P(V)-bis(amidophenolate) ligand cooperation: stoichiometric CO-bond cleavage in aldehydes and ketones.
Karnbrock, Simon B. H.; Golz, Christopher; Alcarazo, Manuel; Chemical communications (Cambridge, England) 60 (2024) 6745–6748; doi:10.1039/d4cc02202e

data_7133148
_publ_section_title
;
 P(V)-bis(amidophenolate) ligand cooperation: stoichiometric
 C&#xe001;O-bond cleavage in aldehydes and ketones.
;
_journal_issue                   53
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              6745
_journal_page_last               6748
_journal_paper_doi               10.1039/d4cc02202e
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C40 H54 N2 O3 P, C32 H12 B F24, 0.88(C7 H8)'
_chemical_formula_sum            'C79 H74 B F24 N2 O3 P'
_chemical_formula_weight         1597.18
_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     dual
_audit_creation_date             2023-01-17
_audit_creation_method
;FinalCif V113 by Daniel Kratzert, Freiburg 2023,
https://dkratzert.de/finalcif.html
;
_audit_update_record
;
2024-05-06 deposited with the CCDC.	2024-06-03 downloaded from the CCDC.
;
_cell_angle_alpha                115.292(3)
_cell_angle_beta                 106.112(3)
_cell_angle_gamma                94.371(4)
_cell_formula_units_Z            2
_cell_length_a                   13.9743(17)
_cell_length_b                   16.814(2)
_cell_length_c                   19.335(3)
_cell_measurement_reflns_used    9304
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      29.040
_cell_measurement_theta_min      2.271
_cell_volume                     3845.7(9)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection
'Bruker BIS V6.2.15/2021-03-15 && APEX4 2022.1-1'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'XT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0412
_diffrn_reflns_av_unetI/netI     0.0208
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            197941
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.203
_diffrn_reflns_theta_min         1.971
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.143
_exptl_absorpt_correction_T_max  0.8016
_exptl_absorpt_correction_T_min  0.7780
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1497 before and 0.0493 after correction.
The Ratio of minimum to maximum transmission is 0.9706.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.379
_exptl_crystal_description       needle
_exptl_crystal_F_000             1644
_exptl_crystal_size_max          0.527
_exptl_crystal_size_mid          0.166
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.596
_refine_diff_density_min         -0.590
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1295
_refine_ls_number_reflns         20799
_refine_ls_number_restraints     662
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0691
_refine_ls_R_factor_gt           0.0543
_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^)+(0.0661P)^2^+2.9479P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1369
_refine_ls_wR_factor_ref         0.1494
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16814
_reflns_number_total             20799
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc02202e2.cif
_cod_data_source_block           mo_1871_sk_0m
_cod_depositor_comments
'Adding full bibliography for 7133142--7133149.cif.'
_cod_original_cell_volume        3845.6(9)
_cod_database_code               7133148
_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
 C80A-C81A
 1.51 with sigma of 0.02
 C80B-C81B
 1.51 with sigma of 0.02
 C81A-C82A = C81A-C86A = C83A-C84A
 1.39 with sigma of 0.02
 C82A-C83A = C84A-C85A = C85A-C86A
 1.38 with sigma of 0.02
 C81B-C82B = C81B-C86B = C83B-C84B
 1.39 with sigma of 0.02
 C82B-C83B = C84B-C85B = C85B-C86B
 1.38 with sigma of 0.02
 C81B-C85B
 2.41 with sigma of 0.04
 C80B-C82B = C80B-C86B
 2.52 with sigma of 0.04
 C81A-C83A
 2.42 with sigma of 0.04
 C80A-C82A = C80A-C86A
 2.52 with sigma of 0.04
 C82A-C84A
 2.39 with sigma of 0.04
 C83B-C85B = C84B-C86B
 2.4 with sigma of 0.04
 C81A-C85A
 2.41 with sigma of 0.04
 C83A-C85A = C84A-C86A
 2.4 with sigma of 0.04
 C82B-C84B
 2.39 with sigma of 0.04
 C81B-C83B
 2.42 with sigma of 0.04
 C87-C92 \\sim C92-C91 \\sim C91-C90 \\sim C90-C89 \\sim C89-C88 \\sim C88-C87
 with sigma of 0.02
 C86-C88 \\sim C86-C92
 with sigma of 0.04
 C87-C89 \\sim C87-C91 \\sim C88-C90 \\sim C92-C88 \\sim C91-C89 \\sim C92-C90
 with sigma of 0.04
 C80B-C86B \\sim C80B-C82B
 with sigma of 0.04
 C80A-C86A \\sim C80A-C82A
 with sigma of 0.04
 C81B-C85B \\sim C81B-C83B \\sim C86B-C84B \\sim C82B-C86B \\sim C83B-C85B
\\sim C82B-C84B
 with sigma of 0.04
 C81A-C82A \\sim C82A-C83A \\sim C83A-C84A \\sim C84A-C85A \\sim C85A-C86A
\\sim C86A-C81A
 with sigma of 0.02
 C81A-C85A \\sim C81A-C83A \\sim C86A-C84A \\sim C82A-C86A \\sim C83A-C85A
\\sim C82A-C84A
 with sigma of 0.04
 C81B-C82B \\sim C82B-C83B \\sim C83B-C84B \\sim C84B-C85B \\sim C85B-C86B
\\sim C86B-C81B
 with sigma of 0.02
 F14A-C64 \\sim F13B-C64
 with sigma of 0.02
 F15A-C64 \\sim F14B-C64
 with sigma of 0.02
 C64-F13A \\sim C64-F15B
 with sigma of 0.02
 C69-C71A \\sim C69-C71B
 with sigma of 0.02
 F24A-F23A \\sim F23B-F22B
 with sigma of 0.04
 F23A-F22A \\sim F22B-F24B
 with sigma of 0.04
 F22A-C71A \\sim F24B-C71B
 with sigma of 0.02
 F23A-C69 \\sim F22B-C69
 with sigma of 0.04
 F23A-C71A \\sim F22B-C71B
 with sigma of 0.02
 F22A-C69 \\sim F24B-C69
 with sigma of 0.04
 F24A-F22A \\sim F23B-F24B
 with sigma of 0.04
 F24A-C71A \\sim F23B-C71B
 with sigma of 0.02
 F24A-C69 \\sim F23B-C69
 with sigma of 0.04
 F18A-C63 \\sim F18B-C63
 with sigma of 0.02
 F17A-C63 \\sim F17B-C63
 with sigma of 0.02
 F16A-C63 \\sim F16B-C63
 with sigma of 0.02
 F21A-C72 \\sim F21B-C72
 with sigma of 0.02
 F20A-C72 \\sim F20B-C72
 with sigma of 0.02
 F19A-C72 \\sim F19B-C72
 with sigma of 0.02
 F12A-C55 \\sim F12B-C55
 with sigma of 0.02
 F10A-C55 \\sim F10B-C55
 with sigma of 0.02
 F11A-C55 \\sim F11B-C55
 with sigma of 0.02
 F2-C48 \\sim F2A-C48
 with sigma of 0.02
 F3-C48 \\sim F3A-C48
 with sigma of 0.02
 F1-C48 \\sim F1A-C48
 with sigma of 0.02
3. Restrained planarity
 C86, C87, C88, C89, C90, C91, C92
 with sigma of 0.1
 C80A, C81A, C82A, C83A, C84A, C85A, C86A
 with sigma of 0.1
 C80B, C81B, C82B, C83B, C84B, C85B, C86B
 with sigma of 0.1
4. Rigid bond restraints
 C80B, C81B, C82B, C83B, C84B, C85B, C86B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Uiso/Uaniso restraints and constraints
C86 \\sim C87 \\sim C88 \\sim C89 \\sim C90 \\sim C91 \\sim C92: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C86 \\sim C90: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C80B \\sim C81B \\sim C82B \\sim C83B \\sim C84B \\sim C85B \\sim C86B: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C80A \\sim C81A \\sim C82A \\sim C83A \\sim C84A \\sim C85A \\sim C86A: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C80B \\sim C81B: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
Uanis(C91) \\sim Ueq, Uanis(C90) \\sim Ueq, Uanis(C89) \\sim Ueq, Uanis(C88)
\\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(C92) \\sim Ueq: with sigma of 0.009 and
sigma for terminal atoms of 0.018
Uanis(C86) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C86B) \\sim Ueq, Uanis(C85B) \\sim Ueq, Uanis(C84B) \\sim Ueq,
Uanis(C83B) \\sim Ueq, Uanis(C82B) \\sim Ueq, Uanis(C81B) \\sim Ueq,
Uanis(C80B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C81A) \\sim Ueq, Uanis(C86A) \\sim Ueq, Uanis(C85A) \\sim Ueq,
Uanis(C84A) \\sim Ueq, Uanis(C83A) \\sim Ueq, Uanis(C82A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
6. Rigid body (RIGU) restrains
 C86, C87, C88, C89, C90, C91, C92
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0002
 C80A, C81A, C82A, C83A, C84A, C85A, C86A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C80B, C81B, C82B, C83B, C84B, C85B, C86B
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0002
 F19A, F20A, F21A, C72
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F19B, F20B, F21B, C72
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F18A, C63, F17A, F16A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C63, F17B, F16B, F18B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F12A, C55, F10A, F11A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F12B, C55, F11B, F10B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
7. Others
 Sof(F13B)=Sof(F14B)=Sof(F15B)=1-FVAR(1)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=FVAR(1)
 Sof(F22B)=Sof(F23B)=Sof(F24B)=Sof(C71B)=1-FVAR(2)
 Sof(F22A)=Sof(F23A)=Sof(F24A)=Sof(C71A)=FVAR(2)
 Sof(F16B)=Sof(F17B)=Sof(F18B)=1-FVAR(3)
 Sof(F16A)=Sof(F17A)=Sof(F18A)=FVAR(3)
 Sof(F19B)=Sof(F20B)=Sof(F21B)=1-FVAR(4)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=FVAR(4)
 Sof(F10B)=Sof(F11B)=Sof(F12B)=1-FVAR(5)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=FVAR(5)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(6)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(6)
 Sof(C80B)=Sof(H80D)=Sof(H80E)=Sof(H80F)=Sof(C81B)=Sof(C82B)=Sof(H82B)=
 Sof(C83B)=Sof(H83B)=Sof(C84B)=Sof(H84B)=Sof(C85B)=Sof(H85B)=Sof(C86B)=
 Sof(H86B)=0.5*(1-FVAR(8))
 Sof(C80A)=Sof(H80A)=Sof(H80B)=Sof(H80C)=Sof(C81A)=Sof(C82A)=Sof(H82A)=
 Sof(C83A)=Sof(H83A)=Sof(C84A)=Sof(H84A)=Sof(C85A)=Sof(H85A)=Sof(C86A)=
 Sof(H86A)=0.5*FVAR(8)
 Fixed Sof: C86(0.38) H86C(0.38) H86D(0.38) H86E(0.38) C87(0.38) C88(0.38)
 H88(0.38) C89(0.38) H89(0.38) C90(0.38) H90(0.38) C91(0.38) H91(0.38)
 C92(0.38) H92(0.38)
8.a Free rotating group:
 C86(C87,C88,C89,C90,C91,C92)
8.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B)
8.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C22(H22), C23(H23), C24(H24), C25(H25), C28(H28), C30(H30),
 C42(H42), C44(H44), C46(H46), C50(H50), C52(H52), C54(H54), C58(H58), C60(H60),
  C62(H62), C66(H66), C68(H68), C70(H70), C82A(H82A), C83A(H83A), C84A(H84A),
 C85A(H85A), C86A(H86A), C82B(H82B), C83B(H83B), C84B(H84B), C85B(H85B),
 C86B(H86B), C88(H88), C89(H89), C90(H90), C91(H91), C92(H92)
8.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C34(H34A,H34B,H34C), C35(H35A,H35B,
 H35C), C36(H36A,H36B,H36C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,
 H40B,H40C), C80A(H80A,H80B,H80C), C80B(H80D,H80E,H80F), C86(H86C,H86D,H86E)
;
_olex2_submission_special_instructions 'No special instructions were received'
_shelx_estimated_absorpt_t_min   0.929
_shelx_estimated_absorpt_t_max   0.986
_shelx_res_checksum              40115
_shelx_hkl_checksum              98645