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_4102742
_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         'C41 H52 N6  Si2 Ti1 . 0.5 (C4 H10 O)'
_chemical_formula_sum            'C43 H57 N6 O0.5 Si2 Ti'
_chemical_formula_weight         770.04
_chemical_name_systematic
;
 Ti(N2Npy){NC(Ph)C(Me)NPh2}(py). 0.5(Et2O)
;
_space_group_IT_number           15
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                90
_cell_angle_beta                 102.0841(15)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   39.2342(10)
_cell_length_b                   10.6636(3)
_cell_length_c                   20.7574(6)
_cell_measurement_reflns_used    7729
_cell_measurement_temperature    150
_cell_measurement_theta_max      25
_cell_measurement_theta_min      5
_cell_volume                     8492.0(4)
_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 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device_type  'Nonius KappaCCD'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.048
_diffrn_reflns_limit_h_max       46
_diffrn_reflns_limit_h_min       -47
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            13456
_diffrn_reflns_theta_full        25.356
_diffrn_reflns_theta_max         25.356
_diffrn_reflns_theta_min         5.113
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.296
_exptl_absorpt_correction_T_max  0.99
_exptl_absorpt_correction_T_min  0.99
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.205
_exptl_crystal_description       needle
_exptl_crystal_F_000             3288
_exptl_crystal_size_max          0.60
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.42
_refine_diff_density_min         -0.32
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   1.1169
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     474
_refine_ls_number_reflns         4782
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0847
_refine_ls_R_factor_gt           0.0437
_refine_ls_shift/su_max          0.001771
_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: 
 1.21 -0.163 1.18 -0.592E-01 0.321 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0555
_refine_ls_wR_factor_gt          0.0431
_refine_ls_wR_factor_ref         0.0431
_reflns_limit_h_max              46
_reflns_limit_h_min              -47
_reflns_limit_k_max              12
_reflns_limit_k_min              0
_reflns_limit_l_max              24
_reflns_limit_l_min              0
_reflns_number_gt                4782
_reflns_number_total             7683
_reflns_threshold_expression     I>3.0\s(I)
_oxford_diffrn_Wilson_B_factor   2.27
_oxford_diffrn_Wilson_scale      49.45
_oxford_refine_ls_scale          0.1432(2)
_cod_data_source_file            ja1036513_si_002_3.cif
_cod_data_source_block           compound_10
_cod_original_sg_symbol_H-M      'C 1 2/c 1 '
_cod_original_formula_sum        'C43 H57 N6 O0.50 Si2 Ti1'
_cod_database_code               4102742