Group 3 dialkyl complexes of a rigid monoanionic NNN-donor pincer ligand: synthesis, structures, unexpected reactivity with CPh<sub>3</sub><sup>+</sup>, and hydroamination catalysis.
Vasanthakumar, Aathith; Gray, Novan A. G.; Franko, Christopher J.; Murphy, Maia C.; Emslie, David J. H.; Dalton transactions (Cambridge, England : 2003)  (2023) –; doi:10.1039/d3dt00530e

data_7712747
_publ_section_title
;
 Group 3 dialkyl complexes of a rigid monoanionic NNN-donor pincer ligand:
 synthesis, structures, unexpected reactivity with
 CPh<sub>3</sub><sup>+</sup>, and hydroamination catalysis.
;
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_paper_doi               10.1039/d3dt00530e
_journal_year                    2023
_chemical_formula_moiety         'C43 H70 N7 Sc Si2, 1.25[C7H8]'
_chemical_formula_sum            'C51.75 H80 N7 Sc Si2'
_chemical_formula_weight         901.36
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2023-02-15
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-17 deposited with the CCDC.	2023-03-31 downloaded from the CCDC.
;
_cell_angle_alpha                94.046(11)
_cell_angle_beta                 93.705(9)
_cell_angle_gamma                110.899(10)
_cell_formula_units_Z            4
_cell_length_a                   14.651(6)
_cell_length_b                   16.119(8)
_cell_length_c                   25.584(10)
_cell_measurement_reflns_used    9935
_cell_measurement_temperature    100
_cell_measurement_theta_max      23.562
_cell_measurement_theta_min      2.204
_cell_volume                     5604(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0657
_diffrn_reflns_av_unetI/netI     0.0557
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            206154
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.414
_diffrn_reflns_theta_min         1.359
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.211
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.6815
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0521 before and 0.0470 after correction.
The Ratio of minimum to maximum transmission is 0.9137.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.068
_exptl_crystal_description       block
_exptl_crystal_F_000             1954
_exptl_crystal_size_max          0.41
_exptl_crystal_size_mid          0.38
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.622
_refine_diff_density_min         -0.724
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1006
_refine_ls_number_reflns         30756
_refine_ls_number_restraints     31
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0961
_refine_ls_R_factor_gt           0.0588
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0734P)^2^+2.0193P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1385
_refine_ls_wR_factor_ref         0.1560
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19906
_reflns_number_total             30756
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00530e2.cif
_cod_data_source_block           AII2ScR2
_cod_database_code               7712747
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.949
_shelx_estimated_absorpt_t_min   0.918
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Si2B-C40A \\sim C40A-Si2A
 with sigma of 0.002
 C41A-Si2A \\sim Si2A-C43A \\sim C41B-Si2B \\sim Si2B-C43B \\sim C42B-Si2B
\\sim C42A-Si2A
 with sigma of 0.002
 C41A-C43A \\sim C43A-C42A \\sim C42A-C41A \\sim C41B-C43B \\sim C43B-C42B
\\sim C42B-C41B
 with sigma of 0.002
3. Uiso/Uaniso restraints and constraints
Uanis(Si2B) = Uanis(Si2A)
Uanis(C42A) = Uanis(C43B)
Uanis(C42B) = Uanis(C41A)
Uanis(C43A) = Uanis(C41B)
4. Others
 Sof(Si2B)=Sof(C41B)=Sof(H41D)=Sof(H41E)=Sof(H41F)=Sof(C42B)=Sof(H42D)=
 Sof(H42E)=Sof(H42F)=Sof(C43B)=Sof(H43D)=Sof(H43E)=Sof(H43F)=1-FVAR(1)
 Sof(Si2A)=Sof(C41A)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C42A)=Sof(H42A)=
 Sof(H42B)=Sof(H42C)=Sof(C43A)=Sof(H43A)=Sof(H43B)=Sof(H43C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C21(H21), C24(H24), C30(H30), C33(H33), C21A(H21A), C24A(H24A), C30A(H30A),
 C33A(H33A)
5.b Secondary CH2 refined with riding coordinates:
 C36(H36C,H36D), C40(H40C,H40D), C36A(H36A,H36B), C40A(H40A,H40B)
5.c Me refined with riding coordinates:
 C17A(H17A,H17B,H17C)
5.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C6(H6), C8(H8), C19(H19), C20(H20), C28(H28), C29(H29),
 C1A(H1A), C3A(H3A), C6A(H6A), C8A(H8A), C19A(H19A), C20A(H20A), C28A(H28A),
 C29A(H29A)
5.e Idealised Me refined as rotating group:
 C14(H14D,H14E,H14F), C15(H15D,H15E,H15F), C16(H16D,H16E,H16F), C17(H17D,H17E,
 H17F), C22(H22D,H22E,H22F), C23(H23D,H23E,H23F), C25(H25D,H25E,H25F), C26(H26D,
 H26E,H26F), C31(H31D,H31E,H31F), C32(H32E,H32F,H32D), C34(H34D,H34E,H34F),
 C35(H35D,H35E,H35F), C37(H37D,H37E,H37F), C38(H38D,H38E,H38F), C39(H39D,H39E,
 H39F), C41(H41G,H41H,H41I), C42(H42G,H42H,H42I), C43(H43G,H43H,H43I),
 C14A(H14A,H14C,H14B), C15A(H15A,H15B,H15C), C16A(H16A,H16B,H16C), C22A(H22A,
 H22B,H22C), C23A(H23A,H23B,H23C), C25A(H25A,H25B,H25C), C26A(H26A,H26B,H26C),
 C31A(H31A,H31B,H31C), C32A(H32A,H32B,H32C), C34A(H34A,H34B,H34C), C35A(H35A,
 H35B,H35C), C37A(H37A,H37B,H37C), C38A(H38A,H38B,H38C), C39A(H39A,H39B,H39C),
 C41A(H41A,H41B,H41C), C42A(H42A,H42B,H42C), C43A(H43A,H43B,H43C), C41B(H41D,
 H41E,H41F), C42B(H42D,H42E,H42F), C43B(H43D,H43E,H43F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 255 electrons were 
found in a volume of 1452\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1.25[C7H8] per Asymmetric Unit 
which account for 250 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              26145
_shelx_hkl_checksum              10071
_shelx_fab_checksum              26861
_olex2_submission_special_instructions 'No special instructions were received'