Incorporation of Pendant Bases into Rh(diphosphine)2 Complexes: Synthesis, Thermodynamic Studies, And Catalytic CO2 Hydrogenation Activity of [Rh(P2N2)2](+) Complexes.
Lilio, Alyssia M.; Reineke, Mark H.; Moore, Curtis E.; Rheingold, Arnold L.; Takase, Michael K.; Kubiak, Clifford P.; Journal of the American Chemical Society 137 (2015) 8251–8260; doi:10.1021/jacs.5b04291

data_4123900
_publ_section_title
;
 Incorporation of Pendant Bases into Rh(diphosphine)2 Complexes:
 Synthesis, Thermodynamic Studies, And Catalytic CO2 Hydrogenation
 Activity of [Rh(P2N2)2](+) Complexes.
;
_journal_issue                   25
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8251
_journal_page_last               8260
_journal_paper_doi               10.1021/jacs.5b04291
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety         'C60 H64 N4 P4 Rh, B F4, 0.5(C4 H10 O)'
_chemical_formula_sum            'C62 H69 B F4 N4 O0.5 P4 Rh'
_chemical_formula_weight         1191.81
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-11-26
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.11.25 svn.r3098 for OlexSys, GUI svn.r4951)
;
_cell_angle_alpha                78.3650(10)
_cell_angle_beta                 88.8020(10)
_cell_angle_gamma                85.9470(10)
_cell_formula_units_Z            4
_cell_length_a                   10.3561(4)
_cell_length_b                   22.3066(9)
_cell_length_c                   25.1180(11)
_cell_measurement_reflns_used    9980
_cell_measurement_temperature    100
_cell_measurement_theta_max      25.277
_cell_measurement_theta_min      2.234
_cell_volume                     5668.9(4)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       'APEX2 v2013.6-2 (Bruker, 2013)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX CCD'
_diffrn_detector_area_resol_mean 8.0
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'Fixed Chi Three-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker D8 APEX'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0694
_diffrn_reflns_av_unetI/netI     0.0683
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            78721
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.410
_diffrn_reflns_theta_min         0.934
_diffrn_source                   'sealed tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_type              fine-focus
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.472
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6926
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0656 before and 0.0556 after correction.
The Ratio of minimum to maximum transmission is 0.9294.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.396
_exptl_crystal_description       plate
_exptl_crystal_F_000             2476
_exptl_crystal_size_max          0.44
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.696
_refine_diff_density_min         -0.631
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1489
_refine_ls_number_reflns         20830
_refine_ls_number_restraints     228
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.0765
_refine_ls_R_factor_gt           0.0435
_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^)+(0.0363P)^2^+3.7886P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0896
_refine_ls_wR_factor_ref         0.1060
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14415
_reflns_number_total             20830
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b04291_si_009.cif
_cod_data_source_block           Alyssia18_0m
_cod_depositor_comments
;
The following automatic conversions were performed:

'_diffrn_radiation_probe' value 'X-ray' changed to 'x-ray' according
to
/usr/data/users/saulius/crontab/automatic-downloads/current/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 3271 2015-04-21 07:52:19Z andrius 
;
_cod_original_formula_sum        'C62 H69 B F4 N4 O0.50 P4 Rh'
_cod_database_code               4123900
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.819
_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
 O2S-C6S = O2S-C7S
 1.45 with sigma of 0.02
 C7S-C8S = C6S-C5S
 1.55 with sigma of 0.02
 C15'-C16C = C15'-C16'
 1.54 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C16C) = Uanis(C16')
Uanis(C16) = Uanis(C16B)
4. Rigid body (RIGU) restrains
 C15', C16C, C16', C21C, C21', C20', C20C, C19', C19C, C18C, C17C, C17', C18'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C8S, C7S, O2S, C6S, C5S
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C4S, C3S, O1S, C2S, C1S
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C16B, C16, C15, C21, C20, C19, C20B, C21B, C17, C17B, C18B, C19B, C18
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Sof(H15C)=Sof(H15D)=Sof(C16B)=Sof(C17B)=Sof(H17B)=Sof(C18B)=Sof(H18B)=
 Sof(C19B)=Sof(H19B)=Sof(C20B)=Sof(H20B)=Sof(C21B)=Sof(H21B)=1-FVAR(1)
 Sof(H15A)=Sof(H15B)=Sof(C16)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18)=Sof(C19)=
 Sof(H19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=FVAR(1)
 Sof(H15G)=Sof(H15H)=Sof(C16C)=Sof(C21C)=Sof(H21C)=Sof(C20C)=Sof(H20C)=
 Sof(C19C)=Sof(H19C)=Sof(C18C)=Sof(H18C)=Sof(C17C)=Sof(H17C)=1-FVAR(2)
 Sof(H15E)=Sof(H15F)=Sof(C16')=Sof(C21')=Sof(H21')=Sof(C20')=Sof(H20')=
 Sof(C19')=Sof(H19')=Sof(C18')=Sof(H18')=Sof(C17')=Sof(H17')=FVAR(2)
 Fixed Sof: O1S(0.5) C1S(0.5) H1SA(0.5) H1SB(0.5) H1SC(0.5) C2S(0.5) H2SA(0.5)
 H2SB(0.5) C3S(0.5) H3SA(0.5) H3SB(0.5) C4S(0.5) H4SA(0.5) H4SB(0.5) H4SC(0.5)
 O2S(0.5) C5S(0.5) H5SA(0.5) H5SB(0.5) H5SC(0.5) C6S(0.5) H6SA(0.5) H6SB(0.5)
 C7S(0.5) H7SA(0.5) H7SB(0.5) C8S(0.5) H8SA(0.5) H8SB(0.5) H8SC(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B),
 C7(H7A,H7B), C8(H8A,H8B), C15(H15A,H15B), C15(H15C,H15D), C22(H22A,H22B),
 C41(H41A,H41B), C54(H54A,H54B), C1'(H1'A,H1'B), C2'(H2'A,H2'B), C3'(H3'A,H3'B),
  C4'(H4'A,H4'B), C5'(H5'A,H5'B), C6'(H6'A,H6'B), C7'(H7'A,H7'B), C8'(H8'A,
 H8'B), C15'(H15E,H15F), C15'(H15G,H15H), C22'(H22C,H22D), C41'(H41C,H41D),
 C54'(H54C,H54D), C2S(H2SA,H2SB), C3S(H3SA,H3SB), C6S(H6SA,H6SB), C7S(H7SA,H7SB)
6.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C24(H24), C25(H25),
 C26(H26), C27(H27), C28(H28), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34),
  C36(H36), C37(H37), C38(H38), C39(H39), C40(H40), C43(H43), C44(H44),
 C45(H45), C46(H46), C47(H47), C49(H49), C50(H50), C51(H51), C52(H52), C53(H53),
  C56(H56), C57(H57), C58(H58), C59(H59), C60(H60), C17(H17), C18(H18),
 C19(H19), C20(H20), C21(H21), C17B(H17B), C18B(H18B), C19B(H19B), C20B(H20B),
 C21B(H21B), C10'(H10'), C11'(H11'), C12'(H12'), C13'(H13'), C14'(H14'),
 C24'(H24'), C25'(H25'), C26'(H26'), C27'(H27'), C28'(H28'), C30'(H30'),
 C31'(H31'), C32'(H32'), C33'(H33'), C34'(H34'), C36'(H36'), C37'(H37'),
 C38'(H38'), C39'(H39'), C40'(H40'), C43'(H43'), C44'(H44'), C45'(H45'),
 C46'(H46'), C47'(H47'), C49'(H49'), C50'(H50'), C51'(H51'), C52'(H52'),
 C53'(H53'), C56'(H56'), C57'(H57'), C58'(H58'), C59'(H59'), C60'(H60'),
 C21'(H21'), C20'(H20'), C19'(H19'), C18'(H18'), C17'(H17'), C21C(H21C),
 C20C(H20C), C19C(H19C), C18C(H18C), C17C(H17C)
6.c Fitted hexagon refined as free rotating group:
 C16(C17,C18,C19,C20,C21), C16'(C21',C20',C19',C18',C17'), C16C(C21C,C20C,C19C,
 C18C,C17C)
6.d Idealised Me refined as rotating group:
 C1S(H1SA,H1SB,H1SC), C4S(H4SA,H4SB,H4SC), C5S(H5SA,H5SB,H5SC), C8S(H8SA,H8SB,
 H8SC)
;
_shelx_res_checksum              76543
_shelx_hkl_checksum              23550
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'