Evolution of a 'privileged' P-alkene ligand: added planar chirality beats BINOL axial chirality in catalytic asymmetric C-C bond formation.
Leinauer, Luisa; Parla, Giorgio; Messelbeger, Julian; Herrera, Alberto; Heinemann, Frank W.; Langer, Jens; Chuchelkin, Ilya; Grasruck, Alexander; Frieß, Sibylle; Chelouan, Ahmed; Gavrilov, Konstantin; Dorta, Romano; Chemical communications (Cambridge, England)  (2023) –; doi:10.1039/d3cc04972h

data_7132374
_publ_section_title
;
 Evolution of a 'privileged' P-alkene ligand: added planar chirality beats
 BINOL axial chirality in catalytic asymmetric C-C bond formation.
;
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_paper_doi               10.1039/d3cc04972h
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C160 H104 Cl2 N4 O8 P4 Rh2, 4(C6 H6), C6 H14'
_chemical_formula_sum            'C190 H142 Cl2 N4 O8 P4 Rh2'
_chemical_formula_weight         3009.67
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-11-04
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_audit_update_record
;
2023-09-18 deposited with the CCDC.	2023-10-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.2954(8)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.44859(10)
_cell_length_b                   37.3327(2)
_cell_length_c                   16.40694(15)
_cell_measurement_reflns_used    47587
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      72.4510
_cell_measurement_theta_min      4.0420
_cell_volume                     7450.06(10)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT n/a (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.989
_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   -121.00   0.00   1.00    2.50    --  -40.61 -19.00 120.00  121
  2  \w   -121.00   0.00   1.00    2.50    --  -40.61 -19.00-120.00  121
  3  \w    -65.00  34.00   1.00    2.50    --  -40.61  38.00-150.00   99
  4  \w     75.00 177.00   1.00   10.00    --  104.57  61.00-150.00  102
  5  \w    103.00 178.00   1.00   10.00    --  104.57  77.00 120.00   75
  6  \w     79.00 178.00   1.00   10.00    --  104.57  45.00   0.00   99
  7  \w     32.00 130.00   1.00   10.00    --  104.57 -45.00  60.00   98
  8  \w     28.00 109.00   1.00   10.00    --  104.57-111.00-180.00   81
  9  \w     28.00 109.00   1.00   10.00    --  104.57-111.00  90.00   81
 10  \w     79.00 178.00   1.00   10.00    --  104.57  45.00  30.00   99
 11  \w    103.00 178.00   1.00   10.00    --  104.57  77.00 150.00   75
 12  \w    104.00 178.00   1.00   10.00    --  104.57 111.00 -30.00   74
 13  \w     52.00 178.00   1.00   10.00    --  104.57  15.00 -30.00  126
 14  \w   -113.00 -12.00   1.00    2.50    --  -40.61 -57.00  60.00  101
 15  \w     12.00 114.00   1.00    2.50    --   40.61  57.00   0.00  102
 16  \w     12.00 114.00   1.00    2.50    --   40.61  57.00-120.00  102
 17  \w     27.00  97.00   1.00    2.50    --   40.61-125.00   0.00   70
 18  \w     75.00 177.00   1.00   10.00    --  104.57  61.00  90.00  102
 19  \w     75.00 171.00   1.00   10.00    --  104.57  61.00 150.00   96
 20  \w    104.00 178.00   1.00   10.00    --  104.57 111.00  60.00   74
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0525091000
_diffrn_orient_matrix_UB_12      0.0333618000
_diffrn_orient_matrix_UB_13      0.0308323000
_diffrn_orient_matrix_UB_21      0.0619651000
_diffrn_orient_matrix_UB_22      -0.0078386000
_diffrn_orient_matrix_UB_23      0.0899666000
_diffrn_orient_matrix_UB_31      0.0972015000
_diffrn_orient_matrix_UB_32      0.0229699000
_diffrn_orient_matrix_UB_33      -0.0139743000
_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  0.0493
_diffrn_reflns_av_unetI/netI     0.0527
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       46
_diffrn_reflns_limit_k_min       -46
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            83261
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.400
_diffrn_reflns_theta_min         3.634
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.031
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.454
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (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 orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.342
_exptl_crystal_description       plate
_exptl_crystal_F_000             3116
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: benzene, n-hexane'
_exptl_crystal_size_max          0.262
_exptl_crystal_size_mid          0.143
_exptl_crystal_size_min          0.047
_refine_diff_density_max         0.884
_refine_diff_density_min         -1.005
_refine_diff_density_rms         0.088
_refine_ls_abs_structure_details
;
 Flack x determined using 12520 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.021(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1943
_refine_ls_number_reflns         28917
_refine_ls_number_restraints     541
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.0527
_refine_ls_R_factor_gt           0.0500
_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^)+(0.0876P)^2^+4.9673P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1298
_refine_ls_wR_factor_ref         0.1315
_reflns_Friedel_coverage         0.948
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.969
_reflns_number_gt                27880
_reflns_number_total             28917
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc04972h2.cif
_cod_data_source_block           rodo191031a
_cod_database_code               7132374
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C190H142Cl2N4O8P4Rh2
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
C185 \\sim C186 \\sim C187 \\sim C188 \\sim C189 \\sim C190 \\sim C191 \\sim
C192 \\sim C193 \\sim C194 \\sim C195 \\sim C196: within 4A with sigma of 0.02
and sigma for terminal atoms of 0.04 within 4A
Uanis(C174) \\sim Ueq, Uanis(C175) \\sim Ueq, Uanis(C176) \\sim Ueq,
Uanis(C177) \\sim Ueq, Uanis(C178) \\sim Ueq, Uanis(C173) \\sim Ueq,
Uanis(C179) \\sim Ueq, Uanis(C184) \\sim Ueq, Uanis(C183) \\sim Ueq,
Uanis(C182) \\sim Ueq, Uanis(C181) \\sim Ueq, Uanis(C180) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
3. Rigid body (RIGU) restrains
 C173, C174, C175, C176, C177, C178, C179, C180, C181, C182, C183, C184
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C190)=Sof(H190)=Sof(C189)=Sof(H189)=Sof(C188)=Sof(H188)=Sof(C187)=
 Sof(H187)=Sof(C186)=Sof(H186)=Sof(C185)=Sof(H185)=1-FVAR(1)
 Sof(C191)=Sof(H191)=Sof(C192)=Sof(H192)=Sof(C193)=Sof(H193)=Sof(C194)=
 Sof(H194)=Sof(C195)=Sof(H195)=Sof(C196)=Sof(H196)=FVAR(1)
 Sof(C181)=Sof(H181)=Sof(C182)=Sof(H182)=Sof(C183)=Sof(H183)=Sof(C184)=
 Sof(H184)=Sof(C179)=Sof(H179)=Sof(C180)=Sof(H180)=1-FVAR(2)
 Sof(C176)=Sof(H176)=Sof(C177)=Sof(H177)=Sof(C178)=Sof(H178)=Sof(C173)=
 Sof(H173)=Sof(C174)=Sof(H174)=Sof(C175)=Sof(H175)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C198(H19d,H19e), C199(H19f,H19g), C200(H20a,H20b), C201(H20c,H20d)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C7(H7), C8(H8), C13(H13), C14(H14), C15(H15),
 C16(H16), C18(H18), C19(H19), C22(H22), C23(H23), C24(H24), C25(H25), C28(H28),
  C30(H30), C31(H31), C32(H32), C33(H33), C36(H36), C37(H37), C38(H38),
 C39(H39), C40(H40), C42(H42), C43(H43), C45(H45), C46(H46), C47(H47), C48(H48),
  C53(H53), C54(H54), C55(H55), C56(H56), C58(H58), C59(H59), C62(H62),
 C63(H63), C64(H64), C65(H65), C68(H68), C70(H70), C71(H71), C72(H72), C73(H73),
  C76(H76), C77(H77), C78(H78), C79(H79), C80(H80), C82(H82), C83(H83),
 C85(H85), C86(H86), C87(H87), C88(H88), C93(H93), C94(H94), C95(H95), C96(H96),
  C98(H98), C99(H99), C102(H102), C103(H103), C104(H104), C105(H105),
 C108(H108), C110(H110), C111(H111), C112(H112), C113(H113), C116(H116),
 C117(H117), C118(H118), C119(H119), C120(H120), C122(H122), C123(H123),
 C125(H125), C126(H126), C127(H127), C128(H128), C133(H133), C134(H134),
 C135(H135), C136(H136), C138(H138), C139(H139), C142(H142), C143(H143),
 C144(H144), C145(H145), C148(H148), C150(H150), C151(H151), C152(H152),
 C153(H153), C156(H156), C157(H157), C158(H158), C159(H159), C160(H160),
 C161(H161), C162(H162), C163(H163), C164(H164), C165(H165), C166(H166),
 C167(H167), C168(H168), C169(H169), C170(H170), C171(H171), C172(H172),
 C176(H176), C177(H177), C178(H178), C173(H173), C174(H174), C175(H175),
 C191(H191), C192(H192), C193(H193), C194(H194), C195(H195), C196(H196),
 C181(H181), C182(H182), C183(H183), C184(H184), C179(H179), C180(H180),
 C190(H190), C189(H189), C188(H188), C187(H187), C186(H186), C185(H185)
5.c Fitted hexagon refined as free rotating group:
 C167(C168,C169,C170,C171,C172), C176(C177,C178,C173,C174,C175), C191(C192,
 C193,C194,C195,C196), C181(C182,C183,C184,C179,C180), C190(C189,C188,C187,C186,
 C185)
5.d Idealised Me refined as rotating group:
 C197(H19a,H19b,H19c), C202(H20e,H20f,H20g)
;
_olex2_date_sample_data_collection 2019-10-31
_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 2.714
_oxdiff_exptl_absorpt_empirical_full_min 0.707