Cationic and Neutral Cp*M(NO)(κ(2)-Ph2PCH2CH2PPh2) Complexes of Molybdenum and Tungsten: Lewis-Acid-Induced Intramolecular C-H Activation.
Handford, Rex C.; Wakeham, Russell J.; Patrick, Brian O.; Legzdins, Peter; Inorganic chemistry 56 (2017) 3612–3622; doi:10.1021/acs.inorgchem.7b00027

data_4345314
_publ_section_title
;
 Cationic and Neutral Cp*M(NO)(\k(2)-Ph2PCH2CH2PPh2) Complexes of
 Molybdenum and Tungsten: Lewis-Acid-Induced Intramolecular C-H
 Activation.
;
_journal_issue                   6
_journal_name_full               'Inorganic chemistry'
_journal_page_first              3612
_journal_page_last               3622
_journal_paper_doi               10.1021/acs.inorgchem.7b00027
_journal_volume                  56
_journal_year                    2017
_chemical_formula_moiety         'C37 H40 N2 O P2 W, 2(C F3 O3 S)'
_chemical_formula_sum            'C39 H40 F6 N2 O7 P2 S2 W'
_chemical_formula_weight         1072.64
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-06-03
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 105.577(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.7531(10)
_cell_length_b                   25.536(3)
_cell_length_c                   15.7710(15)
_cell_measurement_reflns_used    9935
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      30.026
_cell_measurement_theta_min      2.68
_cell_volume                     4171.5(7)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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      90(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 0.999
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_device       'Bruker D8 Kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'TRIUMPH curved-crystal'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0273
_diffrn_reflns_av_unetI/netI     0.0521
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            19288
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.048
_diffrn_reflns_theta_min         1.595
_diffrn_source                   'sealed X-ray tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.024
_exptl_absorpt_correction_T_max  0.834
_exptl_absorpt_correction_T_min  0.626
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0820 before and 0.0435 after correction.
The Ratio of minimum to maximum transmission is 0.7508.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.708
_exptl_crystal_description       needle
_exptl_crystal_F_000             2136
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.610
_refine_diff_density_min         -0.857
_refine_diff_density_rms         0.134
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     624
_refine_ls_number_reflns         11951
_refine_ls_number_restraints     675
_refine_ls_restrained_S_all      1.002
_refine_ls_R_factor_all          0.0485
_refine_ls_R_factor_gt           0.0330
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0289P)^2^+0.9174P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0653
_refine_ls_wR_factor_ref         0.0704
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9593
_reflns_number_total             11951
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic7b00027_si_002.cif
_cod_data_source_block           pl518
_cod_depositor_comments
'Adding full bibliography for 4345311--4345314.cif.'
_cod_database_code               4345314
_shelx_estimated_absorpt_t_max   0.839
_shelx_estimated_absorpt_t_min   0.418
_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
 F4A-F6A
 2.19 with sigma of 0.02
 S2A-S2
 -0.22 with sigma of 0.02
 S2-C39 \\sim S2A-C39A
 with sigma of 0.02
 F6A-C39A \\sim F4A-C39A \\sim F5A-C39A \\sim F5-C39 \\sim F4-C39 \\sim F6-C39
 with sigma of 0.02
 F5A-F6A \\sim F6A-F4A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(F3) = Uanis(F3A)
Uanis(S2A) = Uanis(S2)
Uanis(O7) = Uanis(O7A)
Uanis(O6) = Uanis(O6A)
Uanis(O5) = Uanis(O5A)
Uanis(F5) = Uanis(F5A)
Uanis(F4A) = Uanis(F6)
4. 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
5. Others
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(O2A)=Sof(O3A)=Sof(O4A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(O2)=Sof(O3)=Sof(O4)=FVAR(1)
 Sof(S2A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(O5A)=Sof(O6A)=Sof(O7A)=Sof(C39A)=1-
 FVAR(2)
 Sof(S2)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(O5)=Sof(O6)=Sof(O7)=Sof(C39)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B)
6.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C15(H15), C16(H16), C17(H17), C19(H19), C20(H20),
 C21(H21), C22(H22), C23(H23), C25(H25), C26(H26), C27(H27), C28(H28), C29(H29),
  C31(H31), C32(H32), C33(H33), C34(H34), C35(H35)
6.c 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), C37(H37A,H37B,H37C)
;
_shelx_res_checksum              24169
_shelx_hkl_checksum              91364
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'