Latent Ruthenium Benzylidene Phosphite Complexes for Visible-Light-Induced Olefin Metathesis
Eivgi, Or; Vaisman, Anna; Nechmad, Noy B.; Baranov, Mark; Lemcoff, N. Gabriel; ACS Catalysis  (2020) 2033–2038; doi:10.1021/acscatal.9b05079

data_4517339
_publ_section_title
;
 Latent Ruthenium Benzylidene Phosphite Complexes for
 Visible-Light-Induced Olefin Metathesis
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              2033
_journal_page_last               2038
_journal_paper_doi               10.1021/acscatal.9b05079
_journal_year                    2020
_chemical_formula_moiety         'C49 H50 Cl2 N5 O9 P Ru, 2(C6 H6)'
_chemical_formula_sum            'C61 H62 Cl2 N5 O9 P Ru'
_chemical_formula_weight         1212.09
_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             2019-05-01
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.4110(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.3812(2)
_cell_length_b                   16.1503(2)
_cell_length_c                   26.0144(3)
_cell_measurement_reflns_used    37543
_cell_measurement_temperature    200(50)
_cell_measurement_theta_max      77.5260
_cell_measurement_theta_min      3.1100
_cell_volume                     5942.65(13)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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_environment      N~2~
_diffrn_ambient_temperature      200(50)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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      2.00  27.00   0.50    1.30    --   48.66 -30.00  -4.00   50
  2  \w     45.00  71.00   0.50    5.21    --  105.75 -30.00  -4.00   52
  3  \w     52.00  85.00   0.50    5.21    --  105.75 -45.00 -30.00   66
  4  \w     55.00  82.00   0.50    5.21    --  105.75 -45.00 -90.00   54
  5  \w     52.00  77.00   0.50    5.21    --  105.75 -30.00 -90.00   50
  6  \w     42.00  81.00   0.50    5.21    --  105.75 -30.00-120.00   78
  7  \w     41.00  75.00   0.50    5.21    --  105.75 -30.00-180.00   68
  8  \w     34.00  86.00   0.50    5.21    --  105.75 -45.00-120.00  104
  9  \w     87.00 113.00   0.50    5.21    --  105.75 -77.00-180.00   52
 10  \w     80.00 116.00   0.50    5.21    --  105.75-125.00-120.00   72
 11  \w     59.00 109.00   0.50    5.21    --  105.75 -95.00 -60.00  100
 12  \w     56.00 108.00   0.50    5.21    --  105.75 -95.00 -90.00  104
 13  \w     45.00  71.00   0.50    5.21    --  105.75 -30.00  30.00   52
 14  \w     37.00  71.00   0.50    5.21    --  105.75 -30.00 -30.00   68
 15  \w    123.00 177.00   0.50    5.21    --  105.75  15.00  60.00  108
 16  \w    151.00 177.00   0.50    5.21    --  105.75  30.00 120.00   52
 17  \w    134.00 178.00   0.50    5.21    --  105.75  30.00 155.00   88
 18  \w     98.00 124.00   0.50    5.21    --  105.75  30.00 155.00   52
 19  \w    100.00 137.00   0.50    5.21    --  105.75  30.00 120.00   74
 20  \w     55.00  81.00   0.50    5.21    --  105.75 -15.00 150.00   52
 21  \w     54.00  86.00   0.50    5.21    --  105.75 -45.00 150.00   64
 22  \w     42.00 121.00   0.50    1.30    --   48.66  30.00 155.00  158
 23  \w     35.00 108.00   0.50    5.21    --  105.75 -95.00  90.00  146
 24  \w     33.00  74.00   0.50    1.30    --   48.66-125.00-120.00   82
 25  \w     37.00  63.00   0.50    5.21    --  105.75 -77.00-180.00   52
 26  \w     41.00  77.00   0.50    5.21    --  105.75 -45.00-180.00   72
 27  \w     34.00  69.00   0.50    5.21    --  105.75-125.00-120.00   70
 28  \w     97.00 126.00   0.50    5.21    --  105.75  45.00 -90.00   58
 29  \w    137.00 176.00   0.50    5.21    --  105.75  45.00 -90.00   78
 30  \w    -56.00  24.00   0.50    1.30    --  -48.66  30.00 155.00  160
 31  \w    -50.00 -23.00   0.50    5.21    --  -84.25  45.00   0.00   54
 32  \w    -64.00 -12.00   0.50    5.21    --  -84.25  30.00 155.00  104
 33  \w   -121.00 -41.00   0.50    1.30    --  -48.66 -30.00  -4.00  160
 34  \w   -119.00 -94.00   0.50    1.30    --  -48.66-125.00 120.00   50
 35  \w   -118.00 -72.00   0.50    1.30    --  -48.66-125.00  60.00   92
 36  \w   -156.00 -76.00   0.50    5.21    --  -84.25 -30.00  -4.00  160
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0957253000
_diffrn_orient_matrix_UB_12      0.0096906000
_diffrn_orient_matrix_UB_13      0.0371643000
_diffrn_orient_matrix_UB_21      -0.0511261000
_diffrn_orient_matrix_UB_22      0.0338380000
_diffrn_orient_matrix_UB_23      0.0427941000
_diffrn_orient_matrix_UB_31      -0.0090764000
_diffrn_orient_matrix_UB_32      -0.0886324000
_diffrn_orient_matrix_UB_33      0.0203821000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0510
_diffrn_reflns_av_unetI/netI     0.0334
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            61395
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.422
_diffrn_reflns_theta_min         3.124
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.701
_exptl_absorpt_correction_T_max  0.973
_exptl_absorpt_correction_T_min  0.867
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.355
_exptl_crystal_description       plate
_exptl_crystal_F_000             2512
_exptl_crystal_size_max          0.321
_exptl_crystal_size_mid          0.066
_exptl_crystal_size_min          0.044
_refine_diff_density_max         1.320
_refine_diff_density_min         -0.637
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     708
_refine_ls_number_reflns         10866
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0452
_refine_ls_R_factor_gt           0.0412
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0732P)^2^+2.6566P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1144
_refine_ls_wR_factor_ref         0.1177
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9730
_reflns_number_total             10866
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b05079_si_002.cif
_cod_data_source_block           889_01_05_2019_239
_cod_depositor_comments
'Adding full bibliography for 4517338--4517339.cif.'
_cod_database_code               4517339
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ru C40 N5 O9 P Cl2'
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.31
_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. Uiso/Uaniso restraints and constraints
Uanis(C63) = Uanis(C62) = Uanis(C67) = Uanis(C64) = Uanis(C66) = Uanis(C65)
Uanis(C70) = Uanis(C69) = Uanis(C68) = Uanis(C73) = Uanis(C72) = Uanis(C71)
Uanis(C60) = Uanis(C59) = Uanis(C58) = Uanis(C57) = Uanis(C56) = Uanis(C61)
3. Others
 Sof(C62)=Sof(H62)=Sof(C63)=Sof(H63)=Sof(C64)=Sof(H64)=Sof(C65)=Sof(H65)=
 Sof(C66)=Sof(H66)=Sof(C67)=Sof(H67)=1-FVAR(1)
 Sof(C50)=Sof(H50)=Sof(C51)=Sof(H51)=Sof(C52)=Sof(H52)=Sof(C53)=Sof(H53)=
 Sof(C54)=Sof(H54)=Sof(C55)=Sof(H55)=FVAR(1)
 Sof(C68)=Sof(H68)=Sof(C69)=Sof(H69)=Sof(C70)=Sof(H70)=Sof(C71)=Sof(H71)=
 Sof(C72)=Sof(H72)=Sof(C73)=Sof(H73)=1-FVAR(2)
 Sof(C56)=Sof(H56)=Sof(C57)=Sof(H57)=Sof(C58)=Sof(H58)=Sof(C59)=Sof(H59)=
 Sof(C60)=Sof(H60)=Sof(C61)=Sof(H61)=FVAR(2)
 Fixed Sof: O8(0.5) O9(0.5) O10(0.5) O11(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C14(H14A,H14B), C17(H17A,H17B), C37(H37A,H37B)
4.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C12(H12), C13(H13), C18(H18), C20(H20), C21(H21), C23(H23), C26(H26),
 C28(H28), C29(H29), C33(H33), C35(H35), C38(H38), C39(H39), C40(H40), C41(H41),
  C42(H42), C43(H43), C44(H44), C45(H45), C48(H48), C49(H49), C50(H50),
 C51(H51), C52(H52), C53(H53), C54(H54), C55(H55), C56(H56), C57(H57), C58(H58),
  C59(H59), C60(H60), C61(H61), C62(H62), C63(H63), C64(H64), C65(H65),
 C66(H66), C67(H67), C68(H68), C69(H69), C70(H70), C71(H71), C72(H72), C73(H73)
4.c Fitted hexagon refined as free rotating group:
 C50(C51,C52,C53,C54,C55), C56(C57,C58,C59,C60,C61), C62(C63,C64,C65,C66,C67),
 C68(C69,C70,C71,C72,C73)
4.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C36(H36A,H36B,
 H36C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C)
;
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.960
_oxdiff_exptl_absorpt_empirical_full_min 0.478