Low-valent Homobimetallic Rh Complexes: Influence of Ligands on the Structure and the Intramolecular Reactivity of Rh‒H Intermediates
Jurt, Pascal; Salnikov, Oleg; Gianetti, Thomas L.; Chukanov, Nikita; Baker, Matthew G.; Le Corre, Grégoire; Borger, Jaap E.; Verel, René; Gauthier, Sébastien; Fuhr, Olaf; Kovtunov, Kirill V.; Fedorov, Alexey; Fenske, Dieter; Koptyug, Igor V.; Grützmacher, Hansjörg; Chemical Science  (2019) –; doi:10.1039/C9SC02683E

data_1552036
_publ_section_title
;
 Low-valent Homobimetallic Rh Complexes: Influence of Ligands on the
 Structure and the Intramolecular Reactivity of Rh--H Intermediates
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC02683E
_journal_year                    2019
_chemical_formula_moiety
'0.25(C94 H108.99 N10 P2 Rh4 Si4), 0.5(C47 H56 N5 P Rh2 Si2), 2(C F3 O3 S), 0.88(C7 H8), 0.38(C2 H3 N)'
_chemical_formula_sum            'C55.88 H63.37 F6 N5.38 O6 P Rh2 S2 Si2'
_chemical_formula_weight         1377.33
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-05-29 deposited with the CCDC.    2019-07-08 downloaded from the CCDC.
;
_cell_angle_alpha                116.325(2)
_cell_angle_beta                 96.234(2)
_cell_angle_gamma                102.612(2)
_cell_formula_units_Z            4
_cell_length_a                   12.7709(7)
_cell_length_b                   23.1638(13)
_cell_length_c                   24.3054(14)
_cell_measurement_reflns_used    9938
_cell_measurement_temperature    108(2)
_cell_measurement_theta_max      26.34
_cell_measurement_theta_min      2.28
_cell_volume                     6113.0(6)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      108.1
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.33
_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 APEX-II CCD'
_diffrn_measurement_method       '\f and \w 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  0.1347
_diffrn_reflns_av_unetI/netI     0.0640
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            246112
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.502
_diffrn_reflns_theta_min         2.217
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.744
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.497
_exptl_crystal_description       plate
_exptl_crystal_F_000             2813
_exptl_crystal_recrystallization_method 'from cold Toluene/Acetonitrile'
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.02
_refine_diff_density_max         3.238
_refine_diff_density_min         -2.081
_refine_diff_density_rms         0.212
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1136
_refine_ls_number_reflns         25231
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.1501
_refine_ls_R_factor_gt           0.1086
_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^)+(0.1225P)^2^+107.3760P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2679
_refine_ls_wR_factor_ref         0.2987
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17985
_reflns_number_total             25231
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc02683e2.cif
_cod_data_source_block           pjxr1
_cod_database_code               1552036
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.791
_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. Uiso/Uaniso restraints and constraints
Uiso(F7) = Uiso(F1) = Uiso(F8) = Uiso(C1) = Uiso(O4) = Uiso(O5) = Uiso(S2) =
Uiso(O1)
Uiso(O2) = Uiso(S3) = Uiso(O3) = Uiso(O6) = Uiso(C6) = Uiso(F9) = Uiso(F3) =
Uiso(F2)
Uiso(O8) = Uiso(O7) = Uiso(S4) = Uiso(O9) = Uiso(C2) = Uiso(F6) = Uiso(F4) =
Uiso(F5) = Uiso(F11) = Uiso(C3) = Uiso(F12) = Uiso(O12) = Uiso(S5) = Uiso(O10)
= Uiso(O11) = Uiso(F10)
Uiso(C02B) = Uiso(C02A)
Uiso(C1Y) = Uiso(C033) = Uiso(C1Z) = Uiso(C031)
Uiso(C20) = Uiso(C1AA) = Uiso(C032) = Uiso(C03A)
Uiso(C03F) = Uiso(C03G)
Uiso(Rh04) = Uiso(Rh)
Uiso(C036) = Uiso(C1L)
Uiso(N8) = Uiso(N8A)
Uiso(C034) = Uiso(C1K)
Uiso(N6) = Uiso(N6A)
Uiso(N12) = Uiso(C1P) = Uiso(C1Q) = Uiso(H1QA) = Uiso(H1QB) = Uiso(H1QC)
Uiso(S6) = Uiso(O13) = Uiso(O14) = Uiso(O15) = Uiso(C4) = Uiso(F13) = Uiso(F14)
= Uiso(F15) = Uiso(S7) = Uiso(O19) = Uiso(O1A) = Uiso(O1B) = Uiso(C22) =
Uiso(F19) = Uiso(F1A) = Uiso(F1B) = Uiso(S8) = Uiso(O1C) = Uiso(O1D) =
Uiso(O1E) = Uiso(C23) = Uiso(F17) = Uiso(F1C) = Uiso(F1D)
Uiso(C1M) = Uiso(C042)
Uiso(N7A) = Uiso(N7)
Uiso(C04B) = Uiso(C04A)
Uiso(C03E) = Uiso(C2AA)
Uiso(C03C) = Uiso(C03D)
Uiso(C1D) = Uiso(C1E) = Uiso(C1F) = Uiso(C1G) = Uiso(C1H) = Uiso(C1I) =
Uiso(C1J)
Uiso(C1S) = Uiso(C1R) = Uiso(N13)
Uiso(C16) = Uiso(C18) = Uiso(C19) = Uiso(C1A) = Uiso(C1B) = Uiso(C1C) =
Uiso(C17)
Uiso(C5) = Uiso(C7) = Uiso(C8) = Uiso(C9) = Uiso(C10) = Uiso(C11) = Uiso(C14) =
Uiso(C1U) = Uiso(C1V) = Uiso(C1W) = Uiso(C1X) = Uiso(C1O) = Uiso(C1T) =
Uiso(C1N)
3. Others
 1*[Sof(S6)+Sof(O13)+Sof(O14)+Sof(O15)+Sof(C4)+Sof(F13)+Sof(F14)+Sof(F15)]+1*
 [Sof(S7)+Sof(O19)+Sof(O1A)+Sof(O1B)+Sof(C22)+Sof(F19)+Sof(F1A)+Sof(F1B)]+1*
 [Sof(S8)+Sof(O1C)+Sof(O1D)+Sof(O1E)+Sof(C23)+Sof(F17)+Sof(F1C)+Sof(F1D)]=1
 with esd of 0.0001
 Sof(S3)=Sof(O3)=Sof(O2)=Sof(O6)=Sof(C6)=Sof(F2)=Sof(F3)=Sof(F9)=1-FVAR(1)
 Sof(S2)=Sof(O1)=Sof(O4)=Sof(O5)=Sof(C1)=Sof(F7)=Sof(F8)=Sof(F1)=FVAR(1)
 Sof(S5)=Sof(O10)=Sof(O11)=Sof(O12)=Sof(C3)=Sof(F10)=Sof(F11)=Sof(F12)=1-FVAR(2)
 Sof(S4)=Sof(O7)=Sof(O8)=Sof(O9)=Sof(C2)=Sof(F4)=Sof(F5)=Sof(F6)=FVAR(2)
 Sof(S6)=Sof(O13)=Sof(O14)=Sof(O15)=Sof(C4)=Sof(F13)=Sof(F14)=Sof(F15)=FVAR(3)
 Sof(C1N)=Sof(H1NA)=Sof(H1NB)=Sof(H1NC)=Sof(C1O)=Sof(C1T)=Sof(H1T)=Sof(C1U)=
 Sof(H1U)=Sof(C1V)=Sof(H1V)=Sof(C1W)=Sof(H1W)=Sof(C1X)=Sof(H1X)=1-FVAR(4)
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=
 Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=Sof(C14)=Sof(H14)=FVAR(4)
 Sof(C13A)=Sof(H13A)=Sof(C12A)=Sof(H12A)=Sof(C0AA)=Sof(H0AB)=Sof(C02V)=
 Sof(H6AA)=Sof(C15)=Sof(H15)=Sof(C0)=1-FVAR(5)
 Sof(C028)=Sof(C030)=Sof(H030)=Sof(C02U)=Sof(H02U)=Sof(C03B)=Sof(H03V)=
 Sof(C12)=Sof(C13)=Sof(H13)=FVAR(5)
 Sof(H01A)=Sof(H01B)=Sof(N8)=Sof(C036)=Sof(C03C)=Sof(H03E)=Sof(H03G)=Sof(H03H)=
 Sof(N6A)=Sof(C1K)=Sof(C2AA)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=Sof(N7A)=Sof(C04B)=
 Sof(H04G)=Sof(H04H)=Sof(H04I)=Sof(C1M)=Sof(Rh)=1-FVAR(6)
 Sof(Rh04)=Sof(H01D)=Sof(H01F)=Sof(N6)=Sof(N7)=Sof(C034)=Sof(C03E)=Sof(H03I)=
 Sof(H03J)=Sof(H03K)=Sof(C042)=Sof(C04A)=Sof(H04D)=Sof(H04E)=Sof(H04F)=Sof(N8A)=
 Sof(C1L)=Sof(C03D)=Sof(H03R)=Sof(H03S)=Sof(H03T)=FVAR(6)
 Sof(C02B)=Sof(C1Z)=Sof(H1Z)=Sof(C20)=Sof(H20)=Sof(C03G)=Sof(H03U)=Sof(C1AA)=
 Sof(H1AA)=Sof(C1Y)=Sof(H1Y)=1-FVAR(7)
 Sof(C02A)=Sof(C031)=Sof(H031)=Sof(C03A)=Sof(H03A)=Sof(C03F)=Sof(H03F)=
 Sof(C032)=Sof(H032)=Sof(C033)=Sof(H033)=FVAR(7)
 Sof(S7)=Sof(O19)=Sof(O1A)=Sof(O1B)=Sof(C22)=Sof(F19)=Sof(F1A)=Sof(F1B)=FVAR(8)
 Sof(S8)=Sof(O1C)=Sof(O1D)=Sof(O1E)=Sof(C23)=Sof(F17)=Sof(F1C)=Sof(F1D)=FVAR(9)
 Fixed Sof: C16(0.5) H16A(0.5) H16B(0.5) H16C(0.5) C17(0.5) C18(0.5) H18(0.5)
 C19(0.5) H19(0.5) C1A(0.5) H1A(0.5) C1B(0.5) H1B(0.5) C1C(0.5) H1C(0.5)
 C1D(0.25) H1DA(0.25) H1DB(0.25) H1DC(0.25) C1E(0.25) C1F(0.25) H1F(0.25)
 C1G(0.25) H1G(0.25) C1H(0.25) H1H(0.25) C1I(0.25) H1I(0.25) C1J(0.25)
 H1J(0.25) N12(0.5) C1P(0.5) C1Q(0.5) H1QA(0.5) H1QB(0.5) H1QC(0.5) N13(0.25)
 C1R(0.25) C1S(0.25) H1SA(0.25) H1SB(0.25) H1SC(0.25)
4.a Free rotating group:
 S2(O1,O4,O5,C1,F7,F8,F1), S3(O3,O2,O6,C6,F2,F3,F9), S4(O7,O8,O9,C2,F4,F5,F6),
 S5(O10,O11,O12,C3,F10,F11,F12), S6(O13,O14,O15,C4,F13,F14,F15), C5(C7,C8,C9,
 C10,C11,C14), C16(C17,C18,C19,C1A,C1B,C1C), C1D(C1E,C1F,C1G,C1H,C1I,C1J),
 N12(C1P,C1Q,H1QA,H1QB,H1QC), N13(C1R,C1S,H1SA,H1SB,H1SC), C1N(C1O,C1T,C1U,C1V,
 C1W,C1X), S7(O19,O1A,O1B,C22,F19,F1A,F1B), S8(O1C,O1D,O1E,C23,F17,F1C,F1D)
4.b Ternary CH refined with riding coordinates:
 C00W(H00W), C015(H015), C017(H017), C01D(H01D), C01D(H01A), C01F(H01F),
 C01F(H01B)
4.c Secondary CH2 refined with riding coordinates:
 C01B(H01C,H01E), C029(H02A,H02B)
4.d Aromatic/amide H refined with riding coordinates:
 C00V(H00V), C010(H010), C014(H014), C01C(H01G), C01E(H01H), C01G(H01I),
 C01J(H01J), C01K(H01K), C01L(H01L), C01O(H01O), C01P(H01P), C01Q(H01Q),
 C01S(H01S), C01T(H01T), C01W(H01W), C01X(H01X), C01Z(H01Z), C020(H020),
 C024(H024), C025(H025), C030(H030), C02U(H02U), C03B(H03V), C13(H13),
 C031(H031), C03A(H03A), C03F(H03F), C032(H032), C033(H033), C02D(H02D),
 C02H(H02T), C02N(H02), C02P(H3AA), C02S(H02S), C02W(H02W), C8(H8), C9(H9),
 C10(H10), C11(H11), C14(H14), C13A(H13A), C12A(H12A), C0AA(H0AB), C02V(H6AA),
 C15(H15), C18(H18), C19(H19), C1A(H1A), C1B(H1B), C1C(H1C), C1F(H1F), C1G(H1G),
  C1H(H1H), C1I(H1I), C1J(H1J), C1T(H1T), C1U(H1U), C1V(H1V), C1W(H1W),
 C1X(H1X), C1Z(H1Z), C20(H20), C03G(H03U), C1AA(H1AA), C1Y(H1Y)
4.e Fitted hexagon refined as free rotating group:
 C028(C030,C02U,C03B,C12,C13), C02A(C031,C03A,C03F,C032,C033), C13A(C12A,C0AA,
 C02V,C15,C0), C02B(C1Z,C20,C03G,C1AA,C1Y)
4.f Idealised Me refined as rotating group:
 C01R(H01M,H01N,H01R), C021(H02M,H02N,H02O), C02C(H02P,H02Q,H02R), C02E(H02C,
 H02E,H02F), C02I(H02V,H02X,H02Y), C02K(H02Z,H,HA), C02M(H02G,H02H,H02I),
 C02O(H0AA,HB,HC), C02T(H4AA,HD,HE), C02X(H5AA,HF,HG), C02Z(H02J,H02K,H02L),
 C037(H03B,H03C,H03D), C038(H03W,H03X,H03Y), C039(H03Z,HH,HI), C03C(H03E,H03G,
 H03H), C03E(H03I,H03J,H03K), C03H(H03L,H03M,H03N), C03M(H03,HJ,HK), C03Y(H03O,
 H03P,H03Q), C045(H04A,H04B,H04C), C04A(H04D,H04E,H04F), C30(H30A,H30B,H30C),
 C5(H5A,H5B,H5C), C16(H16A,H16B,H16C), C1D(H1DA,H1DB,H1DC), C2AA(H2AA,H2AB,
 H2AC), C03D(H03R,H03S,H03T), C04B(H04G,H04H,H04I), C1N(H1NA,H1NB,H1NC)
;
_shelx_res_checksum              49631
_olex2_submission_special_instructions 'No special instructions were received'