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_7701854
_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_absolute_configuration ad
_chemical_formula_moiety         'C39 H34 F3 P2 Ru, F6 P'
_chemical_formula_sum            'C39 H34 F9 P3 Ru'
_chemical_formula_weight         867.64
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-02-09
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_audit_update_record
;
2019-09-08 deposited with the CCDC.	2019-11-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.2290(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.7451(2)
_cell_length_b                   9.98170(10)
_cell_length_c                   17.2999(2)
_cell_measurement_reflns_used    15496
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      31.8780
_cell_measurement_theta_min      3.9590
_cell_volume                     3553.84(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_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 0.998
_diffrn_measured_fraction_theta_max 0.998
_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      5.00  94.00   1.00   32.50    --   25.70  57.00  90.00   89
  2  \w    -47.00  70.00   1.00   32.50    --   25.70 -19.00 -90.00  117
  3  \w    -43.00  47.00   1.00   32.50    --   25.70 -57.00-120.00   90
  4  \w    -82.00 -22.00   1.00   32.50    --  -25.86 123.00 -89.00   60
  5  \w    -18.00  99.00   1.00   32.50    --   25.70  19.00   0.00  117
  6  \w     -4.00  21.00   1.00   32.50    --   25.70  77.00-150.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0219274000
_diffrn_orient_matrix_UB_12      0.0537959000
_diffrn_orient_matrix_UB_13      0.0027543000
_diffrn_orient_matrix_UB_21      -0.0263817000
_diffrn_orient_matrix_UB_22      -0.0423108000
_diffrn_orient_matrix_UB_23      -0.0139335000
_diffrn_orient_matrix_UB_31      -0.0032920000
_diffrn_orient_matrix_UB_32      -0.0190236000
_diffrn_orient_matrix_UB_33      0.0388312000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0191
_diffrn_reflns_av_unetI/netI     0.0269
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            20324
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.031
_diffrn_reflns_theta_min         3.372
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.653
_exptl_absorpt_correction_T_max  0.944
_exptl_absorpt_correction_T_min  0.898
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43d (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.622
_exptl_crystal_description       block
_exptl_crystal_F_000             1752
_exptl_crystal_recrystallization_method DCM:Et2O
_exptl_crystal_size_max          0.255
_exptl_crystal_size_mid          0.163
_exptl_crystal_size_min          0.115
_refine_diff_density_max         0.250
_refine_diff_density_min         -0.261
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 4526 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.028(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     469
_refine_ls_number_reflns         9932
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0198
_refine_ls_R_factor_gt           0.0191
_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^)+(0.0215P)^2^+1.0066P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0451
_refine_ls_wR_factor_ref         0.0455
_reflns_Friedel_coverage         0.912
_reflns_Friedel_fraction_full    0.935
_reflns_Friedel_fraction_max     0.912
_reflns_number_gt                9740
_reflns_number_total             9932
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt04307a2.cif
_cod_data_source_block           jml1702
_cod_database_code               7701854
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C39H34F9P3Ru
_chemical_oxdiff_usercomment     'Lewis Hall lmh-3-200'
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     29.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C27(H27A,H27B)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), 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)
;
_olex2_date_sample_data_collection 2017-02-07
_olex2_date_sample_submission    2017-01-31
_olex2_exptl_crystal_mounting_method 'oil on micromount'
_olex2_submission_original_sample_id lmh-3-200
_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 1.598
_oxdiff_exptl_absorpt_empirical_full_min 0.853