The Influence of the Second and Outer Coordination Spheres on Rh(diphosphine)2 CO2 Hydrogenation Catalysts
Bays, John Timothy; Priyadarshani, Nilusha; Jeletic, Matthew S.; Hulley, Elliot B.; Miller, Deanna L.; Linehan, John C.; Shaw, Wendy J.; ACS Catalysis  (2014) 140903144432009–; doi:10.1021/cs5009199

data_4511985
_publ_contact_author_name
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;
_publ_section_title
;
 The Influence of the Second and Outer Coordination Spheres on
 Rh(diphosphine)2 CO2 Hydrogenation Catalysts
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              140903144432009
_journal_paper_doi               10.1021/cs5009199
_journal_year                    2014
_chemical_formula_moiety         '2(C27 H27 N P2 Rh0.5), C F3 O3 S'
_chemical_formula_sum            'C55 H54 F3 N2 O3 P4 Rh S'
_chemical_formula_weight         1106.85
_chemical_name_systematic        Rh(PNMeP)(OTf)2
_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
_audit_creation_date             2014-06-26
_audit_creation_method
;
Olex2 1.2
(compiled 2014.06.23 svn.r2948 for OlexSys, GUI svn.r4855)
;
_cell_angle_alpha                93.743(4)
_cell_angle_beta                 95.848(5)
_cell_angle_gamma                109.218(4)
_cell_formula_units_Z            2
_cell_length_a                   11.1175(10)
_cell_length_b                   13.2349(11)
_cell_length_c                   18.0440(16)
_cell_measurement_reflns_used    9669
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      41.82
_cell_measurement_theta_min      2.81
_cell_volume                     2480.1(4)
_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, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.988
_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  0.0454
_diffrn_reflns_av_unetI/netI     0.0622
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            118433
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         42.721
_diffrn_reflns_theta_min         1.957
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.574
_exptl_absorpt_correction_T_max  0.7484
_exptl_absorpt_correction_T_min  0.6779
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0553 before and 0.0492 after correction.
The Ratio of minimum to maximum transmission is 0.9058.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.482
_exptl_crystal_description       block
_exptl_crystal_F_000             1140
_exptl_crystal_recrystallization_method 'evaporation of tetrahydrofuran'
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.756
_refine_diff_density_min         -0.966
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     627
_refine_ls_number_reflns         35714
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0643
_refine_ls_R_factor_gt           0.0384
_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^)+(0.0316P)^2^+0.3863P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0771
_refine_ls_wR_factor_ref         0.0851
_reflns_Friedel_coverage         0.000
_reflns_number_gt                26165
_reflns_number_total             35714
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs5009199_si_002.cif
_cod_data_source_block           '[Rh(PNMeP)2]OTf'
_cod_database_code               4511985
_shelxl_version_number           2013-4
_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.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C42(H42A,H42B), C40(H40A,H40B), C15(H15A,H15B)
2.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C26(H26), C19(H19), C25(H25), C39(H39), C46(H46), C17(H17),
 C30(H30), C36(H36), C31(H31), C33(H33), C24(H24), C20(H20), C27(H27), C23(H23),
  C4(H4), C5(H5), C12(H12), C3(H3), C9(H9), C6(H6), C2(H2), C8(H8), C11(H11),
 C10(H10), C45(H45), C51(H51), C53(H53), C54(H54), C50(H50), C18(H18), C48(H48),
  C37(H37), C32(H32), C35(H35), C38(H38), C29(H29), C44(H44), C47(H47), C52(H52)
2.c Idealised Me refined as rotating group:
 C41(H41A,H41B,H41C), C14(H14A,H14B,H14C)
;
_olex2_exptl_crystal_mounting_method 'mounted on nylon loop'
_olex2_submission_original_sample_id TB_001
_olex2_submission_special_instructions 'No special instructions were received'