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_7132375
_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, 7.5(C6 H6), 0.25(C5 H12)'
_chemical_formula_sum            'C206.25 H152 Cl2 N4 O8 P4 Rh2'
_chemical_formula_weight         3214.91
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_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             2023-07-07
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-09-18 deposited with the CCDC.	2023-10-31 downloaded from the CCDC.
;
_cell_angle_alpha                67.834(2)
_cell_angle_beta                 80.669(3)
_cell_angle_gamma                76.916(3)
_cell_formula_units_Z            2
_cell_length_a                   17.4039(12)
_cell_length_b                   19.9901(14)
_cell_length_c                   25.7764(17)
_cell_measurement_reflns_used    9611
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.47
_cell_measurement_theta_min      2.29
_cell_volume                     8060.1(10)
_computing_cell_refinement       'SAINT V8.38A (Bruker AXS, 2016)'
_computing_data_collection       'Bruker APEX3 (Bruker AXS, 2015)'
_computing_data_reduction        'SAINT V8.38A (Bruker AXS, 2016)'
_computing_molecular_graphics    'SHELXTL 6.12 (Bruker AXS, 2002)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELX XT 2014/5 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker Kappa ImuS Duo Photon II CPAD'
_diffrn_measurement_method       '\f and \w 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  0.0852
_diffrn_reflns_av_unetI/netI     0.0709
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            472238
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.575
_diffrn_reflns_theta_min         1.850
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.342
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6987
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0896 before and 0.0702 after correction.
The Ratio of minimum to maximum transmission is 0.9365.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.325
_exptl_crystal_description       block
_exptl_crystal_F_000             3331
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: benzene, n-pentane'
_exptl_crystal_size_max          0.338
_exptl_crystal_size_mid          0.225
_exptl_crystal_size_min          0.174
_refine_diff_density_max         1.093
_refine_diff_density_min         -0.894
_refine_diff_density_rms         0.079
_refine_ls_abs_structure_details
;
 Flack x determined using 30411 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.009(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           fullcycle
_refine_ls_number_parameters     4072
_refine_ls_number_reflns         90374
_refine_ls_number_restraints     304
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0720
_refine_ls_R_factor_gt           0.0510
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0516P)^2^+4.3469P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1072
_refine_ls_wR_factor_ref         0.1170
_reflns_Friedel_coverage         0.999
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                74503
_reflns_number_total             90374
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc04972h2.cif
_cod_data_source_block           rd2209
_cod_database_code               7132375
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.893
_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
 C551-C552 = C552-C553 = C553-C554 = C554-C555
 1.54 with sigma of 0.01
 C551-C553 = C552-C554 = C553-C555
 2.9 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C451 \\sim C452 \\sim C453 \\sim C454 \\sim C455 \\sim C456: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C461 \\sim C462 \\sim C463 \\sim C464 \\sim C465 \\sim C466: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C471 \\sim C472 \\sim C473 \\sim C474 \\sim C475 \\sim C476: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C501 \\sim C502 \\sim C503 \\sim C504 \\sim C505 \\sim C506: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C531 \\sim C532 \\sim C533 \\sim C534 \\sim C535 \\sim C536: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C541 \\sim C542 \\sim C543 \\sim C544 \\sim C545 \\sim C546: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C551 \\sim C552 \\sim C553 \\sim C554 \\sim C555: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
Uanis(C475) \\sim Ueq, Uanis(C481) \\sim Ueq, Uanis(C504) \\sim Ueq,
Uanis(C521) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C551) \\sim Ueq, Uanis(C552) \\sim Ueq, Uanis(C553) \\sim Ueq,
Uanis(C554) \\sim Ueq, Uanis(C555) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Fixed Sof: C551(0.5) H55A(0.5) H55B(0.5) H55C(0.5) C552(0.5) H55D(0.5)
 H55E(0.5) C553(0.5) H55F(0.5) H55G(0.5) C554(0.5) H55H(0.5) H55I(0.5)
 C555(0.5) H55J(0.5) H55K(0.5) H55L(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C552(H55D,H55E), C553(H55F,H55G), C554(H55H,H55I)
5.b Me refined with riding coordinates:
 C551(H55A,H55B,H55C), C555(H55J,H55K,H55L)
5.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), C22(H22), C23(H23),
  C25(H25), C26(H26), C27(H27), C28(H28), C33(H33), C34(H34), C35(H35),
 C36(H36), C38(H38), C39(H39), C42(H42), C43(H43), C44(H44), C45(H45), C48(H48),
  C50(H50), C51(H51), C52(H52), C53(H53), C56(H56), C57(H57), C58(H58),
 C59(H59), C60(H60), C62(H62), C63(H63), C65(H65), C66(H66), C67(H67), C68(H68),
  C73(H73), C74(H74), C75(H75), C76(H76), C78(H78), C79(H79), C82(H82),
 C83(H83), C84(H84), C85(H85), C88(H88), C90(H90), C91(H91), C92(H92), C93(H93),
  C96(H96), C97(H97), C98(H98), C99(H99), C100(H100), C102(H102), C103(H103),
 C105(H105), C106(H106), C107(H107), C108(H108), C113(H113), C114(H114),
 C115(H115), C116(H116), C118(H118), C119(H119), C122(H122), C123(H123),
 C124(H124), C125(H125), C128(H128), C130(H130), C131(H131), C132(H132),
 C133(H133), C136(H136), C137(H137), C138(H138), C139(H139), C140(H140),
 C142(H142), C143(H143), C145(H145), C146(H146), C147(H147), C148(H148),
 C153(H153), C154(H154), C155(H155), C156(H156), C158(H158), C159(H159),
 C162(H162), C163(H163), C164(H164), C165(H165), C168(H168), C170(H170),
 C171(H171), C172(H172), C173(H173), C176(H176), C177(H177), C178(H178),
 C179(H179), C180(H180), C182(H182), C183(H183), C185(H185), C186(H186),
 C187(H187), C188(H188), C193(H193), C194(H194), C195(H195), C196(H196),
 C198(H198), C199(H199), C202(H202), C203(H203), C204(H204), C205(H205),
 C208(H208), C210(H210), C211(H211), C212(H212), C213(H213), C216(H216),
 C217(H217), C218(H218), C219(H219), C220(H220), C222(H222), C223(H223),
 C225(H225), C226(H226), C227(H227), C228(H228), C233(H233), C234(H234),
 C235(H235), C236(H236), C238(H238), C239(H239), C242(H242), C243(H243),
 C244(H244), C245(H245), C248(H248), C250(H250), C251(H251), C252(H252),
 C253(H253), C256(H256), C257(H257), C258(H258), C259(H259), C260(H260),
 C262(H262), C263(H263), C265(H265), C266(H266), C267(H267), C268(H268),
 C273(H273), C274(H274), C275(H275), C276(H276), C278(H278), C279(H279),
 C282(H282), C283(H283), C284(H284), C285(H285), C288(H288), C290(H290),
 C291(H291), C292(H292), C293(H293), C296(H296), C297(H297), C298(H298),
 C299(H299), C300(H300), C302(H302), C303(H303), C305(H305), C306(H306),
 C307(H307), C308(H308), C313(H313), C314(H314), C315(H315), C316(H316),
 C318(H318), C319(H319), C401(H401), C402(H402), C403(H403), C404(H404),
 C405(H405), C406(H406), C411(H411), C412(H412), C413(H413), C414(H414),
 C415(H415), C416(H416), C421(H421), C422(H422), C423(H423), C424(H424),
 C425(H425), C426(H426), C431(H431), C432(H432), C433(H433), C434(H434),
 C435(H435), C436(H436), C441(H441), C442(H442), C443(H443), C444(H444),
 C445(H445), C446(H446), C451(H451), C452(H452), C453(H453), C454(H454),
 C455(H455), C456(H456), C461(H461), C462(H462), C463(H463), C464(H464),
 C465(H465), C466(H466), C471(H471), C472(H472), C473(H473), C474(H474),
 C475(H475), C476(H476), C481(H481), C482(H482), C483(H483), C484(H484),
 C485(H485), C486(H486), C491(H491), C492(H492), C493(H493), C494(H494),
 C495(H495), C496(H496), C501(H501), C502(H502), C503(H503), C504(H504),
 C505(H505), C506(H506), C511(H511), C512(H512), C513(H513), C514(H514),
 C515(H515), C516(H516), C521(H521), C522(H522), C523(H523), C524(H524),
 C525(H525), C526(H526), C531(H531), C532(H532), C533(H533), C534(H534),
 C535(H535), C536(H536), C541(H541), C542(H542), C543(H543), C544(H544),
 C545(H545), C546(H546)
5.d Fitted hexagon refined as free rotating group:
 C461(C462,C463,C464,C465,C466), C521(C522,C523,C524,C525,C526)
;
_shelx_res_checksum              99770
_shelx_hkl_checksum              55372
_olex2_submission_special_instructions 'No special instructions were received'