Synthesis and Reactivity of Dioxazirconacyclohexenes: Development of a Zirconium‒Oxo-Mediated Alkyne‒Aldehyde Coupling Reaction
Kortman, Gregory D.; Orr, Meghan J.; Hull, Kami L.; Organometallics 34 (2015) 1013–; doi:10.1021/om5008727

data_4085591
_publ_section_title
;
 Synthesis and Reactivity of Dioxazirconacyclohexenes: Development of a
 Zirconium--Oxo-Mediated Alkyne--Aldehyde Coupling Reaction
;
_journal_issue                   6
_journal_name_full               Organometallics
_journal_page_first              1013
_journal_paper_doi               10.1021/om5008727
_journal_volume                  34
_journal_year                    2015
_chemical_formula_moiety         'C42 H45 F3 O2 Zr, C6 H6'
_chemical_formula_sum            'C48 H51 F3 O2 Zr'
_chemical_formula_weight         808.10
_chemical_name_systematic
'Bis(pentamethylcyclopentadienyl)-zirconium (IV) (Z)-1,2-diphenyl-3-(4-(trifluoromethyl)phenyl)prop-1-ene-1,3-bis(olate)'
_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             2014-07-14
_audit_creation_method
;
Olex2 1.2
(compiled 2014.06.27 svn.r2953 for OlexSys, GUI svn.r4855)
;
_cell_angle_alpha                78.945(4)
_cell_angle_beta                 87.194(5)
_cell_angle_gamma                83.212(5)
_cell_formula_units_Z            2
_cell_length_a                   10.0520(9)
_cell_length_b                   10.4234(10)
_cell_length_c                   20.1422(19)
_cell_measurement_temperature    173.15
_cell_volume                     2056.0(3)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2013)'
_diffrn_ambient_temperature      173.15
_diffrn_detector                 CCD
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_device       'Bruker D8 Venture/Photon 100'
_diffrn_measurement_method       'profile data from \f and \w scans'
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0621
_diffrn_reflns_av_unetI/netI     0.0394
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            54297
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.307
_diffrn_reflns_theta_min         2.003
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.318
_exptl_absorpt_correction_T_max  0.96709
_exptl_absorpt_correction_T_min  0.89129
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details   'SHELXTL/XPREP V2013/3 (Bruker, 2013)'
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.305
_exptl_crystal_description       plate
_exptl_crystal_F_000             844
_exptl_crystal_recrystallization_method
'grown from slow evaporation of a pentane/benzene mixture (20:1) at room temperature.'
_exptl_crystal_size_max          0.476
_exptl_crystal_size_mid          0.243
_exptl_crystal_size_min          0.163
_refine_diff_density_max         0.421
_refine_diff_density_min         -0.471
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     506
_refine_ls_number_reflns         8248
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0413
_refine_ls_R_factor_gt           0.0337
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0316P)^2^+1.2174P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0783
_refine_ls_wR_factor_ref         0.0830
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7209
_reflns_number_total             8248
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5008727_si_001.cif
_cod_data_source_block           cmo1jcopy
_cod_depositor_comments          'Adding full bibliography for 4085591.cif.'
_cod_database_code               4085591
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.950
_shelx_estimated_absorpt_t_min   0.863
_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. Restrained distances
 C42-F1
 1.36 with sigma of 0.0001
3. Uiso/Uaniso restraints and constraints
Uanis(F2) = Uanis(F2D)
Uanis(F3) = Uanis(F3D)
Uanis(F1) = Uanis(F1D)
Uanis(C1S) = Uanis(C1D)
Uanis(C2S) = Uanis(C2D)
Uanis(C3S) = Uanis(C3D)
Uanis(C4S) = Uanis(C4D)
Uanis(C5S) = Uanis(C5D)
Uanis(C6S) = Uanis(C6D)
4. Others
 Sof(F1D)=Sof(F2D)=Sof(F3D)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
 Sof(C1D)=Sof(H1D)=Sof(C2D)=Sof(H2D)=Sof(C3D)=Sof(H3D)=Sof(C4D)=Sof(H4D)=
 Sof(C5D)=Sof(H5D)=Sof(C6D)=Sof(H6D)=1-FVAR(2)
 Sof(C1S)=Sof(H1S)=Sof(C2S)=Sof(H2S)=Sof(C3S)=Sof(H3S)=Sof(C4S)=Sof(H4S)=
 Sof(C5S)=Sof(H5S)=Sof(C6S)=Sof(H6S)=FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C25(H25), C26(H26), C27(H27), C28(H28), C29(H29), C31(H31), C32(H32),
 C33(H33), C34(H34), C35(H35), C37(H37), C38(H38), C40(H40), C41(H41), C1S(H1S),
  C2S(H2S), C3S(H3S), C4S(H4S), C5S(H5S), C6S(H6S), C1D(H1D), C2D(H2D),
 C3D(H3D), C4D(H4D), C5D(H5D), C6D(H6D)
5.b Fitted hexagon refined as free rotating group:
 C1S(C2S,C3S,C4S,C5S,C6S), C1D(C2D,C3D,C4D,C5D,C6D)
5.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              31411
_shelx_hkl_checksum              94823
_olex2_exptl_crystal_mounting_method
'the crystal was mounted using oil (Parantone-N, Exxon) to a 0.3 mm cryo-loop (Hampton Research) with the (-2, 1, -1) scattering plane roughly normal to the spinle axis.'
_olex2_submission_original_sample_id 2GDK-155
_olex2_submission_special_instructions 'No special instructions were received'