Catalytic Dehydrocoupling of Amine–Boranes using Cationic Zirconium(IV)–Phosphine Frustrated Lewis Pairs
Metters, Owen J.; Flynn, Stephanie R.; Dowds, Christiana K.; Sparkes, Hazel A.; Manners, Ian; Wass, Duncan F.; ACS Catalysis 6 (2016) 6601–; doi:10.1021/acscatal.6b02211

data_4513944
_publ_section_title
;
 Catalytic Dehydrocoupling of Amine--Boranes using Cationic
 Zirconium(IV)--Phosphine Frustrated Lewis Pairs
;
_journal_issue                   10
_journal_name_full               'ACS Catalysis'
_journal_page_first              6601
_journal_paper_doi               10.1021/acscatal.6b02211
_journal_volume                  6
_journal_year                    2016
_chemical_formula_moiety         'C35 H59 B N O Zr, B C24 F20, 0.5(C6 H5 Cl)'
_chemical_formula_sum            'C62 H61.5 B2 Cl0.5 F20 N O Zr'
_chemical_formula_weight         1347.18
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2016-02-24
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                68.2519(9)
_cell_angle_beta                 74.0118(10)
_cell_angle_gamma                72.1388(10)
_cell_formula_units_Z            2
_cell_length_a                   10.8416(2)
_cell_length_b                   16.5385(3)
_cell_length_c                   18.9008(3)
_cell_measurement_reflns_used    9890
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.86
_cell_measurement_theta_min      2.33
_cell_volume                     2945.45(9)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'Bruker Apex II kappa CCD area detector'
_diffrn_measurement_device_type  'Bruker Apex II kappa CCD area detector'
_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  0.0304
_diffrn_reflns_av_unetI/netI     0.0285
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            54910
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.933
_diffrn_reflns_theta_min         1.497
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.316
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.7052
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0462 before and 0.0409 after correction.
The Ratio of minimum to maximum transmission is 0.9458.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.519
_exptl_crystal_description       block
_exptl_crystal_F_000             1374
_exptl_crystal_size_max          0.57
_exptl_crystal_size_mid          0.38
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.150
_refine_diff_density_min         -0.782
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     979
_refine_ls_number_reflns         14101
_refine_ls_number_restraints     492
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0439
_refine_ls_R_factor_gt           0.0362
_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^)+(0.0420P)^2^+2.3678P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0877
_refine_ls_wR_factor_ref         0.0925
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12266
_reflns_number_total             14101
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs6b02211_si_002.cif
_cod_data_source_block           21
_cod_depositor_comments
'Adding full bibliography for 4513943--4513945.cif.'
_cod_original_formula_sum        'C62 H61.50 B2 Cl0.50 F20 N O Zr'
_cod_database_code               4513944
_shelxl_version_number           2013-4
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
C63 \\sim C62 \\sim C61 \\sim C60 \\sim C65 \\sim C64: within 2A with sigma of
0.003 and sigma for terminal atoms of 0.006
C48 \\sim C53 \\sim C53A \\sim C51 \\sim C52 \\sim C52A \\sim C51A \\sim C50
\\sim C50A \\sim C49 \\sim C49A \\sim C48A: within 2A with sigma of 0.003 and
sigma for terminal atoms of 0.006
F15 \\sim F15A \\sim F14 \\sim F14A \\sim F13A \\sim F13 \\sim F12A \\sim F12
\\sim F11A \\sim F11: within 2A with sigma of 0.003 and sigma for terminal
atoms of 0.006
C49A \\sim C49 \\sim F11A \\sim F11: within 2A with sigma of 0.003 and sigma
for terminal atoms of 0.006
C56A \\sim C56 \\sim C57A \\sim C57 \\sim C58A \\sim C58 \\sim C59A \\sim C59
\\sim C54A \\sim C54 \\sim C55A \\sim C55: within 2A with sigma of 0.003 and
sigma for terminal atoms of 0.006
F20A \\sim F20 \\sim F19A \\sim F19 \\sim F18 \\sim F18A \\sim F17 \\sim F17A
\\sim F16 \\sim F16A: within 2A with sigma of 0.003 and sigma for terminal
atoms of 0.006
Uanis(C48) = Uanis(C48A)
Uanis(C54) = Uanis(C54A)
3. Others
 Fixed Sof: F11(0.59824) F20(0.59824) F16(0.59824) F18(0.59824) F15(0.59824)
 F14(0.59824) F19(0.59824) F13(0.59824) F17(0.59824) F12(0.59824) C48(0.59824)
 C49(0.59824) C50(0.59824) C51(0.59824) C52(0.59824) C53(0.59824) C54(0.59824)
 C59(0.59824) C58(0.59824) C57(0.59824) C56(0.59824) C55(0.59824) Cl1(0.5)
 C60(0.5) C61(0.5) H61(0.5) C62(0.5) H62(0.5) C63(0.5) H63(0.5) C64(0.5)
 H64(0.5) C65(0.5) H65(0.5) C54A(0.40176) C59A(0.40176) C58A(0.40176)
 C57A(0.40176) C56A(0.40176) C55A(0.40176) F20A(0.40176) F19A(0.40176)
 F18A(0.40176) F17A(0.40176) F16A(0.40176) C48A(0.40176) C53A(0.40176)
 C52A(0.40176) C51A(0.40176) C50A(0.40176) C49A(0.40176) F15A(0.40176)
 F14A(0.40176) F13A(0.40176) F12A(0.40176) F11A(0.40176)
4.a Ternary CH refined with riding coordinates:
 C24(H24), C21(H21)
4.b Aromatic/amide H refined with riding coordinates:
 C29(H29), C31(H31), C61(H61), C62(H62), C63(H63), C64(H64), C65(H65)
4.c Fitted hexagon refined as free rotating group:
 C48(C49,C50,C51,C52,C53), C54(C59,C58,C57,C56,C55), C60(C61,C62,C63,C64,C65),
 C54A(C59A,C58A,C57A,C56A,C55A), C48A(C53A,C52A,C51A,C50A,C49A)
4.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C20(H20A,H20B,H20C), C33(H33A,H33B,H33C), C7(H7A,H7B,H7C),
 C35(H35A,H35B,H35C), C9(H9A,H9B,H9C), C19(H19A,H19B,H19C), C17(H17A,H17B,H17C),
  C26(H26A,H26B,H26C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C), C23(H23A,H23B,
 H23C), C22(H22A,H22B,H22C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C34(H34A,
 H34B,H34C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              35318
_shelx_hkl_checksum              33403
_olex2_submission_special_instructions 'No special instructions were received'