Second sphere ligand modifications enable a recyclable catalyst for oxidant-free alcohol oxidation to carboxylates.
Dahl, Eric W.; Louis-Goff, Thomas; Szymczak, Nathaniel K.; Chemical communications (Cambridge, England) 53 (2017) 2287–2289; doi:10.1039/c6cc10206a

data_7119586
_publ_section_title
;
 Second sphere ligand modifications enable a recyclable catalyst for
 oxidant-free alcohol oxidation to carboxylates.
;
_journal_issue                   14
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              2287
_journal_page_last               2289
_journal_paper_doi               10.1039/c6cc10206a
_journal_volume                  53
_journal_year                    2017
_chemical_formula_moiety         'C69 H64 N5 P2 Ru, 2(F3 P0.5), 2(C7 H8)'
_chemical_formula_sum            'C83 H80 F6 N5 P3 Ru'
_chemical_formula_weight         1455.50
_chemical_name_systematic
'6,6"-(2,4,6-trimethylphenylamino terpyridine)-bis-triphenylphosphino-hydrido-ruthenium hexafluorophosphate'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2016-12-19
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2016-12-19 deposited with the CCDC.
2017-01-25 downloaded from the CCDC.
;
_cell_angle_alpha                89.405(6)
_cell_angle_beta                 87.338(6)
_cell_angle_gamma                67.798(5)
_cell_formula_units_Z            2
_cell_length_a                   13.1893(2)
_cell_length_b                   13.5036(3)
_cell_length_c                   20.9744(15)
_cell_measurement_reflns_used    32657
_cell_measurement_temperature    85
_cell_measurement_theta_max      68.30
_cell_measurement_theta_min      3.50
_cell_volume                     3454.8(3)
_computing_cell_refinement       'CrystalClear-SM Expert 2.0 r16'
_computing_data_collection
'CrystalClear-SM Expert 2.0 r16 (Rigaku, 2014)'
_computing_data_reduction        'CrystalClear-SM Expert 2.0 r16'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      85
_diffrn_measured_fraction_theta_full 0.978
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_device_type  'Rigaku Saturn70 CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54187
_diffrn_reflns_av_R_equivalents  0.0823
_diffrn_reflns_av_unetI/netI     0.0779
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            52601
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.687
_diffrn_reflns_theta_max         68.249
_diffrn_reflns_theta_min         3.535
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    3.040
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.686
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Jacobson, R. (1998) Private communication'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.399
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             1512
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.01
_refine_diff_density_max         2.146
_refine_diff_density_min         -1.180
_refine_diff_density_rms         0.127
_refine_ls_extinction_coef       0.00163(19)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.113
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     910
_refine_ls_number_reflns         12345
_refine_ls_number_restraints     46
_refine_ls_restrained_S_all      1.113
_refine_ls_R_factor_all          0.0781
_refine_ls_R_factor_gt           0.0699
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1144P)^2^+3.9697P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1881
_refine_ls_wR_factor_ref         0.1969
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10477
_reflns_number_total             12345
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cc10206a2.cif
_cod_data_source_block           shelx
_cod_depositor_comments
'Adding full bibliography for 7119586--7119587.cif.'
_cod_database_code               7119586
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All H(H) groups, All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N5-H5 \\sim N4-H4
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C1A) = Uanis(C77)
Uanis(C81) = Uanis(C4AA) = Uanis(C78) = Uanis(C7AA)
Uanis(C82) = Uanis(C80) = Uanis(C9AA) = Uanis(C6AA)
Uanis(C5AA) = Uanis(C83) = Uanis(C79) = Uanis(C8AA)
Uanis(C4AA) = Uanis(C78)
4. Same fragment restrains
{C1A, C4AA, C5AA, C6AA, C7AA, C9AA, C8AA} sigma for 1-2: 0.02, 1-3: 0.02
{C77, C78, C83, C82, C81, C80, C79} sigma for 1-2: 0.02, 1-3: 0.02
as
{C70, C71, C76, C75, C74, C73, C72}
5. Others
 Fixed Sof: C77(0.5) H77A(0.5) H77B(0.5) H77C(0.5) C78(0.5) C83(0.5) H83(0.5)
 C82(0.5) H82(0.5) C81(0.5) H81(0.5) C80(0.5) H80(0.5) C79(0.5) H79(0.5)
 C1A(0.5) H1AA(0.5) H1AB(0.5) H1AC(0.5) C4AA(0.5) C5AA(0.5) H5AA(0.5) C6AA(0.5)
 H6AA(0.5) C7AA(0.5) H7AA(0.5) C9AA(0.5) H9AA(0.5) C8AA(0.5) H8AA(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C39(H39), C2(H2), C53(H53), C59(H59), C35(H35), C51(H51), C54(H54), C27(H27),
 C65(H65), C12(H12), C3(H3), C60(H60), C7(H7), C49(H49), C61(H61), C57(H57),
 C45(H45), C4(H4A), C47(H47), C9(H9), C13(H13), C48(H48), C8(H8), C18(H18),
 C29(H29), C69(H69), C14(H14), C44(H44), C50(H50), C38(H38), C37(H37), C56(H56),
  C55(H55), C20(H20), C41(H41), C36(H36), C76(H76), C75(H75), C74(H74),
 C73(H73), C72(H72), C43(H43), C68(H68), C67(H67), C66(H66), C42(H42), C63(H63),
  C62(H62), C83(H83), C82(H82), C81(H81), C80(H80), C79(H79), C5AA(H5AA),
 C6AA(H6AA), C7AA(H7AA), C9AA(H9AA), C8AA(H8AA)
6.b Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C33(H33A,H33B,H33C), C31(H31A,H31B,H31C), C24(H24A,H24B,
 H24C), C32(H32A,H32B,H32C), C22(H22A,H22B,H22C), C70(H70A,H70B,H70C), C77(H77A,
 H77B,H77C), C1A(H1AA,H1AB,H1AC)
;
_shelx_res_checksum              43105
_shelx_shelxl_version_number     2016/6
_olex2_submission_special_instructions 'No special instructions were received'