Thermodynamic and Structural Factors That Influence the Redox Potentials of Tungsten‒Alkylidyne Complexes
Rudshteyn, Benjamin; Vibbert, Hunter B.; May, Richard; Wasserman, Eric; Warnke, Ingolf; Hopkins, Michael D.; Batista, Victor S.; ACS Catalysis 7 (2017) 6134–; doi:10.1021/acscatal.7b01636

data_4514190
_publ_section_title
;
 Thermodynamic and Structural Factors That Influence the Redox Potentials
 of Tungsten--Alkylidyne Complexes
;
_journal_issue                   9
_journal_name_full               'ACS Catalysis'
_journal_page_first              6134
_journal_paper_doi               10.1021/acscatal.7b01636
_journal_volume                  7
_journal_year                    2017
_chemical_formula_moiety         'C23 H44 Cl N P4 W, C4 H8 O'
_chemical_formula_sum            'C27 H52 Cl N O P4 W'
_chemical_formula_weight         749.87
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-11-23
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.148(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.5317(6)
_cell_length_b                   16.7932(7)
_cell_length_c                   14.6934(6)
_cell_measurement_reflns_used    9353
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.64
_cell_measurement_theta_min      2.31
_cell_volume                     3325.5(2)
_computing_cell_refinement       'SAINT V.8.34A (Bruker AXS Inc., 2013)'
_computing_data_collection       'APEX2 v.2014.9-0 (Bruker AXS Inc., 2014)'
_computing_data_reduction        'SAINT V.8.34A (Bruker AXS Inc., 2013)'
_computing_molecular_graphics
;
OLEX2: a complete structure solution, refinement and analysis program 
Dolomanov et al., 2009

Mercury: visualization and analysis of crystal structures
Macrae, et al., 2006

O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann.
J. Appl. Cryst. (2009). 42, 339-341;

C. F. Macrae, P. R. Edgington, P. McCabe, E. Pidcock, G. P. Shields, R. Taylor,
M. Towler and J. van de Streek, J. Appl. Cryst. (2006). 39, 453-457.
;
_computing_publication_material
;
 APEX3 v.2015.5-2 (Bruker AXS Inc., 2015)
 OLEX2 (Dolomanov et al., 2009)
;
_computing_structure_refinement  'XL-2014/7 (Sheldrick, 2015b)'
_computing_structure_solution    'XT 2014/5 (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 10.4167
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.921
_diffrn_measurement_device_type  'Bruker D8 Venture PHOTON 100 CMOS'
_diffrn_measurement_method       'omega and phi scans'
_diffrn_radiation_monochromator  mirrors
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0455
_diffrn_reflns_av_unetI/netI     0.0239
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.921
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            198766
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.921
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.546
_diffrn_reflns_theta_min         2.305
_diffrn_source                   'INCOATEC ImuS micro-focus source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.766
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6515
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0596 before and 0.0496 after correction.
The Ratio of minimum to maximum transmission is 0.8732.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.498
_exptl_crystal_description       block
_exptl_crystal_F_000             1520
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.686
_refine_diff_density_min         -0.401
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     361
_refine_ls_number_reflns         9390
_refine_ls_number_restraints     253
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.0395
_refine_ls_R_factor_gt           0.0209
_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^)+(0.0114P)^2^+2.7836P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0338
_refine_ls_wR_factor_ref         0.0370
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7477
_reflns_number_total             9390
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs7b01636_si_004.cif
_cod_data_source_block           0166_hunter
_cod_database_code               4514190
_shelx_estimated_absorpt_t_max   0.806
_shelx_estimated_absorpt_t_min   0.640
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 P2-C18 \\sim P2-C17 \\sim P1-C13 \\sim P1-C14 \\sim P3-C20 \\sim P3-C19 \\sim
P4-C23 \\sim P4-C23A \\sim P4-
 C24 \\sim P4-C24A
 with sigma of 0.02
 P1-C15 \\sim P2-C16 \\sim P3-C21A \\sim P3-C21 \\sim P4-C22A \\sim P4-C22
 with sigma of 0.02
 C16-C15 \\sim C22A-C21A \\sim C22-C21
 with sigma of 0.02
 C27-C26 \\sim C27-C26A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C19 \\sim C20 \\sim P3 \\sim P4 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim
C21A \\sim C22A \\sim C23A \\sim C24A: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(C21A) = Uanis(C21)
Uanis(C26A) = Uanis(C26)
4. Rigid body (RIGU) restrains
 C19, C20, P3, P4, C21, C22, C23, C24, C21A, C22A, C23A, C24A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C21A)=Sof(H21C)=Sof(H21D)=Sof(C22A)=Sof(H22C)=Sof(H22D)=Sof(C23A)=
 Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=1-FVAR(1)
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C23)=Sof(H23A)=
 Sof(H23B)=Sof(H23C)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(1)
 Sof(H25C)=Sof(H25D)=Sof(C26A)=Sof(H26C)=Sof(H26D)=Sof(H27C)=Sof(H27D)=1-FVAR(2)
 Sof(H25A)=Sof(H25B)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H27A)=Sof(H27B)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C15(H15A,H15B),
 C16(H16A,H16B), C21(H21A,H21B), C22(H22A,H22B), C21A(H21C,H21D), C22A(H22C,
 H22D), C25(H25A,H25B), C25(H25C,H25D), C26(H26A,H26B), C26A(H26C,H26D),
 C27(H27A,H27B), C27(H27C,H27D), C28(H28A,H28B)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C7(H7), C8(H8)
6.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C23(H23A,H23B,H23C), C24(H24A,
 H24B,H24C), C23A(H23D,H23E,H23F), C24A(H24D,H24E,H24F)
;
_shelx_res_checksum              14731
_shelx_hkl_checksum              60958
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'