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_4102741
_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         'C36 H42 F5 N5 Si2 Ti1'
_chemical_formula_sum            'C36 H42 F5 N5 Si2 Ti'
_chemical_formula_weight         743.83
_chemical_name_systematic
;
Ti(N2Npy){N(NPh2)C(Me)C(C6F5)}
;
_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
_audit_creation_date             09-10-08
_audit_creation_method           CRYSTALS_ver_12.86
_cell_angle_alpha                103.8462(4)
_cell_angle_beta                 94.6175(5)
_cell_angle_gamma                115.8704(5)
_cell_formula_units_Z            4
_cell_length_a                   14.7234(2)
_cell_length_b                   16.5773(2)
_cell_length_c                   20.6285(3)
_cell_measurement_reflns_used    17151
_cell_measurement_temperature    150
_cell_measurement_theta_max      27
_cell_measurement_theta_min      5
_cell_volume                     4298.99(10)
_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 0.989
_diffrn_measured_fraction_theta_max 0.984
_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  0.041
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            69483
_diffrn_reflns_theta_full        25.898
_diffrn_reflns_theta_max         27.551
_diffrn_reflns_theta_min         5.111
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.305
_exptl_absorpt_correction_T_max  0.94
_exptl_absorpt_correction_T_min  0.82
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.149
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             1552
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.20
_platon_squeeze_details
; 
The discrete Fourier transform of the void region were treated as 
contributions to the A and B parts of the calculated structure factors.
;
_refine_diff_density_max         0.30
_refine_diff_density_min         -0.30
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   1.1066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     883
_refine_ls_number_reflns         13688
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0728
_refine_ls_R_factor_gt           0.0515
_refine_ls_shift/su_max          0.000769
_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: 
 0.912 0.408 0.606 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0594
_refine_ls_wR_factor_gt          0.0484
_refine_ls_wR_factor_ref         0.0460
_reflns_limit_h_max              19
_reflns_limit_h_min              -19
_reflns_limit_k_max              20
_reflns_limit_k_min              -21
_reflns_limit_l_max              26
_reflns_limit_l_min              0
_reflns_number_gt                15055
_reflns_number_total             19545
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   2.17
_oxford_diffrn_Wilson_scale      11.34
_oxford_refine_ls_r_factor_ref   0.0449
_oxford_refine_ls_scale          0.3416(3)
_oxford_reflns_number_all        19545
_oxford_reflns_threshold_expression_ref I>3.0\s(I)
_oxford_structure_analysis_title DS29
_cod_data_source_file            ja1036513_si_002_2.cif
_cod_data_source_block           compound_4
_cod_original_sg_symbol_H-M      'P -1 '
_cod_original_formula_sum        'C36 H42 F5 N5 Si2 Ti1'
_cod_database_code               4102741