Synthesis of Heavy Fluorous Ruthenium Metathesis Catalysts Using the Stereoselective Addition of Polyfluoroalkyllithium to Sterically Hindered Diimines
Hošek, Jan; Rybáčková, Markéta; Čejka, Jan; Cvačka, Josef; Kvíčala, Jaroslav; Organometallics 34 (2015) 3327–; doi:10.1021/acs.organomet.5b00325

data_4086011
_publ_section_title
;
 Synthesis of Heavy Fluorous Ruthenium Metathesis Catalysts Using the
 Stereoselective Addition of Polyfluoroalkyllithium to Sterically Hindered
 Diimines
;
_journal_issue                   13
_journal_name_full               Organometallics
_journal_page_first              3327
_journal_paper_doi               10.1021/acs.organomet.5b00325
_journal_volume                  34
_journal_year                    2015
_chemical_formula_moiety         'C53 H42 Cl2 F39 N2 O1 Ru1'
_chemical_formula_sum            'C53 H42 Cl2 F39 N2 O Ru'
_chemical_formula_weight         1635.83
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_cell_angle_alpha                82.152(2)
_cell_angle_beta                 86.678(3)
_cell_angle_gamma                70.303(3)
_cell_formula_units_Z            2
_cell_length_a                   11.1744(4)
_cell_length_b                   12.2338(3)
_cell_length_c                   24.4267(7)
_cell_measurement_reflns_used    10206
_cell_measurement_temperature    180
_cell_measurement_theta_max      76
_cell_measurement_theta_min      4
_cell_volume                     3114.17(17)
_computing_cell_refinement       'CrysAlis, (Oxford Diffraction, 2002)'
_computing_data_collection       'Xcalibur, (Oxford Diffraction, 2002)'
_computing_data_reduction        'CrysAlis, (Oxford Diffraction, 2002)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'SHELXS 86 (Sheldrick, 1986)'
_diffrn_ambient_temperature      180
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.956
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Oxford Diffraction XCALIBUR'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54180
_diffrn_reflns_av_R_equivalents  0.038
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            22523
_diffrn_reflns_theta_full        67.730
_diffrn_reflns_theta_max         76.101
_diffrn_reflns_theta_min         4.202
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.293
_exptl_absorpt_correction_T_max  0.55
_exptl_absorpt_correction_T_min  0.39
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrysAlis, (Oxford Diffraction, 2002)'
_exptl_crystal_colour            green
_exptl_crystal_density_diffrn    1.744
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1622
_exptl_crystal_size_max          0.210
_exptl_crystal_size_mid          0.170
_exptl_crystal_size_min          0.140
_refine_diff_density_max         2.20
_refine_diff_density_min         -2.06
_refine_ls_extinction_coef       11(3)
_refine_ls_extinction_method     'Larson (1970), Equation 22'
_refine_ls_goodness_of_fit_ref   0.9691
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     884
_refine_ls_number_reflns         12437
_refine_ls_number_restraints     252
_refine_ls_R_factor_all          0.1168
_refine_ls_R_factor_gt           0.1058
_refine_ls_shift/su_max          0.0009674
_refine_ls_shift/su_mean         0.0000648
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) 
 [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] 
 where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax 
 Method = Robust Weighting (Prince, 1982) 
 W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ 
 A~i~ are: 
 0.557E+04 0.939E+04 0.596E+04 0.258E+04 642. 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.3075
_refine_ls_wR_factor_gt          0.2903
_refine_ls_wR_factor_ref         0.3075
_reflns_limit_h_max              14
_reflns_limit_h_min              -14
_reflns_limit_k_max              15
_reflns_limit_k_min              -14
_reflns_limit_l_max              30
_reflns_limit_l_min              0
_reflns_number_gt                10477
_reflns_number_total             12437
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   2.89
_oxford_diffrn_Wilson_scale      0.17
_oxford_refine_ls_r_factor_ref   0.1168
_oxford_refine_ls_scale          2.90(6)
_oxford_reflns_number_all        12437
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_cod_data_source_file            om5b00325_si_002.cif
_cod_data_source_block           jh339
_cod_depositor_comments
'Adding full bibliography for 4086010--4086011.cif.'
_cod_original_cell_volume        3114.16(17)
_cod_original_sg_symbol_H-M      'P -1 '
_cod_original_formula_sum        'C53 H42 Cl2 F39 N2 O1 Ru1'
_cod_database_code               4086011
_iucr_refine_instruction_details_constraints
;
BLOCK SCALE X'S, U'S 
CONT EXTPARAM 
RIDE C   (   6,X'S) H   (  61,X'S) 
RIDE C   (   7,X'S) H   (  71,X'S) 
RIDE C   (  11,X'S) H   ( 111,X'S) 
RIDE C   (  13,X'S) H   ( 131,X'S) 
RIDE C   (  15,X'S) H   ( 151,X'S) H   ( 152,X'S) H   ( 153,X'S) 
RIDE C   (  16,X'S) H   ( 162,X'S) H   ( 163,X'S) H   ( 161,X'S) 
RIDE C   (  17,X'S) H   ( 171,X'S) H   ( 173,X'S) H   ( 172,X'S) 
RIDE C   (  20,X'S) H   ( 201,X'S) 
RIDE C   (  22,X'S) H   ( 221,X'S) 
RIDE C   (  24,X'S) H   ( 241,X'S) H   ( 243,X'S) H   ( 242,X'S) 
RIDE C   (  25,X'S) H   ( 252,X'S) H   ( 251,X'S) H   ( 253,X'S) 
RIDE C   (  26,X'S) H   ( 261,X'S) H   ( 263,X'S) H   ( 262,X'S) 
RIDE C   (  27,X'S) H   ( 272,X'S) H   ( 271,X'S) 
RIDE C   (  28,X'S) H   ( 281,X'S) H   ( 282,X'S) 
RIDE C   (  48,X'S) H   ( 481,X'S) H   ( 482,X'S) 
RIDE C   (  49,X'S) H   ( 491,X'S) H   ( 492,X'S) 
RIDE C   (  72,X'S) H   ( 721,X'S) 
RIDE C   (  73,X'S) H   ( 731,X'S) 
RIDE C   (  75,X'S) H   ( 751,X'S) 
RIDE C   (  77,X'S) H   ( 771,X'S) 
RIDE C   (  78,X'S) H   ( 781,X'S) H   ( 783,X'S) H   ( 782,X'S) 
RIDE C   (  79,X'S) H   ( 792,X'S) H   ( 791,X'S) H   ( 793,X'S) 
END                                                                             
;
_iucr_refine_instruction_details_restraints
;
NO 
REM   SHIFTLIMIT   START (DO NOT REMOVE THIS LINE) 
REM   SHIFTLIMIT   END (DO NOT REMOVE THIS LINE) 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
DISTANCE 1.550000 , 0.015000 = C(27) TO C(28) 
DISTANCE 1.550000 , 0.010000 = C(28) TO C(29) 
DISTANCE 1.550000 , 0.010000 = C(29) TO C(30) 
DISTANCE 1.550000 , 0.010000 = C(54) TO C(53) 
DISTANCE 1.550000 , 0.010000 = C(32) TO C(33) 
DISTANCE 1.550000 , 0.010000 = C(33) TO C(34) 
DISTANCE 1.350000 , 0.010000 = C(29) TO F(35) 
DISTANCE 1.350000 , 0.010000 = C(29) TO F(36) 
DISTANCE 1.350000 , 0.020000 = C(30) TO F(37) 
DISTANCE 1.350000 , 0.0010000 = C(30) TO F(38) 
DISTANCE 1.350000 , 0.020000 = C(31) TO F(39) 
DISTANCE 1.350000 , 0.010000 = C(31) TO F(40) 
DISTANCE 1.350000 , 0.010000 = C(32) TO F(42) 
DISTANCE 1.350000 , 0.020000 = C(33) TO F(44) 
DISTANCE 1.350000 , 0.020000 = C(33) TO F(43) 
DISTANCE 1.350000 , 0.0050000 = C(34) TO F(45) 
DISTANCE 1.350000 , 0.0050000 = C(34) TO F(46) 
DISTANCE 1.350000 , 0.010000 = C(34) TO F(47) 
DISTANCE 1.350000 , 0.020000 = C(51) TO F(58) 
DISTANCE 1.350000 , 0.020000 = C(51) TO F(59) 
DISTANCE 1.350000 , 0.0050000 = C(52) TO F(60) 
DISTANCE 1.350000 , 0.0050000 = C(53) TO F(62) 
DISTANCE 1.350000 , 0.0050000 = C(54) TO F(65) 
DISTANCE 1.350000 , 0.0050000 = C(55) TO F(66) 
DISTANCE 1.350000 , 0.0050000 = C(55) TO F(67) 
DISTANCE 1.350000 , 0.0050000 = C(55) TO F(68) 
DISTANCE 1.350000 , 0.0200000 = C(85) TO F(96) 
DISTANCE 1.350000 , 0.0200000 = C(85) TO F(98) 
REM DELU 0.001 FOR C(28) UNTIL F(47) 
REM DELU 0.001 FOR C(49) UNTIL F(68) 
REM SIMU 0.001 FOR C(28) UNTIL F(47) 
REM SIMU 0.001 FOR C(49) UNTIL F(68) 
DELU 0.001 C(27) C(28) C(29) F(35) F(36) 
DELU 0.01 C(30) F(37) F(38) C(31) F(39) F(40) 
DELU 0.01 C(32) F(41) F(42) C(33) F(43) F(44) 
DELU 0.01 C(34) F(45) F(46) F(47) 
SIMU 0.001 C(27) C(28) C(29) F(35) F(36) 
SIMU 0.01 C(30) F(37) F(38) C(31) F(39) F(40) 
SIMU 0.01 C(32) F(41) F(42) C(33) F(43) F(44) 
SIMU 0.01 C(34) F(45) F(46) F(47) 
REM DRUHY RETEZEC 
DELU 0.01 C(51) F(58) F(59) C(52) F(60) F(61) 
DELU 0.01 C(53) F(62) F(63) C(54) F(64) F(65) 
DELU 0.01 C(55) F(66) F(67) F(68) 
SIMU 0.01 C(51) F(58) F(59) C(52) F(60) F(61) 
SIMU 0.01 C(53) F(62) F(63) C(54) F(64) F(65) 
SIMU 0.01 C(55) F(66) F(67) F(68) 
REM ETHYLEN 
DELU 0.01 C(6) C(27) C(28) 
SIMU 0.01 C(6) C(27) C(28) 
END                                                                             
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