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_7119587
_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         'C51 H48 Cl2 N5 P Ru, 5/3(C6 H6)'
_chemical_formula_sum            'C61 H58 Cl2 N5 P Ru'
_chemical_formula_weight         1064.06
_chemical_name_systematic
'6,6"-(2,4,6-trimethylphenylamino terpyridine)-triphenylphosphino-ruthenium dichloride'
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-11-07
_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                113.710(2)
_cell_angle_beta                 96.4927(17)
_cell_angle_gamma                113.636(2)
_cell_formula_units_Z            6
_cell_length_a                   20.7269(4)
_cell_length_b                   21.4370(5)
_cell_length_c                   22.2463(4)
_cell_measurement_reflns_used    23722
_cell_measurement_temperature    85
_cell_measurement_theta_max      69.0780
_cell_measurement_theta_min      2.4520
_cell_volume                     7835.2(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_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_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.980
_diffrn_measured_fraction_theta_max 0.964
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -110.00  70.00   1.00   10.00    --  -20.00   0.00-180.00  180
  2  \w    -45.00   0.00   1.00   10.00    --  -20.00  72.00   0.00   45
  3  \w    -45.00   0.00   1.00   10.00    --  -20.00  72.00   0.00   45
  4  \w    -25.00  43.00   1.00   10.00    --  -20.00  36.00 120.00   68
  5  \w    -45.00   0.00   1.00   10.00    --  -20.00  72.00-180.00   45
  6  \w   -173.00-128.00   1.00   45.00    --  -92.00 -36.00 120.00   45
  7  \w   -133.00 -88.00   1.00   45.00    --  -92.00 -36.00 -60.00   45
  8  \w   -104.00 -59.00   1.00   45.00    --  -92.00  36.00  60.00   45
  9  \w   -122.00 -77.00   1.00   45.00    --  -92.00 -72.00  60.00   45
 10  \w   -174.00 -78.00   1.00   45.00    --  -92.00 -72.00-120.00   96
 11  \w    -93.00 -35.00   1.00   45.00    --  -92.00  36.00-120.00   58
 12  \w   -176.00 -77.00   1.00   45.00    --  -92.00 -72.00 -60.00   99
 13  \w   -147.00 -75.00   1.00   45.00    --  -92.00 -72.00-180.00   72
 14  \w   -176.00 -77.00   1.00   45.00    --  -92.00 -72.00 120.00   99
 15  \w   -177.00-116.00   1.00   45.00    --  -92.00 -36.00  60.00   61
 16  \w    -87.00  -9.00   1.00   45.00    --  -92.00  36.00 -60.00   78
 17  \w   -102.00 -14.00   1.00   45.00    --  -92.00  36.00   0.00   88
 18  \w   -102.00 -21.00   1.00   45.00    --  -92.00  72.00 120.00   81
 19  \w   -175.00-104.00   1.00   45.00    --  -92.00 -36.00   0.00   71
 20  \w   -104.00 -52.00   1.00   45.00    --  -92.00  72.00  60.00   52
 21  \w   -109.00 -14.00   1.00   45.00    --  -92.00  72.00-120.00   95
 22  \w   -105.00 -24.00   1.00   45.00    --  -92.00  36.00-120.00   81
 23  \w   -105.00  -2.00   1.00   45.00    --  -92.00  36.00-180.00  103
 24  \w   -106.00  -2.00   1.00   45.00    --  -92.00  72.00 -60.00  104
 25  \w   -106.00  -2.00   1.00   45.00    --  -92.00  72.00 -60.00  104
 26  \w   -107.00 -29.00   1.00   45.00    --  -92.00  72.00   0.00   78
 27  \w   -117.00 -72.00   1.00   45.00    --  -92.00  72.00 180.00   45
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  'Rigaku Saturn70 CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0851131000
_diffrn_orient_matrix_UB_12      -0.0502973000
_diffrn_orient_matrix_UB_13      -0.0214102000
_diffrn_orient_matrix_UB_21      0.0053790000
_diffrn_orient_matrix_UB_22      -0.0742099000
_diffrn_orient_matrix_UB_23      -0.0409930000
_diffrn_orient_matrix_UB_31      0.0098768000
_diffrn_orient_matrix_UB_32      -0.0088032000
_diffrn_orient_matrix_UB_33      0.0653200000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1811
_diffrn_reflns_av_unetI/netI     0.1270
_diffrn_reflns_Laue_measured_fraction_full 0.980
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            120755
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.732
_diffrn_reflns_theta_min         2.462
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.001
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83893
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.353
_exptl_crystal_description       plate
_exptl_crystal_F_000             3312
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: benzene'
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.01
_refine_diff_density_max         2.490
_refine_diff_density_min         -2.499
_refine_diff_density_rms         0.165
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1819
_refine_ls_number_reflns         28479
_refine_ls_number_restraints     144
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.1085
_refine_ls_R_factor_gt           0.0840
_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^)+(0.1563P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2162
_refine_ls_wR_factor_ref         0.2548
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20501
_reflns_number_total             28479
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cc10206a2.cif
_cod_data_source_block           tlg172
_cod_depositor_comments
;
Adding full bibliography for 7119586--7119587.cif.

2017-11-13
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C183 H174 Cl6 N15 P3 Ru3'
_cod_original_formula_weight         3192.18
_cod_original_formula_moiety         '3(C51 H48 Cl2 N5 P Ru), 5(C6 H6)'
_cod_original_formula_units_Z            2
_cod_original_cell_volume        7835.1(3)
_cod_database_code               7119587
_chemical_oxdiff_formula         'C51 H48 Cl2 N5 P1 Ru1 '
_reflns_odcompleteness_completeness 96.38
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.60
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All N(H) groups
2. Uiso/Uaniso restraints and constraints
C178 \\sim C179 \\sim C180 \\sim C181 \\sim C182 \\sim C183: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C160 \\sim C161 \\sim C162 \\sim C163 \\sim C164 \\sim C165: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C172 \\sim C173 \\sim C174 \\sim C175 \\sim C176 \\sim C177: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C183) = Uanis(C182) = Uanis(C181) = Uanis(C180) = Uanis(C179) =
Uanis(C178)
Uanis(C173) = Uanis(C174) = Uanis(C175) = Uanis(C176) = Uanis(C177) =
Uanis(C172)
Uanis(C171) = Uanis(C166) = Uanis(C167) = Uanis(C168) = Uanis(C169) =
Uanis(C170)
3. Same fragment restrains
{C178, C179, C180, C181, C182, C183} sigma for 1-2: 0.02, 1-3: 0.02
{C172, C173, C174, C175, C176, C177} sigma for 1-2: 0.02, 1-3: 0.02
as
{C154, C155, C156, C157, C158, C159}
4.a Aromatic/amide H refined with riding coordinates:
 N9(H9), N10(H10), C53(H53), C54(H54), C55(H55), C58(H58), C59(H59), C60(H60),
 C63(H63), C64(H64), C65(H65), C69(H69), C71(H71), C78(H78), C80(H80), C86(H86),
  C87(H87), C88(H88), C89(H89), C90(H90), C92(H92), C93(H93), C94(H94),
 C95(H95), C96(H96), C98(H98), C99(H99), C100(H100), C101(H101), C102(H102),
 N4(H4), N5(H5), C2(H2), C3(H3), C4(H4A), C7(H7), C8(H8), C9(H9A), C12(H12),
 C13(H13), C14(H14), C18(H18), C20(H20), C27(H27), C29(H29), C34(H34), C35(H35),
  C36(H36), C37(H37), C38(H38), C41(H41), C42(H42), C43(H43), C44(H44),
 C45(H45), C47(H47), C48(H48), C49(H49), C50(H50), C51(H51), N14(H14A),
 N15(H15), C104(H104), C105(H105), C106(H106), C109(H109), C110(H110),
 C111(H111), C114(H114), C115(H115), C116(H116), C120(H120), C122(H122),
 C129(H129), C131(H131), C137(H137), C138(H138), C139(H139), C140(H140),
 C141(H141), C143(H143), C144(H144), C145(H145), C146(H146), C147(H147),
 C149(H149), C150(H150), C151(H151), C152(H152), C153(H153), C172(H172),
 C173(H173), C174(H174), C175(H175), C176(H176), C177(H177), C166(H166),
 C167(H167), C168(H168), C169(H169), C170(H170), C171(H171), C160(H160),
 C161(H161), C162(H162), C163(H163), C164(H164), C165(H165), C178(H178),
 C179(H179), C180(H180), C181(H181), C182(H182), C183(H183), C154(H154),
 C155(H155), C156(H156), C157(H157), C158(H158), C159(H159)
4.b Idealised Me refined as rotating group:
 C73(H73A,H73B,H73C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C82(H82A,H82B,
 H82C), C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C), C24(H24A,H24B,H24C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C),
 C33(H33A,H33B,H33C), C124(H12A,H12B,H12C), C125(H12D,H12E,H12F), C126(H12G,
 H12H,H12I), C133(H13A,H13B,H13C), C134(H13D,H13E,H13F), C135(H13G,H13H,H13I)
;
_shelx_res_checksum              63855
_shelx_shelxl_version_number     2016/6
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.743
_oxdiff_exptl_absorpt_empirical_full_min 0.399