A green route to platinum N-heterocyclic carbene complexes: mechanism and expanded scope
Maliszewski, Benon P.; Ritacco, Ida; Beliš, Marek; Hashim, Ishfaq Ibni; Tzouras, Nikolaos V.; Caporaso, Lucia; Cavallo, Luigi; Van Hecke, Kristof; Nahra, Fady; Cazin, Catherine S. J.; Nolan, Steven P.; Dalton Transactions  (2022) –; doi:10.1039/D2DT00504B

data_7709907
_publ_section_title
;
 A green route to platinum N-heterocyclic carbene complexes: mechanism and
 expanded scope
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT00504B
_journal_year                    2022
_chemical_formula_moiety
'2(C79 H78 Cl2 N2 Pt S), 0.5(C0.33 H0.66 Cl0.66), C5 H12, 0.834(C H2 Cl2)'
_chemical_formula_sum            'C164 H170 Cl6 N4 Pt2 S2'
_chemical_formula_weight         2864.03
_chemical_name_systematic        BM205
_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     direct
_audit_creation_date             2021-04-09
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-01-20 deposited with the CCDC.	2022-03-31 downloaded from the CCDC.
;
_cell_angle_alpha                75.8770(10)
_cell_angle_beta                 83.6710(10)
_cell_angle_gamma                67.8700(10)
_cell_formula_units_Z            2
_cell_length_a                   18.2626(2)
_cell_length_b                   19.2984(3)
_cell_length_c                   22.0694(3)
_cell_measurement_reflns_used    54272
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      28.5220
_cell_measurement_theta_min      2.7390
_cell_volume                     6985.88(17)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector_area_resol_mean 10.4839
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.879
_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    -65.00  36.00   1.00   15.00    --    7.68 -57.00-120.00  101
  2  \w    -20.00  81.00   1.00   15.00    --    7.68  57.00-180.00  101
  3  \w    -20.00  81.00   1.00   15.00    --    7.68  57.00  30.00  101
  4  \w    -15.00  49.00   1.00   15.00    --    7.68 -99.00  30.00   64
  5  \w    -20.00  81.00   1.00   15.00    --    7.68  57.00 -90.00  101
  6  \w    -15.00  49.00   1.00   15.00    --    7.68 -99.00  90.00   64
  7  \w    -15.00  49.00   1.00   15.00    --    7.68 -99.00 -30.00   64
  8  \w    -41.00   5.00   1.00   15.00    --   -8.77  77.00 150.00   46
  9  \w    -41.00  21.00   1.00   15.00    --   -8.77  77.00 120.00   62
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0418
_diffrn_reflns_av_unetI/netI     0.0446
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.879
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            137143
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.879
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.708
_diffrn_reflns_theta_min         2.547
_exptl_absorpt_coefficient_mu    2.199
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.449
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.362
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2944
_exptl_crystal_preparation       Synthesis
_exptl_crystal_recrystallization_method 'Pentane diffusion into DCM'
_exptl_crystal_size_max          0.248
_exptl_crystal_size_mid          0.152
_exptl_crystal_size_min          0.137
_refine_diff_density_max         1.900
_refine_diff_density_min         -2.002
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1636
_refine_ls_number_reflns         31765
_refine_ls_number_restraints     17
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0564
_refine_ls_R_factor_gt           0.0405
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0296P)^2^+20.1507P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0832
_refine_ls_wR_factor_ref         0.0904
_reflns_Friedel_coverage         0.000
_reflns_number_gt                26325
_reflns_number_total             31765
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00504b2.cif
_cod_data_source_block           bm205
_cod_database_code               7709907
_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
 C85B-Cl3B = C85B-Cl4B
 1.75 with sigma of 0.01
 Cl3B-Cl4B
 2.9 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C85A) = Uanis(C85B)
Uanis(Cl3A) = Uanis(Cl3B)
Uanis(Cl4A) = Uanis(Cl4B)
4. Rigid body (RIGU) restrains
 Cl3A, Cl4A, C85A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Cl3B, Cl4B, C85B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(Cl3B)=Sof(Cl4B)=Sof(C85B)=Sof(H85C)=Sof(H85D)=1-FVAR(1)
 Sof(Cl3A)=Sof(Cl4A)=Sof(C85A)=Sof(H85A)=Sof(H85B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C10(H10), C26(H26), C47(H47), C63(H63), C95(H95), C111(H111), C132(H132),
 C148(H148)
6.b Secondary CH2 refined with riding coordinates:
 C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B), C85A(H85A,H85B), C85B(H85C,
 H85D)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C8(H8), C12(H12), C13(H13), C15(H15), C16(H16),
 C19(H19), C20(H20), C22(H22), C23(H23), C28(H28), C29(H29), C31(H31), C32(H32),
  C35(H35), C36(H36), C38(H38), C39(H39), C43(H43), C45(H45), C49(H49),
 C50(H50), C52(H52), C53(H53), C56(H56), C57(H57), C59(H59), C60(H60), C65(H65),
  C66(H66), C68(H68), C69(H69), C72(H72), C73(H73), C75(H75), C76(H76),
 C87(H87), C88(H88), C91(H91), C93(H93), C97(H97), C98(H98), C100(H100),
 C101(H101), C104(H104), C105(H105), C107(H107), C108(H108), C113(H113),
 C114(H114), C116(H116), C117(H117), C120(H120), C121(H121), C123(H123),
 C124(H124), C128(H128), C130(H130), C134(H134), C135(H135), C137(H137),
 C138(H138), C141(H141), C142(H142), C144(H144), C145(H145), C150(H150),
 C151(H151), C153(H153), C154(H154), C157(H157), C158(H158), C160(H160),
 C161(H161)
6.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C33(H33A,H33B,
 H33C), C40(H40A,H40B,H40C), C54(H54A,H54B,H54C), C61(H61A,H61B,H61C), C62(H62A,
 H62B,H62C), C70(H70A,H70B,H70C), C77(H77A,H77B,H77C), C78(H78A,H78B,H78C),
 C79(H79A,H79B,H79C), C102(H10A,H10B,H10C), C109(H10D,H10E,H10F), C110(H11A,
 H11B,H11C), C118(H11D,H11E,H11F), C125(H12A,H12B,H12C), C139(H13A,H13B,H13C),
 C146(H14D,H14E,H14F), C147(H14A,H14B,H14C), C155(H15A,H15B,H15C), C162(H16A,
 H16B,H16C), C163(H16D,H16E,H16F), C164(H16G,H16H,H16I), C80(H80A,H80B,H80C),
 C84(H84A,H84B,H84C)
;
_shelx_res_checksum              12762
_shelx_hkl_checksum              62852
_olex2_exptl_crystal_mounting_method 'mounted on a LithoLoop'
_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
- B-factor correction
;