Developing P-Stereogenic, Planar‒Chiral P-Alkene Ligands: Monodentate, Bidentate, and Double Agostic Coordination Modes on Ru(II)
Herrera, Alberto; Grasruck, Alexander; Heinemann, Frank W.; Scheurer, Andreas; Chelouan, Ahmed; Frieß, Sibylle; Seidel, Falk; Dorta, Romano; Organometallics 36 (2017) 714–; doi:10.1021/acs.organomet.6b00879

data_4087142
_publ_section_title
;
 Developing P-Stereogenic, Planar--Chiral P-Alkene Ligands: Monodentate,
 Bidentate, and Double Agostic Coordination Modes on Ru(II)
;
_journal_issue                   3
_journal_name_full               Organometallics
_journal_page_first              714
_journal_paper_doi               10.1021/acs.organomet.6b00879
_journal_volume                  36
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C35 H40 Cl2 N P Ru, C H2 Cl2'
_chemical_formula_sum            'C36 H42 Cl4 N P Ru'
_chemical_formula_weight         762.54
_chemical_name_systematic
;
 ? 
;
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-10-27
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                103.571(3)
_cell_angle_beta                 97.882(3)
_cell_angle_gamma                97.018(3)
_cell_formula_units_Z            3
_cell_length_a                   10.0993(11)
_cell_length_b                   14.0965(15)
_cell_length_c                   19.409(2)
_cell_measurement_reflns_used    9087
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.76
_cell_measurement_theta_min      2.35
_cell_volume                     2626.2(5)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'SHELXTL 6.12 (Bruker AXS, 2002)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/6 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXTL 6.12 (Bruker AXS, 2002)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 83.33
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker Kappa APEX II CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  'Quazar focussing montel optics'
_diffrn_radiation_source         'ImuS high brilliance micro-focus tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0479
_diffrn_reflns_av_unetI/netI     0.0346
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            173930
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.782
_diffrn_reflns_theta_min         1.096
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.825
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6690
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1029 before and 0.0573 after correction.
The Ratio of minimum to maximum transmission is 0.8970.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.446
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1176
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.706
_refine_diff_density_min         -1.068
_refine_diff_density_rms         0.085
_refine_ls_abs_structure_details
;
 Flack x determined using 12006 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.008(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1288
_refine_ls_number_reflns         27265
_refine_ls_number_restraints     264
_refine_ls_restrained_S_all      1.094
_refine_ls_R_factor_all          0.0390
_refine_ls_R_factor_gt           0.0334
_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^)+(0.0469P)^2^+2.2630P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0814
_refine_ls_wR_factor_ref         0.0851
_reflns_Friedel_coverage         0.996
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                25429
_reflns_number_total             27265
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00879_si_001.cif
_cod_data_source_block           rd1614
_cod_depositor_comments
;

2026-05-15
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C108 H126 Cl12 N3 P3 Ru3'
_cod_original_formula_weight         2287.63
_cod_original_formula_moiety         '3(C35 H40 Cl2 N P Ru), 3(C H2 Cl2)'
_cod_original_formula_units_Z            1
_cod_database_code               4087142
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.937
_shelx_estimated_absorpt_t_min   0.846
_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
 C108-Cl11
 1.75 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C106 \\sim Cl7 \\sim C116 \\sim Cl7A \\sim Cl8: within 2A with sigma of 0.005
and sigma for terminal atoms of 0.01
C107 \\sim Cl9 \\sim Cl10: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
C108 \\sim Cl11 \\sim Cl12: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C109 \\sim Cl13 \\sim Cl14: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C110 \\sim Cl15 \\sim Cl16: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C111 \\sim Cl17 \\sim Cl18: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C106) \\sim Ueq, Uanis(Cl7) \\sim Ueq, Uanis(C116) \\sim Ueq, Uanis(Cl7A)
\\sim Ueq, Uanis(Cl8) \\sim Ueq, Uanis(C107) \\sim Ueq, Uanis(Cl9) \\sim Ueq,
Uanis(Cl10) \\sim Ueq, Uanis(C108) \\sim Ueq, Uanis(Cl11) \\sim Ueq,
Uanis(Cl12) \\sim Ueq, Uanis(C109) \\sim Ueq, Uanis(Cl13) \\sim Ueq,
Uanis(Cl14) \\sim Ueq, Uanis(C110) \\sim Ueq, Uanis(Cl15) \\sim Ueq,
Uanis(Cl16) \\sim Ueq, Uanis(C111) \\sim Ueq, Uanis(Cl17) \\sim Ueq,
Uanis(Cl18) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(Cl10) \\sim Ueq, Uanis(Cl13) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.006
Uanis(Cl11) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
4. Same fragment restrains
{C107, Cl9, Cl10} sigma for 1-2: 0.02, 1-3: 0.04
as
{C108, Cl11, Cl12}
{C107, Cl9, Cl10} sigma for 1-2: 0.02, 1-3: 0.04
as
{C109, Cl13, Cl14}
{C107, Cl9, Cl10} sigma for 1-2: 0.02, 1-3: 0.04
as
{C110, Cl15, Cl16}
{C107, Cl9, Cl10} sigma for 1-2: 0.02, 1-3: 0.04
as
{C111, Cl17, Cl18}
5. Others
 1*[Sof(C108)+Sof(H10N)+Sof(H10O)+Sof(Cl11)+Sof(Cl12)]+1*[Sof(C109)+Sof(H10P)+
 Sof(H10Q)+Sof(Cl13)+Sof(Cl14)]+1*[Sof(C110)+Sof(H11C)+Sof(H11D)+Sof(Cl15)+
 Sof(Cl16)]=1 with esd of 0.001
 1*[Sof(C107)+Sof(H10L)+Sof(H10M)+Sof(Cl9)+Sof(Cl10)]+1*[Sof(C111)+Sof(H11E)+
 Sof(H11F)+Sof(Cl17)+Sof(Cl18)]=1 with esd of 0.001
 Sof(C116)=Sof(H11A)=Sof(H11B)=Sof(Cl7A)=1-FVAR(1)
 Sof(C106)=Sof(H10J)=Sof(H10K)=Sof(Cl7)=FVAR(1)
 Sof(C107)=Sof(H10L)=Sof(H10M)=Sof(Cl9)=Sof(Cl10)=FVAR(2)
 Sof(C108)=Sof(H10N)=Sof(H10O)=Sof(Cl11)=Sof(Cl12)=FVAR(3)
 Sof(C109)=Sof(H10P)=Sof(H10Q)=Sof(Cl13)=Sof(Cl14)=FVAR(4)
 Sof(C110)=Sof(H11C)=Sof(H11D)=Sof(Cl15)=Sof(Cl16)=FVAR(5)
 Sof(C111)=Sof(H11E)=Sof(H11F)=Sof(Cl17)=Sof(Cl18)=FVAR(6)
6.a Ternary CH refined with riding coordinates:
 C32(H32), C67(H67), C102(H102)
6.b Secondary CH2 refined with riding coordinates:
 C106(H10J,H10K), C116(H11A,H11B), C107(H10L,H10M), C108(H10N,H10O), C109(H10P,
 H10Q), C110(H11C,H11D), C111(H11E,H11F)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C10(H10), C11(H11), C12(H12),
 C13(H13), C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C27(H27), C28(H28),
  C30(H30), C31(H31), C37(H37), C38(H38), C39(H39), C40(H40), C43(H43),
 C45(H45), C46(H46), C47(H47), C48(H48), C51(H51), C52(H52), C53(H53), C54(H54),
  C55(H55), C62(H62), C63(H63), C65(H65), C66(H66), C72(H72), C73(H73),
 C74(H74), C75(H75), C78(H78), C80(H80), C81(H81), C82(H82), C83(H83), C86(H86),
  C87(H87), C88(H88), C89(H89), C90(H90), C97(H97), C98(H98), C100(H100),
 C101(H101)
6.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C57(H57A,
 H57B,H57C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C),
 C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C92(H92A,H92B,
 H92C), C93(H93A,H93B,H93C), C94(H94A,H94B,H94C), C95(H95A,H95B,H95C),
 C103(H10A,H10B,H10C), C104(H10D,H10E,H10F), C105(H10G,H10H,H10I)
;
_shelx_res_checksum              66598
_shelx_hkl_checksum              21055
_olex2_submission_special_instructions 'No special instructions were received'