Trivalent Titanocene Alkyls and Hydrides as Well-Defined, Highly Active, and Broad Scope Precatalysts for Dehydropolymerization of Amine-Boranes.
LaPierre, Etienne A.; Patrick, Brian O.; Manners, Ian; Journal of the American Chemical Society  (2019) –; doi:10.1021/jacs.9b11112

data_4133764
_publ_section_title
;
 Trivalent Titanocene Alkyls and Hydrides as Well-Defined, Highly Active,
 and Broad Scope Precatalysts for Dehydropolymerization of Amine-Boranes.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b11112
_journal_year                    2019
_chemical_formula_moiety         '1(C21 H36.99 B1 N1 Ti)'
_chemical_formula_sum            'C21 H37 B N Ti'
_chemical_formula_weight         362.22
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                71.520(4)
_cell_angle_beta                 84.686(4)
_cell_angle_gamma                76.424(4)
_cell_formula_units_Z            6
_cell_length_a                   8.5727(8)
_cell_length_b                   16.9926(15)
_cell_length_c                   23.2758(18)
_cell_measurement_reflns_used    9640
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      22.42
_cell_measurement_theta_min      2.44
_cell_volume                     3125.3(5)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2016)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2016)'
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.961
_diffrn_measured_fraction_theta_max 0.962
_diffrn_measurement_device       'Bruker-Nonius Kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0691
_diffrn_reflns_Laue_measured_fraction_full 0.961
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            12416
_diffrn_reflns_point_group_measured_fraction_full 0.961
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        22.479
_diffrn_reflns_theta_max         22.479
_diffrn_reflns_theta_min         0.923
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.413
_exptl_absorpt_correction_T_max  0.984
_exptl_absorpt_correction_T_min  0.878
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.

Final HKLF 4 output contains 43520 reflections, Rint = 0.0802
 (13373 with I > 3sig(I), Rint = 0.0421)
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.155
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1182
_exptl_crystal_recrystallization_method
'The material was recrystallised from hexanes by slow evaporation'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.376
_refine_diff_density_min         -0.382
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     901
_refine_ls_number_reflns         12416
_refine_ls_number_restraints     2811
_refine_ls_restrained_S_all      0.984
_refine_ls_R_factor_all          0.1126
_refine_ls_R_factor_gt           0.0658
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0543P)^2^+4.4143P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1362
_refine_ls_wR_factor_ref         0.1667
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8520
_reflns_number_total             12416
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b11112_si_002.cif
_cod_data_source_block           im003
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_database_code               4133764
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.984
_shelx_estimated_absorpt_t_min   0.922
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.7166(10)
 0.2834(10)
2. Fixed Uiso
 At 1.2 times of:
  All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All B(H,H,H) groups, All C(H,H,H) groups
3. Restrained distances
 C30A-C25A \\sim C30-C25 \\sim C31A-C26A \\sim C31-C26 \\sim C27A-C22A \\sim
C27-C22 \\sim C28A-C23A ~
 C28-C23 \\sim C29A-C24A \\sim C29-C24
 with sigma of 0.01
 Ti2-N2 \\sim Ti2-N2A
 with sigma of 0.01
 N2A-B2A \\sim N2-B2
 with sigma of 0.01
 N2-C42 \\sim N2A-C42A
 with sigma of 0.01
 B2-C42 \\sim B2A-C42A \\sim B2B-C42B
 with sigma of 0.01
 Ti3-N3 \\sim Ti2-N2
 with sigma of 0.01
 N3-B3 \\sim N2-B2
 with sigma of 0.01
 N2A-C42A \\sim N2B-C42B \\sim N3-C63
 with sigma of 0.01
 C20A-C15A \\sim C18-C13 \\sim C16A-C11A \\sim C19-C14 \\sim C17A-C12A \\sim
C20-C15 \\sim C18A-C13A ~
 C16-C11 \\sim C19A-C14A \\sim C17-C12
 with sigma of 0.01
 N1-C21A \\sim N1-C21
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(C23) = Uanis(C23A)
Uanis(C26) = Uanis(C26A)
Uanis(C31) = Uanis(C31A)
Uanis(N2A) = Uanis(N2B) = Uanis(N2)
Uanis(B2A) = Uanis(B2B) = Uanis(B2)
Uanis(C11) = Uanis(C13A)
Uanis(C15) = Uanis(C12A)
Uanis(C11A) = Uanis(C14)
Uanis(C13) = Uanis(C15A)
Uanis(C14A) = Uanis(C12)
Uanis(C20A) = Uanis(C18)
Uanis(C20) = Uanis(C17A)
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 1*[Sof(N2)+Sof(H2)+Sof(B2)+Sof(H2A)+Sof(H2B)+Sof(H2C)+Sof(C42)+Sof(H42A)+
 Sof(H42B)+Sof(H42C)]+1*[Sof(N2A)+Sof(H2AA)+Sof(C42A)+Sof(H42D)+Sof(H42E)+
 Sof(H42F)+Sof(B2A)+Sof(H2AB)+Sof(H2AC)+Sof(H2AD)]+1*[Sof(B2B)+Sof(H2BA)+
 Sof(H2BB)+Sof(H2BC)+Sof(C42B)+Sof(H42G)+Sof(H42H)+Sof(H42I)+Sof(N2B)+
 Sof(H2BD)]=1 with esd of 0.001
 Sof(C1)=Sof(C2)=Sof(C3)=Sof(C4)=Sof(C5)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=
 Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=1-FVAR(1)
 Sof(C1A)=Sof(C2A)=Sof(C3A)=Sof(C4A)=Sof(C5A)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=
 Sof(H6AC)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=
 Sof(H8AC)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(C10A)=Sof(H10D)=Sof(H10E)=
 Sof(H10F)=FVAR(1)
 Sof(C11A)=Sof(C12A)=Sof(C13A)=Sof(C14A)=Sof(C15A)=Sof(C16A)=Sof(H16D)=
 Sof(H16E)=Sof(H16F)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(C18A)=
 Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C19A)=Sof(H19D)=Sof(H19E)=Sof(H19F)=
 Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(2)
 Sof(C11)=Sof(C12)=Sof(C13)=Sof(C14)=Sof(C15)=Sof(C16)=Sof(H16A)=Sof(H16B)=
 Sof(H16C)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18)=Sof(H18A)=Sof(H18B)=
 Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C20)=Sof(H20A)=Sof(H20B)=
 Sof(H20C)=FVAR(2)
 Sof(C22A)=Sof(C23A)=Sof(C24A)=Sof(C25A)=Sof(C26A)=Sof(C27A)=Sof(H27D)=
 Sof(H27E)=Sof(H27F)=Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29A)=
 Sof(H29D)=Sof(H29E)=Sof(H29F)=Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=
 Sof(C31A)=Sof(H31D)=Sof(H31E)=Sof(H31F)=1-FVAR(3)
 Sof(C22)=Sof(C23)=Sof(C24)=Sof(C25)=Sof(C26)=Sof(C27)=Sof(H27A)=Sof(H27B)=
 Sof(H27C)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29)=Sof(H29A)=Sof(H29B)=
 Sof(H29C)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C31)=Sof(H31A)=Sof(H31B)=
 Sof(H31C)=FVAR(3)
 Sof(H1BB)=Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=1-FVAR(4)
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(H1AA)=FVAR(4)
 Sof(N2)=Sof(H2)=Sof(B2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C42)=Sof(H42A)=
 Sof(H42B)=Sof(H42C)=FVAR(5)
 Sof(N2A)=Sof(H2AA)=Sof(C42A)=Sof(H42D)=Sof(H42E)=Sof(H42F)=Sof(B2A)=Sof(H2AB)=
 Sof(H2AC)=Sof(H2AD)=FVAR(6)
 Sof(B2B)=Sof(H2BA)=Sof(H2BB)=Sof(H2BC)=Sof(C42B)=Sof(H42G)=Sof(H42H)=
 Sof(H42I)=Sof(N2B)=Sof(H2BD)=FVAR(7)
7.a Ternary CH refined with riding coordinates:
 N1(H1AA), N1(H1BB), N3(H3), N2(H2), N2A(H2AA), N2B(H2BD)
7.b Me refined with riding coordinates:
 C42(H42A,H42B,H42C), C42A(H42D,H42E,H42F)
7.c Fitted pentagon refined as free rotating group:
 C1(C2,C3,C4,C5), C11(C12,C13,C14,C15), C1A(C2A,C3A,C4A,C5A), C11A(C12A,C13A,
 C14A,C15A), C22(C23,C24,C25,C26), C32(C33,C34,C35,C36), C22A(C23A,C24A,C25A,
 C26A), C43(C44,C45,C46,C47), C53(C54,C55,C56,C57)
7.d 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), C6A(H6AA,H6AB,H6AC), C7A(H7AA,H7AB,
 H7AC), C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,H9AC), C10A(H10D,H10E,H10F),
 C16A(H16D,H16E,H16F), C17A(H17D,H17E,H17F), C18A(H18D,H18E,H18F), C19A(H19D,
 H19E,H19F), C20A(H20D,H20E,H20F), C21(H21A,H21B,H21C), C27(H27A,H27B,H27C),
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,
 H31C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,
 H40B,H40C), C41(H41A,H41B,H41C), C27A(H27D,H27E,H27F), C28A(H28D,H28E,H28F),
 C29A(H29D,H29E,H29F), C30A(H30D,H30E,H30F), C31A(H31D,H31E,H31F), C48(H48A,
 H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C),
 C52(H52A,H52B,H52C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,
 H60C), C61(H61A,H61B,H61C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C),
 C21A(H21D,H21E,H21F), B2(H2A,H2B,H2C), B2A(H2AB,H2AC,H2AD), B2B(H2BA,H2BB,
 H2BC), C42B(H42G,H42H,H42I)
;
_shelx_res_checksum              15717
_shelx_hkl_checksum              28733
_olex2_diffrn_ambient_temperature_device Kryoflex
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mylar loop in oil'
_olex2_submission_original_sample_id 190421EL2
_olex2_submission_special_instructions 'No special instructions were received'