  -9.84  31.50    --   720
  2  \w    -65.46   0.04   0.50    4.00    --  -19.34  94.56 145.16  131
  3  \w    -60.89   0.11   0.50    4.00    --  -14.77  94.56 -34.84  122
  4  \w   -100.81  15.69   0.50    4.00    --   -9.84 -59.25 -51.92  233
  5  \w    -65.46   0.04   0.50    4.00    --  -19.34  94.56  73.16  131
  6  \f   -349.73  10.27   0.50    4.00   6.61  -9.84 -31.50    --   720
  7  \w    -65.46   0.04   0.50    4.00    --  -19.34  94.56   1.16  131
  8  \w   -100.81  15.69   0.50    4.00    --   -9.84 -59.25 164.08  233
  9  \f   -339.92  20.08   0.50    4.00  15.81  -9.84 -59.25    --   720
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0632
_diffrn_reflns_av_unetI/netI     0.0298
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            165754
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.000
_diffrn_reflns_theta_min         1.821
_exptl_absorpt_coefficient_mu    0.514
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71572
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.376
_exptl_crystal_description       block
_exptl_crystal_F_000             1214
_exptl_crystal_size_max          0.089
_exptl_crystal_size_mid          0.078
_exptl_crystal_size_min          0.045
_refine_diff_density_max         1.547
_refine_diff_density_min         -0.997
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     696
_refine_ls_number_reflns         16437
_refine_ls_number_restraints     80
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0431
_refine_ls_R_factor_gt           0.0363
_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^)+(0.0385P)^2^+2.6962P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0865
_refine_ls_wR_factor_ref         0.0918
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14557
_reflns_number_total             16437
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00940a2.cif
_cod_data_source_block           compound_3
_cod_depositor_comments
'Adding full bibliography for 7716295--7716298.cif.'
_cod_original_cell_volume        2820.02(11)
_cod_original_formula_sum        'C65.30 H65.80 Cl2.80 N O2.60 P2 Ru'
_cod_database_code               7716295
_shelx_shelxl_version_number     2018/3
_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. Restrained distances
 O5-C1C
 1.41 with sigma of 0.02
 O2-C1F
 1.41 with sigma of 0.02
 O2-C1G
 1.42 with sigma of 0.02
 O5-C1D
 1.42 with sigma of 0.02
 C1B-C1C
 1.48 with sigma of 0.02
 C1A-C1F
 1.48 with sigma of 0.02
 C1D-C1E
 1.5 with sigma of 0.02
 C1G-C1H
 1.5 with sigma of 0.02
 O3-C1J
 1.41 with sigma of 0.02
 O3-C1K
 1.42 with sigma of 0.02
 C1I-C1J
 1.48 with sigma of 0.02
 C1K-C1L
 1.5 with sigma of 0.02
 O5-C1B = O5-C1E
 2.37 with sigma of 0.04
 O2-C1A = O2-C1H
 2.37 with sigma of 0.04
 O3-C1I = O3-C1L
 2.37 with sigma of 0.04
 C1A-C1F \\sim C1G-C1H
 with sigma of 0.02
 C1B-C1C \\sim C1D-C1E
 with sigma of 0.02
 O2-C1F \\sim O2-C1G
 with sigma of 0.02
 O5-C1C \\sim O5-C1D
 with sigma of 0.02
 C1A-O2 \\sim O2-C1H
 with sigma of 0.04
 C1B-O5 \\sim O5-C1E
 with sigma of 0.04
 C1I-C1J \\sim C1K-C1L
 with sigma of 0.02
 O3-C1J \\sim O3-C1K
 with sigma of 0.02
 C1I-O3 \\sim O3-C1L
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O2 \\sim C1A \\sim C1F \\sim C1G \\sim C1H: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
O5 \\sim C1B \\sim C1C \\sim C1D \\sim C1E: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
C1C \\sim O5 \\sim C1D \\sim C1B \\sim C1E: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
O3 \\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
O2 \\sim C1F \\sim C1G \\sim C1A \\sim C1H: within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01 within 2A
C1G \\sim O2 \\sim C1F \\sim C1A \\sim C1H: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 O2, C1A, C1F, C1G, C1H
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O5, C1B, C1C, C1D, C1E
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O3, C1I, C1J, C1K, C1L
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: Cl2(0.9) Cl3(0.9) C59(0.9) H59a(0.9) H59b(0.9) O5(0.1) C1B(0.1)
 H1Ba(0.1) H1Bb(0.1) H1Bc(0.1) C1C(0.1) H1Ca(0.1) H1Cb(0.1) C1D(0.1) H1Da(0.1)
 H1Db(0.1) C1E(0.1) H1Ea(0.1) H1Eb(0.1) H1Ec(0.1) O2(0.5) C1A(0.5) H1Aa(0.5)
 H1Ab(0.5) H1Ac(0.5) C1F(0.5) H1Fa(0.5) H1Fb(0.5) C1G(0.5) H1Ga(0.5) H1Gb(0.5)
 C1H(0.5) H1Ha(0.5) H1Hb(0.5) H1Hc(0.5)
6.a Ternary CH refined with riding coordinates:
 C8(H8), C21(H21), C46(H46)
6.b Secondary CH2 refined with riding coordinates:
 C59(H59a,H59b), C1C(H1Ca,H1Cb), C1D(H1Da,H1Db), C1F(H1Fa,H1Fb), C1G(H1Ga,
 H1Gb), C1J(H1Ja,H1Jb), C1K(H1Ka,H1Kb)
6.c Aromatic/amide H refined with riding coordinates:
 C27(H27), C32(H32), C3(H3), C33(H33), C16(H16), C17(H17), C31(H31), C29(H29),
 C5(H5), C25(H25), C26(H26), C18(H18), C23(H23), C20(H20), C30(H30), C45(H45),
 C35(H35), C14(H14), C24(H24), C10(H10), C44(H44), C48(H48), C19(H19), C36(H36),
  C41(H41), C52(H52), C58(H58), C50(H50), C39(H39), C13(H13), C43(H43),
 C49(H49), C42(H42), C11(H11), C54(H54), C38(H38), C37(H37), C12(H12), C51(H51),
  C57(H57), C56(H56), C55(H55)
6.d Idealised Me refined as rotating group:
 C7(H7a,H7b,H7c), C1B(H1Ba,H1Bb,H1Bc), C1E(H1Ea,H1Eb,H1Ec), C1A(H1Aa,H1Ab,
 H1Ac), C1H(H1Ha,H1Hb,H1Hc), C1I(H1Ia,H1Ib,H1Ic), C1L(H1La,H1Lb,H1Lc)
;
_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
- Detector area scaling
;