Solvent- and anion-dependent rearrangement of fluorinated carbene ligands provides access to fluorinated alkenes
Hall, Lewis; Milner, Lucy; Hart, Sam; Whitwood, Adrian Charles; Lynam, Jason Martin; Slattery, John M.; Dalton Transactions  (2019) –; doi:10.1039/C9DT04307A

data_7701855
_publ_section_title
;
 Solvent- and anion-dependent rearrangement of fluorinated carbene ligands
 provides access to fluorinated alkenes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/C9DT04307A
_journal_year                    2019
_chemical_formula_moiety         'C39 H34.25 F1.25 P2 Ru, F5.27 P0.27 Si0.73'
_chemical_formula_sum            'C39 H34.25 F6.53 P2.28 Ru Si0.73'
_chemical_formula_weight         818.78
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-07-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.07.20 svn.r3457 for OlexSys, GUI svn.r5370)
;
_audit_update_record
;
2019-09-08 deposited with the CCDC.	2019-11-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.0299(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.4924(2)
_cell_length_b                   15.7881(2)
_cell_length_c                   17.8372(3)
_cell_measurement_reflns_used    10187
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      70.8870
_cell_measurement_theta_min      4.9830
_cell_volume                     3491.61(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      110.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -22.00  32.00   1.00    1.00    --    0.00  37.00   0.00   54
  2  \w     37.00  67.00   1.00    1.00    --    0.00  37.00   0.00   30
  3  \w     74.00 112.00   1.00    4.00    --   54.00  57.00  90.00   38
  4  \w     83.00 156.00   1.00    8.00    --  108.00  37.00 150.00   73
  5  \w    149.00 176.00   1.00    8.00    --  108.00  63.00  90.00   27
  6  \w    122.00 164.00   1.00    8.00    --  108.00 111.00   0.00   42
  7  \w    115.00 174.00   1.00    8.00    --  108.00 111.00 120.00   59
  8  \w    106.00 178.00   1.00    8.00    --  108.00  25.00  90.00   72
  9  \w     98.00 173.00   1.00    8.00    --  108.00  37.00  30.00   75
 10  \w    153.00 178.00   1.00    8.00    --  108.00  50.00-120.00   25
 11  \w     86.00 124.00   1.00    8.00    --  108.00  50.00-120.00   38
 12  \w     78.00 159.00   1.00    8.00    --  108.00  77.00 -90.00   81
 13  \w     86.00 170.00   1.00    8.00    --  108.00  77.00 -30.00   84
 14  \w     90.00 117.00   1.00    8.00    --  108.00  63.00  90.00   27
 15  \w     65.00  92.00   1.00    4.00    --   54.00 -19.00 -30.00   27
 16  \w     36.00 122.00   1.00    8.00    --  108.00 -37.00-150.00   86
 17  \w     51.00 112.00   1.00    8.00    --  108.00-111.00 -30.00   61
 18  \w     55.00  82.00   1.00    8.00    --  108.00-111.00   0.00   27
 19  \w     36.00 143.00   1.00    8.00    --  108.00 -91.00 150.00  107
 20  \w     34.00 123.00   1.00    4.00    --   54.00  57.00 150.00   89
 21  \w     60.00 151.00   1.00    8.00    --  108.00 178.00 150.00   91
 22  \w     10.00  60.00   1.00    4.00    --   54.00  19.00 -60.00   50
 23  \w    -14.00  74.00   1.00    4.00    --   54.00 -57.00   0.00   88
 24  \w    -16.00   9.00   1.00    4.00    --   54.00 -19.00 -30.00   25
 25  \w    -15.00  73.00   1.00    4.00    --   54.00 -77.00 -60.00   88
 26  \w     23.00 100.00   1.00    4.00    --   54.00-125.00-180.00   77
 27  \w    -14.00  58.00   1.00    4.00    --   54.00 -57.00-150.00   72
 28  \w    -30.00  60.00   1.00    1.00    --    0.00  77.00-180.00   90
 29  \w    -35.00  -8.00   1.00    1.00    --    0.00  90.00 -15.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0035272000
_diffrn_orient_matrix_UB_12      -0.0266169000
_diffrn_orient_matrix_UB_13      -0.0833414000
_diffrn_orient_matrix_UB_21      -0.0547799000
_diffrn_orient_matrix_UB_22      0.0845176000
_diffrn_orient_matrix_UB_23      -0.0247463000
_diffrn_orient_matrix_UB_31      0.1116776000
_diffrn_orient_matrix_UB_32      0.0405880000
_diffrn_orient_matrix_UB_33      -0.0029653000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0299
_diffrn_reflns_av_unetI/netI     0.0250
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            24639
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.077
_diffrn_reflns_theta_max         67.077
_diffrn_reflns_theta_min         3.565
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.414
_exptl_absorpt_correction_T_max  0.865
_exptl_absorpt_correction_T_min  0.586
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.29d (Rigaku Oxford Diffraction, 2017)
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 dark green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.558
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1661
_exptl_crystal_recrystallization_method
'evaporation of dichloromethane/diethyl ether'
_exptl_crystal_size_max          0.157
_exptl_crystal_size_mid          0.082
_exptl_crystal_size_min          0.072
_refine_diff_density_max         1.205
_refine_diff_density_min         -0.934
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     515
_refine_ls_number_reflns         6231
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0412
_refine_ls_R_factor_gt           0.0358
_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^)+(0.0588P)^2^+4.0540P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0932
_refine_ls_wR_factor_ref         0.0982
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5539
_reflns_number_total             6231
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt04307a2.cif
_cod_data_source_block           jml1715
_cod_original_cell_volume        3491.59(9)
_cod_database_code               7701855
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C39 H34.25 F6.525 P2.275 Ru Si0.725'
_chemical_oxdiff_usercomment     'Lewis Hall lmh-225 smaller crystals'
_reflns_odcompleteness_completeness 99.97
_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
2. Restrained planarity
 C7, C8, C9, C10, C11, C12, C13
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
Uanis(Si1) = Uanis(P3)
Uanis(C8) = Uanis(C8A)
Uanis(C13A) = Uanis(C13)
Uanis(C9A) = Uanis(C9)
Uanis(C10A) = Uanis(C10)
Uanis(C11A) = Uanis(C11)
Uanis(C12A) = Uanis(C12)
Uanis(C7) = Uanis(C7A)
Uanis(F2B) = Uanis(F1)
4. Others
 1*[Sof(H7AA)+Sof(F2A)]+1*[Sof(H7AB)+Sof(F2B)]+1*[Sof(C7)+Sof(C7A)+Sof(C8)+
 Sof(C13)+Sof(H13)+Sof(C12)+Sof(H12)+Sof(C11)+Sof(H11)+Sof(C10)+Sof(H10)+
 Sof(C9)+Sof(H9)+Sof(C8A)+Sof(C9A)+Sof(H9A)+Sof(C10A)+Sof(H10A)+Sof(C11A)+
 Sof(H11A)+Sof(C12A)+Sof(H12A)+Sof(C13A)+Sof(H13A)+Sof(F1)+Sof(F1A)]=1 with esd
 of 0.001
 Sof(F5B)=Sof(F6B)=Sof(F7B)=Sof(F8B)=Sof(P3)=1-FVAR(1)
 Sof(F5A)=Sof(F6A)=Sof(F7A)=Sof(Si1)=FVAR(1)
 Sof(C7A)=Sof(C8A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10A)=Sof(C11A)=Sof(H11A)=
 Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(H13A)=Sof(F1A)=1-FVAR(2)
 Sof(C7)=Sof(C8)=Sof(C13)=Sof(H13)=Sof(C12)=Sof(H12)=Sof(C11)=Sof(H11)=
 Sof(C10)=Sof(H10)=Sof(C9)=Sof(H9)=Sof(F1)=FVAR(2)
 Sof(H7AA)=Sof(F2A)=FVAR(3)
 Sof(H7AB)=Sof(F2B)=FVAR(4)
5.a Riding coordinates:
 C7A(H7AA,H7AB)
5.b Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C27(H27A,H27B)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C13(H13), C12(H12), C11(H11),
 C10(H10), C9(H9), C9A(H9A), C10A(H10A), C11A(H11A), C12A(H12A), C13A(H13A),
 C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C21(H21), C22(H22), C23(H23),
  C24(H24), C25(H25), C29(H29), C30(H30), C31(H31), C32(H32), C33(H33),
 C35(H35), C36(H36), C37(H37), C38(H38), C39(H39)
5.d Fitted hexagon refined as free rotating group:
 C8(C13,C12,C11,C10,C9)
;
_olex2_date_sample_data_collection 2017-05-23
_olex2_date_sample_submission    2017-05-17
_olex2_exptl_crystal_mounting_method 'oil on 150 micrometre micromount'
_olex2_submission_original_sample_id 'lmh-225 green crystal'
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.164
_oxdiff_exptl_absorpt_empirical_full_min 0.902