Electrostatic vs. Inductive Effects in Phosphine Ligand Donor Properties and Reactivity
Kelty, Margaret L.; McNeece, Andrew J.; Kurutz, Josh W.; Filatov, Alexander S.; Anderson, John S.; Chemical Science  (2022) –; doi:10.1039/D1SC04277G

data_1566622
_publ_section_title
;
 Electrostatic vs. Inductive Effects in Phosphine Ligand Donor Properties
 and Reactivity
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC04277G
_journal_year                    2022
_chemical_formula_moiety         '0.25(C60.02 H64.02 B4 F12 K4 O2 P4)'
_chemical_formula_sum            'C15 H16 B F3 K O0.5 P'
_chemical_formula_weight         342.21
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-09-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-06-16 deposited with the CCDC.	2022-03-15 downloaded from the CCDC.
;
_cell_angle_alpha                78.455(2)
_cell_angle_beta                 89.976(2)
_cell_angle_gamma                89.948(2)
_cell_formula_units_Z            8
_cell_length_a                   5.6907(4)
_cell_length_b                   21.5917(16)
_cell_length_c                   26.847(2)
_cell_measurement_reflns_used    9979
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      23.11
_cell_measurement_theta_min      2.22
_cell_volume                     3232.0(4)
_computing_cell_refinement       'SAINT V.8.35A (Bruker AXS Inc., 2013)'
_computing_data_collection       'APEX3 v.2015.9-0 (Bruker AXS Inc., 2015)'
_computing_data_reduction        'SAINT V.8.35A (Bruker AXS Inc., 2013)'
_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    'XT 2014/5 (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 10.4167
_diffrn_detector_type            CMOS
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       'omega and phi scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0722
_diffrn_reflns_av_unetI/netI     0.0549
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            54508
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        23.376
_diffrn_reflns_theta_max         23.376
_diffrn_reflns_theta_min         1.980
_exptl_absorpt_coefficient_mu    0.450
_exptl_absorpt_correction_T_max  0.7449
_exptl_absorpt_correction_T_min  0.6341
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1427 before and 0.0597 after correction.
The Ratio of minimum to maximum transmission is 0.8513.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.407
_exptl_crystal_description       block
_exptl_crystal_F_000             1408
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.303
_refine_diff_density_min         -0.259
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1070
_refine_ls_number_reflns         9397
_refine_ls_number_restraints     2441
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0748
_refine_ls_R_factor_gt           0.0430
_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^)+(0.0357P)^2^+1.6740P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0798
_refine_ls_wR_factor_ref         0.0897
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6933
_reflns_number_total             9397
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc04277g2.cif
_cod_data_source_block           0916_am_2
_cod_original_cell_volume        3231.9(4)
_cod_original_formula_sum        'C15 H16 B F3 K O0.50 P'
_cod_database_code               1566622
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.961
_shelx_estimated_absorpt_t_min   0.858
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5192(13)
 0.4808(13)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Restrained distances
 P3-C31 \\sim P3-C18A
 with sigma of 0.02
 C31-C36 \\sim C18A-C23A
 with sigma of 0.02
 C31-C32 \\sim C18A-C19A
 with sigma of 0.02
 C33-C32 \\sim C20A-C19A
 with sigma of 0.02
 C36-C32 \\sim C23A-C19A
 with sigma of 0.04
 C36-C35 \\sim C23A-C22A
 with sigma of 0.02
 C33-C35 \\sim C20A-C22A
 with sigma of 0.04
 P3-C36 \\sim P3-C23A
 with sigma of 0.04
 P3-C32 \\sim P3-C19A
 with sigma of 0.04
 C31-C33 \\sim C18A-C20A
 with sigma of 0.04
 C31-C35 \\sim C18A-C22A
 with sigma of 0.04
 P1-C3 \\sim P1-C3A
 with sigma of 0.04
 C5-C3 \\sim C5A-C3A
 with sigma of 0.04
 C5-C4 \\sim C5A-C4A
 with sigma of 0.02
 C7-C3 \\sim C7A-C3A
 with sigma of 0.04
 C2-C4 \\sim C2A-C4A
 with sigma of 0.04
 C5-C6 \\sim C5A-C6A
 with sigma of 0.02
 P1-C7 \\sim P1-C7A
 with sigma of 0.04
 C5-C7 \\sim C5A-C7A
 with sigma of 0.04
 C2-C7 \\sim C2A-C7A
 with sigma of 0.02
 C2-C3 \\sim C2A-C3A
 with sigma of 0.02
 C7-C6 \\sim C7A-C6A
 with sigma of 0.02
 C4-C6 \\sim C4A-C6A
 with sigma of 0.04
 C3-C4 \\sim C3A-C4A
 with sigma of 0.02
 C2-C6 \\sim C2A-C6A
 with sigma of 0.04
 P1-C2 \\sim P1-C2A
 with sigma of 0.02
 C16-C15 \\sim C15A-C16A
 with sigma of 0.02
 C16-C17 \\sim C15A-C14A
 with sigma of 0.02
 O1-C15 \\sim O1A-C16A
 with sigma of 0.04
 C16-C14 \\sim C15A-C17A
 with sigma of 0.04
 C14-C17 \\sim C17A-C14A
 with sigma of 0.04
 C14-C15 \\sim C17A-C16A
 with sigma of 0.02
 O1-C16 \\sim O1A-C15A
 with sigma of 0.04
 K1-C14 \\sim K1-C17A
 with sigma of 0.04
 C15-C17 \\sim C16A-C14A
 with sigma of 0.04
 K1-C17 \\sim K1-C14A
 with sigma of 0.04
 K1-O1 \\sim K1-O1A
 with sigma of 0.02
 O1-C14 \\sim O1A-C17A
 with sigma of 0.02
 O1-C17 \\sim O1A-C14A
 with sigma of 0.02
 C45-C46 \\sim C30A-C29A
 with sigma of 0.02
 C45-C44 \\sim C30A-C31A
 with sigma of 0.02
 O2-C44 \\sim O2A-C31A
 with sigma of 0.02
 C46-C44 \\sim C29A-C31A
 with sigma of 0.04
 C47-C46 \\sim C28A-C29A
 with sigma of 0.02
 C45-C47 \\sim C30A-C28A
 with sigma of 0.04
 C47-C44 \\sim C28A-C31A
 with sigma of 0.04
 K3-C47 \\sim K3-C28A
 with sigma of 0.04
 K3-C44 \\sim K3-C31A
 with sigma of 0.04
 O2-C45 \\sim O2A-C30A
 with sigma of 0.04
 O2-C46 \\sim O2A-C29A
 with sigma of 0.04
 O2-C47 \\sim O2A-C28A
 with sigma of 0.02
 C37-C39 \\sim C37-C25A
 with sigma of 0.04
 K3-O2 \\sim K3-O2A
 with sigma of 0.02
 C37-C38 \\sim C37-C24A
 with sigma of 0.02
 C42-C41 \\sim C27A-C26A
 with sigma of 0.02
 C37-C42 \\sim C37-C27A
 with sigma of 0.02
 C37-C41 \\sim C37-C26A
 with sigma of 0.04
 C40-C39 \\sim C40-C25A
 with sigma of 0.02
 C42-C40 \\sim C27A-C40
 with sigma of 0.04
 C38-C39 \\sim C24A-C25A
 with sigma of 0.02
 C40-C38 \\sim C40-C24A
 with sigma of 0.04
 C40-C41 \\sim C40-C26A
 with sigma of 0.02
 C32-C33 \\sim C35-C36 \\sim C36-C31 \\sim C32-C31
 with sigma of 0.005
 C13-C12 \\sim C9A-C10A
 with sigma of 0.02
 C11-C12 \\sim C11A-C10A
 with sigma of 0.02
 C13-C8 \\sim C9A-C8A
 with sigma of 0.02
 C12-C8 \\sim C10A-C8A
 with sigma of 0.04
 C10-C9 \\sim C12A-C13A
 with sigma of 0.02
 C8-C9 \\sim C8A-C13A
 with sigma of 0.02
 C12-C10 \\sim C10A-C12A
 with sigma of 0.04
 C10-C8 \\sim C12A-C8A
 with sigma of 0.04
 P1-C13 \\sim P1-C9A
 with sigma of 0.04
 P1-C9 \\sim P1-C13A
 with sigma of 0.04
 C11-C13 \\sim C11A-C9A
 with sigma of 0.04
 C11-C9 \\sim C11A-C13A
 with sigma of 0.04
 P1-C8 \\sim P1-C8A
 with sigma of 0.02
 C11-C10 \\sim C11A-C12A
 with sigma of 0.02
 C13-C9 \\sim C9A-C13A
 with sigma of 0.04
 P3-C31 \\sim P3-C18A \\sim P3-C37 \\sim P2-C24 \\sim P2-C18 \\sim P1-C8 \\sim
P1-C8A \\sim P1-C2A \\sim P1-C2
 \\sim P4-C49 \\sim P4-C55
 with sigma of 0.02
 O2-C47 \\sim O2A-C31A \\sim O2-C44 \\sim O2A-C28A \\sim O1A-C17A \\sim O1-C17
\\sim O1-C14 \\sim O1A-C14A
 with sigma of 0.02
4. Restrained planarity
 C21A, C31, C32, C33, C35, C36
 with sigma of 0.001
 C18A, C19A, C20A, C22A, C23A
 with sigma of 0.001
5. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(F2) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C10A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C2) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C39) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C18A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
6. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(C18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20A)=Sof(C22A)=Sof(H22A)=
 Sof(C23A)=Sof(H23A)=1-FVAR(1)
 Sof(C21A)=Sof(H21A)=Sof(C31)=Sof(C32)=Sof(H32)=Sof(C33)=Sof(H33)=Sof(C34)=
 Sof(H34)=Sof(C35)=Sof(H35)=Sof(C36)=Sof(H36)=FVAR(1)
 Sof(C2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=
 Sof(H6A)=Sof(C7A)=Sof(H7A)=1-FVAR(2)
 Sof(C2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=
 Sof(C7)=Sof(H7)=FVAR(2)
 Sof(O1A)=Sof(C14A)=Sof(H14A)=Sof(H14B)=Sof(C15A)=Sof(H15A)=Sof(H15B)=
 Sof(C16A)=Sof(H16A)=Sof(H16B)=Sof(C17A)=Sof(H17A)=Sof(H17B)=1-FVAR(3)
 Sof(O1)=Sof(C14)=Sof(H14C)=Sof(H14D)=Sof(C15)=Sof(H15C)=Sof(H15D)=Sof(C16)=
 Sof(H16C)=Sof(H16D)=Sof(C17)=Sof(H17C)=Sof(H17D)=FVAR(3)
 Sof(O2A)=Sof(C28A)=Sof(H28A)=Sof(H28B)=Sof(C29A)=Sof(H29A)=Sof(H29B)=
 Sof(C30A)=Sof(H30C)=Sof(H30D)=Sof(C31A)=Sof(H31A)=Sof(H31B)=1-FVAR(4)
 Sof(O2)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C46)=
 Sof(H46A)=Sof(H46B)=Sof(C47)=Sof(H47A)=Sof(H47B)=FVAR(4)
 Sof(H40A)=Sof(C24A)=Sof(H24A)=Sof(C25A)=Sof(H25A)=Sof(C26A)=Sof(H26A)=
 Sof(C27A)=Sof(H27A)=1-FVAR(5)
 Sof(H40)=Sof(C38)=Sof(H38)=Sof(C39)=Sof(H39)=Sof(C41)=Sof(H41)=Sof(C42)=
 Sof(H42)=FVAR(5)
 Sof(C8A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10A)=Sof(C11A)=Sof(H11A)=Sof(C12A)=
 Sof(H12A)=Sof(C13A)=Sof(H13A)=1-FVAR(6)
 Sof(C8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12)=
 Sof(C13)=Sof(H13)=FVAR(6)
8.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C30(H30A,H30B), C43(H43A,H43B), C48(H48A,H48B), C14A(H14A,H14B),
 C15A(H15A,H15B), C16A(H16A,H16B), C17A(H17A,H17B), C28A(H28A,H28B), C29A(H29A,
 H29B), C30A(H30C,H30D), C31A(H31A,H31B), C14(H14C,H14D), C15(H15C,H15D),
 C16(H16C,H16D), C17(H17C,H17D), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B),
  C47(H47A,H47B)
8.b Aromatic/amide H refined with riding coordinates:
 C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C25(H25), C26(H26),
 C27(H27), C28(H28), C29(H29), C40(H40), C40(H40A), C50(H50), C51(H51),
 C52(H52), C53(H53), C54(H54), C56(H56), C57(H57), C58(H58), C59(H59), C60(H60),
  C3A(H3A), C4A(H4A), C5A(H5A), C6A(H6A), C7A(H7A), C9A(H9A), C10A(H10A),
 C11A(H11A), C12A(H12A), C13A(H13A), C19A(H19A), C20A(H20A), C21A(H21A),
 C22A(H22A), C23A(H23A), C24A(H24A), C25A(H25A), C26A(H26A), C27A(H27A), C3(H3),
  C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C38(H38), C39(H39),
  C41(H41), C42(H42)
;
_shelx_res_checksum              84759
_olex2_submission_special_instructions 'No special instructions were received'