A Ruthenium(II) Bis(Phosphinophosphinine) Complex as a Precatalyst for Transfer-Hydrogenation and Hydrogen-Borrowing Reactions
Newland, Robert J.; Wyatt, Mark Francis; Wingad, Richard; Mansell, Stephen M.; Dalton Trans.  (2017) –; doi:10.1039/C7DT01022B

data_7042664
_publ_section_title
;
 A Ruthenium(II) Bis(Phosphinophosphinine) Complex as a Precatalyst for
 Transfer-Hydrogenation and Hydrogen-Borrowing Reactions
;
_journal_name_full               'Dalton Trans.'
_journal_paper_doi               10.1039/C7DT01022B
_journal_year                    2017
_chemical_formula_moiety         'C42 H48 Cl2 P4 Ru Si2, C6 H6'
_chemical_formula_sum            'C48 H54 Cl2 P4 Ru Si2'
_chemical_formula_weight         982.94
_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   mixed
_audit_creation_date             2017-04-04
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_audit_update_record
;
2017-04-05 deposited with the CCDC.
2017-04-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.042(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.2383(11)
_cell_length_b                   25.4095(17)
_cell_length_c                   10.8916(6)
_cell_measurement_reflns_used    5733
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      23.92
_cell_measurement_theta_min      2.33
_cell_volume                     5141.8(5)
_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  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_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  0.1045
_diffrn_reflns_av_unetI/netI     0.1060
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            46318
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        24.777
_diffrn_reflns_theta_max         24.777
_diffrn_reflns_theta_min         1.942
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.610
_exptl_absorpt_correction_T_max  0.7451
_exptl_absorpt_correction_T_min  0.6267
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.0917 before and 0.0667 after correction.
The Ratio of minimum to maximum transmission is 0.8411.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.270
_exptl_crystal_description       Plate
_exptl_crystal_F_000             2032
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.02
_platon_squeeze_details
;
There are solvent accessible voids in this structure.
Although no disordered solvent moelcules could be identified
and modelled, SQUEEZE revealed residual electron denisty
in these voids, probably two half molecules of C6H6.

TITL p21onc_m_a.res in P2(1)/c                                                  
CELL   19.2383   25.4095   10.8916     90.00    105.04     90.00                
SPGR P21/c                                                                      
Q101 0.787 0.569 0.753 !       1.36 eA-3                                        
Q102 0.734 0.923 0.145 !       1.28 eA-3                                        
C103 0.087 0.766 0.328 !       1.28 eA-3                                        
C104 0.892 0.242 0.067 !       1.23 eA-3                                        
C105 0.866 0.218 0.716 !       1.13 eA-3                                        
C106 0.092 0.749 0.765 !       1.09 eA-3                                        
C107 0.799 0.274 0.327 !       1.06 eA-3                                        
C108 0.941 0.234 0.806 !       1.06 eA-3                                        
C109 0.924 0.228 0.892 !       1.03 eA-3                                        
C110 0.806 0.279 0.247 !       0.95 eA-3                                        
C111 0.083 0.784 0.015 !       0.94 eA-3                                        
C112 0.128 0.691 0.832 !       0.93 eA-3                                        
Q113 0.426 0.780 0.655 !       0.92 eA-3                                        
C114 0.121 0.786 0.120 !       0.91 eA-3                                        
Q115 0.715 0.961 0.314 !       0.88 eA-3                                        
C116 0.838 0.241 0.666 !       0.87 eA-3                                        
Q117 0.753 0.281 0.098 !       0.87 eA-3                                        
C118 0.863 0.288 0.483 !       0.87 eA-3                                        
C119 0.910 0.313 0.128 !       0.87 eA-3                                        
C120 0.858 0.267 0.127 !       0.87 eA-3                                        
Q121 0.877 0.234 0.155 !       0.87 eA-3                                        
Q122 0.022 0.656 0.420 !       0.86 eA-3                                        
Q123 0.819 0.212 0.161 !       0.86 eA-3                                        
Q124 0.625 0.314 0.813 !       0.85 eA-3                                        
Q125 0.986 0.750 0.223 !       0.85 eA-3                                        
C126 0.096 0.737 0.157 !       0.85 eA-3                                        
C127 0.949 0.266 0.612 !       0.85 eA-3                                        
C128 0.162 0.760 0.950 !       0.84 eA-3                                        
Q129 0.193 0.462 0.260 !       0.84 eA-3                                        
Q130 0.209 0.501 0.357 !       0.84 eA-3                                        
Q131 0.833 0.884 0.443 !       0.84 eA-3                                        
Q132 0.827 0.280 0.012 !       0.84 eA-3                                        
Q133 0.669 0.522 0.733 !       0.83 eA-3                                        
Q134 0.426 0.250 0.030 !       0.83 eA-3                                        
C135 0.957 0.244 0.858 !       0.83 eA-3                                        
C136 0.854 0.259 0.409 !       0.83 eA-3                                        
C137 0.845 0.305 0.274 !       0.82 eA-3                                        
Q138 0.290 0.360 0.421 !       0.82 eA-3                                        
Q139 0.201 0.759 0.419 !       0.81 eA-3                                        
Q140 0.374 0.780 0.691 !       0.81 eA-3                                        
Q141 0.787 0.561 0.111 !       0.81 eA-3                                        
Q142 0.742 0.585 0.403 !       0.79 eA-3                                        
Q143 0.246 0.132 0.441 !       0.79 eA-3                                        
Q144 0.021 0.766 0.453 !       0.79 eA-3                                        
Q145 0.918 0.211 0.232 !       0.79 eA-3                                        
C146 0.160 0.704 0.877 !       0.78 eA-3                                        
Q147 0.305 0.447 0.309 !       0.78 eA-3                                        
Q148 0.254 0.041 0.873 !       0.78 eA-3                                        
Q149 0.161 0.969 0.234 !       0.77 eA-3                                        
Q150 0.796 0.210 0.061 !       0.77 eA-3                                        
Q151 0.671 0.234 0.419 !       0.77 eA-3                                        
Q152 0.767 0.882 0.187 !       0.76 eA-3                                        
Q153 0.736 0.500 0.677 !       0.76 eA-3                                        
C154 0.195 0.789 0.061 !       0.76 eA-3                                        
Q155 0.883 0.546 0.204 !       0.76 eA-3                                        
C156 0.159 0.795 0.108 !       0.76 eA-3                                        
Q157 0.751 0.554 0.461 !       0.75 eA-3                                        
Q158 0.789 0.516 0.339 !       0.75 eA-3                                        
Q159 0.133 0.733 0.269 !       0.75 eA-3                                        
Q160 0.054 0.047 0.111 !       0.75 eA-3                                        
Q161 0.807 0.400 0.697 !       0.75 eA-3                                        
Q162 0.662 0.297 0.894 !       0.74 eA-3                                        
Q163 0.934 0.891 0.284 !       0.74 eA-3                                        
Q164 0.633 0.414 0.904 !       0.73 eA-3                                        
Q165 0.680 0.430 0.608 !       0.73 eA-3                                        
Q166 0.939 0.727 0.033 !       0.73 eA-3                                        
Q167 0.551 0.720 0.018 !       0.73 eA-3                                        
Q168 0.910 0.545 0.611 !       0.72 eA-3                                        
Q169 0.358 0.171 0.348 !       0.72 eA-3                                        
Q170 0.637 0.758 0.052 !       0.72 eA-3                                        
Q171 0.226 0.726 0.017 !       0.72 eA-3                                        
C172 0.905 0.295 0.562 !       0.72 eA-3                                        
Q173 0.805 0.267 0.157 !       0.72 eA-3                                        
Q174 0.019 0.086 0.661 !       0.72 eA-3                                        
Q175 0.691 0.929 0.231 !       0.71 eA-3                                        
Q176 0.864 0.345 0.125 !       0.71 eA-3                                        
Q177 0.324 0.500 0.202 !       0.71 eA-3                                        
Q178 0.582 0.657 0.079 !       0.71 eA-3                                        
C179 0.846 0.257 0.301 !       0.71 eA-3                                        
Q180 0.597 0.485 0.401 !       0.71 eA-3                                        
C181 0.869 0.227 0.487 !       0.70 eA-3                                        
Q182 0.667 0.982 0.144 !       0.70 eA-3                                        
Q183 0.333 0.813 0.750 !       0.70 eA-3                                        
Q184 0.767 0.094 0.348 !       0.70 eA-3                                        
Q185 0.602 0.477-0.005 !       0.70 eA-3                                        
Q186 0.447 0.881 0.890 !       0.70 eA-3                                        
Q187 0.220 0.336 0.298 !       0.70 eA-3                                        
Q188 0.987 0.016 0.394 !       0.70 eA-3                                        
Q189 0.758 0.047 0.346 !       0.70 eA-3                                        
Q190 0.209 0.711 0.924 !       0.70 eA-3                                        
Q191 0.700 0.587 0.466 !       0.70 eA-3                                        
Q192 0.909 0.319 0.356 !       0.69 eA-3                                        
C193 0.083 0.706 0.727 !       0.69 eA-3                                        
Q194 0.337 0.687 0.375 !       0.69 eA-3                                        
Q195 0.568 0.119 0.469 !       0.69 eA-3                                        
Q196 0.924 0.109 0.526 !       0.69 eA-3                                        
Q197 0.243 0.172 0.306 !       0.69 eA-3                                        
Q198 0.268 0.937 0.496 !       0.69 eA-3                                        
Q199 0.295 0.218 0.817 !       0.68 eA-3                                        
;
_refine_diff_density_max         0.846
_refine_diff_density_min         -0.611
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     516
_refine_ls_number_reflns         8777
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.1197
_refine_ls_R_factor_gt           0.0624
_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^)+(0.0591P)^2^+9.9258P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1271
_refine_ls_wR_factor_ref         0.1476
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5464
_reflns_number_total             8777
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt01022b2.cif
_cod_data_source_block           4
_cod_database_code               7042664
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.988
_shelx_estimated_absorpt_t_min   0.711
_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
2. Rigid body (RIGU) restrains
 C43, C44, C45, C46, C47, C48
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3.a Me refined with riding coordinates:
 C6(H6A,H6B,H6C)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C17(H17), C18(H18),
 C19(H19), C20(H20), C21(H21), C24(H24), C32(H32), C33(H33), C34(H34), C35(H35),
  C36(H36), C38(H38), C39(H39), C40(H40), C41(H41), C42(H42), C43(H43),
 C44(H44), C45(H45), C46(H46), C47(H47), C48(H48)
3.c Fitted hexagon refined as free rotating group:
 C43(C44,C45,C46,C47,C48)
3.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C27(H27A,H27B,H27C),
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C)
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'