Ruthenium mediated halogenation of white phosphorus: synthesis and reactivity of the unprecedented P<sub>4</sub>Cl<sub>2</sub> moiety.
Bispinghoff, Mark; Benkő, Zoltán; Grützmacher, Hansjörg; Calvo, Fuencisla Delgado; Caporali, Maria; Peruzzini, Maurizio; Dalton transactions (Cambridge, England : 2003) 48 (2019) 3593–3600; doi:10.1039/c8dt01840e

data_7047958
_publ_section_title
;
 Ruthenium mediated halogenation of white phosphorus: synthesis and
 reactivity of the unprecedented P<sub>4</sub>Cl<sub>2</sub> moiety.
;
_journal_issue                   11
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              3593
_journal_page_last               3600
_journal_paper_doi               10.1039/c8dt01840e
_journal_volume                  48
_journal_year                    2019
_chemical_formula_moiety         'C38.03 H63.04 Cl2 P5 Ru2, C4 H10 O2'
_chemical_formula_sum            'C42.03 H73.04 Cl2 O2 P5 Ru2'
_chemical_formula_weight         1038.30
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_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             2018-07-31
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-07-31 deposited with the CCDC.
2018-11-05 downloaded from the CCDC.
;
_cell_angle_alpha                70.6590(10)
_cell_angle_beta                 79.0950(10)
_cell_angle_gamma                88.9330(10)
_cell_formula_units_Z            2
_cell_length_a                   12.7474(2)
_cell_length_b                   13.3991(2)
_cell_length_c                   14.5781(3)
_cell_measurement_reflns_used    9764
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      33.12
_cell_measurement_theta_min      2.35
_cell_volume                     2304.44(7)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'fixed chi three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0216
_diffrn_reflns_av_unetI/netI     0.0166
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            46733
_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         25.681
_diffrn_reflns_theta_min         1.509
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.979
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.496
_exptl_crystal_description       block
_exptl_crystal_F_000             1076
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: 1,2-Dimethoxyethane'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.280
_refine_diff_density_min         -0.370
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     566
_refine_ls_number_reflns         8757
_refine_ls_number_restraints     436
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0258
_refine_ls_R_factor_gt           0.0226
_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^)+(0.0261P)^2^+2.8052P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0561
_refine_ls_wR_factor_ref         0.0587
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7995
_reflns_number_total             8757
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8dt01840e2.cif
_cod_data_source_block           cpstarru2p4cl2pcy3
_cod_depositor_comments
'Adding full bibliography for 7047955--7047958.cif.'
_cod_database_code               7047958
_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
 C20B-C16B \\sim C16C-C20C \\sim C20A-C16A \\sim C17C-C16C \\sim C20B-C19B
\\sim C20A-C19A \\sim C20C-
 C19C \\sim C18A-C17A \\sim C19B-C18B \\sim C19C-C18C \\sim C19A-C18A \\sim
C18B-C17B \\sim C17C-C18C ~
 C17B-C16B \\sim C17A-C16A
 with sigma of 0.02
 C19C-C14C \\sim C19B-C14B \\sim C19A-C14A \\sim C20C-C15C \\sim C20A-C15A
\\sim C20B-C15B \\sim C16C-
 C11C \\sim C16B-C11B \\sim C16A-C11A \\sim C17C-C12C \\sim C17B-C12B \\sim
C17A-C12A \\sim C18C-C13C ~
 C18B-C13B \\sim C18A-C13A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C13A) = Uanis(C13B) = Uanis(C13C) = Uanis(C12A) = Uanis(C12B) =
Uanis(C12C) = Uanis(C11A) = Uanis(C11B) = Uanis(C11C) = Uanis(C15A) =
Uanis(C15B) = Uanis(C15C) = Uanis(C14A) = Uanis(C14B) = Uanis(C14C)
Uanis(C18A) = Uanis(C16C)
4. Rigid body (RIGU) restrains
 C15B, C14B, C13B, C12B, C11B, C17B, C18B, C19B, C20B, C16B, C19A, C14A, C13A,
 C12A, C11A, C15A, C18A, C17A, C16A, C20A, C11C, C15C, C14C, C13C, C12C, C18C,
 C19C, C20C, C16C, C17C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 1*[Sof(C19A)+Sof(H19D)+Sof(H19E)+Sof(H19F)+Sof(C14A)+Sof(C13A)+Sof(C12A)+
 Sof(C11A)+Sof(C15A)+Sof(C18A)+Sof(H18D)+Sof(H18E)+Sof(H18F)+Sof(C17A)+
 Sof(H17D)+Sof(H17E)+Sof(H17F)+Sof(C16A)+Sof(H16D)+Sof(H16E)+Sof(H16F)+
 Sof(C20A)+Sof(H20D)+Sof(H20E)+Sof(H20F)]+1*[Sof(C15B)+Sof(C14B)+Sof(C13B)+
 Sof(C12B)+Sof(C11B)+Sof(C17B)+Sof(H17A)+Sof(H17B)+Sof(H17C)+Sof(C18B)+
 Sof(H18A)+Sof(H18B)+Sof(H18C)+Sof(C19B)+Sof(H19A)+Sof(H19B)+Sof(H19C)+
 Sof(C20B)+Sof(H20A)+Sof(H20B)+Sof(H20C)+Sof(C16B)+Sof(H16A)+Sof(H16B)+
 Sof(H16C)]+1*[Sof(C11C)+Sof(C15C)+Sof(C14C)+Sof(C13C)+Sof(C12C)+Sof(C18C)+
 Sof(H18G)+Sof(H18H)+Sof(H18I)+Sof(C19C)+Sof(H19G)+Sof(H19H)+Sof(H19I)+
 Sof(C20C)+Sof(H20G)+Sof(H20H)+Sof(H20I)+Sof(C16C)+Sof(H16G)+Sof(H16H)+
 Sof(H16I)+Sof(C17C)+Sof(H17G)+Sof(H17H)+Sof(H17I)]=1 with esd of 0.001
 Sof(C19A)=Sof(H19D)=Sof(H19E)=Sof(H19F)=Sof(C14A)=Sof(C13A)=Sof(C12A)=
 Sof(C11A)=Sof(C15A)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C17A)=
 Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=
 Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=FVAR(1)
 Sof(C15B)=Sof(C14B)=Sof(C13B)=Sof(C12B)=Sof(C11B)=Sof(C17B)=Sof(H17A)=
 Sof(H17B)=Sof(H17C)=Sof(C18B)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19B)=
 Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C20B)=Sof(H20A)=Sof(H20B)=Sof(H20C)=
 Sof(C16B)=Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(2)
 Sof(C11C)=Sof(C15C)=Sof(C14C)=Sof(C13C)=Sof(C12C)=Sof(C18C)=Sof(H18G)=
 Sof(H18H)=Sof(H18I)=Sof(C19C)=Sof(H19G)=Sof(H19H)=Sof(H19I)=Sof(C20C)=
 Sof(H20G)=Sof(H20H)=Sof(H20I)=Sof(C16C)=Sof(H16G)=Sof(H16H)=Sof(H16I)=
 Sof(C17C)=Sof(H17G)=Sof(H17H)=Sof(H17I)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C21(H21), C27(H27), C33(H33)
6.b Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,
 H26B), C28(H28A,H28B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B),
 C32(H32A,H32B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B),
  C38(H38A,H38B), C41(H41A,H41B), C40(H40A,H40B)
6.c Fitted pentagon refined as free rotating group:
 C15B(C14B,C13B,C12B,C11B), C14A(C13A,C12A,C11A,C15A), C11C(C15C,C14C,C13C,C12C)
6.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C),
 C9(H9A,H9B,H9C), C17B(H17A,H17B,H17C), C18B(H18A,H18B,H18C), C19B(H19A,H19B,
 H19C), C20B(H20A,H20B,H20C), C16B(H16A,H16B,H16C), C19A(H19D,H19E,H19F),
 C18A(H18D,H18E,H18F), C17A(H17D,H17E,H17F), C16A(H16D,H16E,H16F), C20A(H20D,
 H20E,H20F), C39(H39A,H39B,H39C), C42(H42A,H42B,H42C), C18C(H18G,H18H,H18I),
 C19C(H19G,H19H,H19I), C20C(H20G,H20H,H20I), C16C(H16G,H16H,H16I), C17C(H17G,
 H17H,H17I)
;
_shelx_res_checksum              69693
_olex2_submission_special_instructions 'No special instructions were received'