M=Nα Cycloaddition and Nα-Nβ Insertion in the Reactions of Titanium Hydrazido Compounds with Alkynes: A Combined Experimental and Computational Study
A. Daniel Schofield; Ainara Nova; Jonathan D. Selby; Catherine D. Manley; Andrew D. Schwarz; Eric Clot; Philip Mountford; Journal of the American Chemical Society 132 (2010) 10484–10497; doi:10.1021/ja1036513

data_4102744
_publ_contact_author
;
 Professor P Mountford           
 Chemistry Reaearch Laboratory
 Mansfield Road
 Oxford
 OX1 3TA
 UK
;
_publ_contact_author_email       Philip.Mountford@chem.ox.ac.uk
_publ_contact_author_fax         '+44 1865 285141'
_publ_contact_author_phone       '+44 1865 285140'
_publ_section_title
;
 M=N\a Cycloaddition and N\a-N\b Insertion in the Reactions of Titanium
 Hydrazido Compounds with Alkynes: A Combined Experimental and
 Computational Study
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10484
_journal_page_last               10497
_journal_paper_doi               10.1021/ja1036513
_journal_volume                  132
_journal_year                    2010
_chemical_formula_moiety         'C12 H6 F4'
_chemical_formula_sum            'C12 H6 F4'
_chemical_formula_weight         226.17
_chemical_name_systematic
;
MeCC(2,3,5,6-C6F4)CCMe
;
_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   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                108.7974(19)
_cell_angle_beta                 98.662(2)
_cell_angle_gamma                108.823(2)
_cell_formula_units_Z            1
_cell_length_a                   5.0929(2)
_cell_length_b                   7.3053(3)
_cell_length_c                   7.6069(4)
_cell_measurement_reflns_used    999
_cell_measurement_temperature    150
_cell_measurement_theta_max      27
_cell_measurement_theta_min      5
_cell_volume                     243.14(2)
_computing_cell_refinement       'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_computing_data_collection       'COLLECT (Nonius, 1997-2001).'
_computing_data_reduction        'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_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    'SIR92 (Altomare et al., 1994)'
_diffrn_ambient_temperature      150
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_device       'Nonius KappaCCD'
_diffrn_measurement_device_type  Area
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.026
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            3462
_diffrn_reflns_theta_full        27.030
_diffrn_reflns_theta_max         27.582
_diffrn_reflns_theta_min         5.153
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.143
_exptl_absorpt_correction_T_max  0.97
_exptl_absorpt_correction_T_min  0.89
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.545
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             114
_exptl_crystal_size_max          0.40
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.20
_refine_diff_density_max         0.45
_refine_diff_density_min         -0.47
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   1.0765
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     73
_refine_ls_number_reflns         980
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0560
_refine_ls_R_factor_gt           0.0530
_refine_ls_shift/su_max          0.000110
_refine_ls_structure_factor_coef F
_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: 
 1.63 0.742 1.06 -0.597E-01 0.216 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0650
_refine_ls_wR_factor_gt          0.0617
_refine_ls_wR_factor_ref         0.0609
_reflns_limit_h_max              6
_reflns_limit_h_min              -6
_reflns_limit_k_max              8
_reflns_limit_k_min              -9
_reflns_limit_l_max              9
_reflns_limit_l_min              0
_reflns_number_gt                1018
_reflns_number_total             1109
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   2.00
_oxford_diffrn_Wilson_scale      0.06
_oxford_refine_ls_r_factor_ref   0.0519
_oxford_refine_ls_scale          4.55(2)
_oxford_reflns_number_all        1109
_oxford_reflns_threshold_expression_ref I>3.0\s(I)
_cod_data_source_file            ja1036513_si_002_5.cif
_cod_data_source_block           compound_19
_cod_original_sg_symbol_H-M      'P -1 '
_cod_database_code               4102744