Controlled cis Labilization of CO from Manganese(I) Mixed Carbonyl/Isocyanide Complexes: An Entry Point to Coordinatively Unsaturated Metallo-Lewis Acids
Agnew, Douglas W.; Moore, Curtis E.; Rheingold, Arnold L.; Figueroa, Joshua S.; Organometallics 36 (2017) 363–; doi:10.1021/acs.organomet.6b00792

data_4086816
_publ_section_title
;
 Controlled cis Labilization of CO from Manganese(I) Mixed
 Carbonyl/Isocyanide Complexes: An Entry Point to Coordinatively
 Unsaturated Metallo-Lewis Acids
;
_journal_issue                   2
_journal_name_full               Organometallics
_journal_page_first              363
_journal_paper_doi               10.1021/acs.organomet.6b00792
_journal_volume                  36
_journal_year                    2017
_chemical_formula_moiety         'C69 H83 Mn N2 O4, 0.5(C4 H10 O)'
_chemical_formula_sum            'C71 H88 Mn N2 O4.5'
_chemical_formula_weight         1096.37
_chemical_name_systematic
;
 ?
;
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-06-02
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.16 svn.r3265 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 116.3112(13)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   25.996(2)
_cell_length_b                   21.874(2)
_cell_length_c                   25.178(2)
_cell_measurement_reflns_used    9882
_cell_measurement_temperature    100
_cell_measurement_theta_max      26.98
_cell_measurement_theta_min      2.44
_cell_volume                     12833.9(18)
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_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  0.0384
_diffrn_reflns_av_unetI/netI     0.0362
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            112890
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.159
_diffrn_reflns_theta_min         0.874
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.254
_exptl_absorpt_correction_type   none
_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    1.134
_exptl_crystal_description       block
_exptl_crystal_F_000             4706
_exptl_crystal_recrystallization_method
'Grown from et2o/tms2o solution at -40C.'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.555
_refine_diff_density_min         -1.506
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1447
_refine_ls_number_reflns         28414
_refine_ls_number_restraints     81
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0811
_refine_ls_R_factor_gt           0.0614
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0828P)^2^+14.2277P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1594
_refine_ls_wR_factor_ref         0.1739
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22034
_reflns_number_total             28414
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00792_si_002.cif
_cod_data_source_block           jfig967
_cod_depositor_comments
;
Adding full bibliography for 4086816--4086827.cif.

2026-05-15
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C142 H174.61 Mn2 N4 O9'
_cod_original_formula_weight         2191.34
_cod_original_formula_moiety         '2(C69 H83 Mn N2 O4), C4 H9 O'
_cod_original_formula_units_Z            4
_cod_original_cell_volume        12834(2)
_cod_database_code               4086816
_shelxl_version_number           2013-2
_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
Uanis(C114) \\sim Ueq, Uanis(C113) \\sim Ueq, Uanis(C112) \\sim Ueq,
Uanis(C111) \\sim Ueq, Uanis(C110) \\sim Ueq, Uanis(C109) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.2
Uanis(C16) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C20)
\\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C18) \\sim Ueq: with sigma of 0.1 and
sigma for terminal atoms of 0.2
Uanis(C26A) = Uanis(C26)
Uanis(C108) = Uanis(C106) = Uanis(C107)
3. Rigid body (RIGU) restrains
 C107, C108, C106
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=1-FVAR(1)
 Sof(H17)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C55(H55), C47(H47), C63(H63), C87(H87), C22(H22), C66(H66), C106(H106),
 C36(H36), C94(H94), C33(H33), C129(H129), C121(H121), C99(H99), C124(H124),
 C17(H17), C136(H136)
5.b Secondary CH2 refined with riding coordinates:
 C2S(H2SA,H2SB)
5.c Aromatic/amide H refined with riding coordinates:
 C41(H41), C90(H90), C92(H92), C43(H43), C42(H42), C91(H91), C83(H83),
 C81(H81), C50(H50), C51(H51), C82(H82), C13(H13), C52(H52), C102(H102),
 C11(H11), C60(H60), C61(H61), C59(H59), C104(H104), C119(H119), C20(H20),
 C113(H113), C103(H103), C117(H117), C30(H30), C31(H31), C112(H112), C111(H111),
  C18(H18), C12(H12), C118(H118), C133(H133), C134(H134), C19(H19), C132(H132),
 C29(H29), C3S(H3S)
5.d Idealised Me refined as rotating group:
 C78(H78A,H78B,H78C), C65(H65A,H65B,H65C), C48(H48A,H48B,H48C), C88(H88A,H88B,
 H88C), C64(H64A,H64B,H64C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C54(H54A,H54B,
 H54C), C77(H77A,H77B,H77C), C76(H76A,H76B,H76C), C56(H56A,H56B,H56C), C6(H6A,
 H6B,H6C), C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C67(H67A,H67B,H67C),
 C123(H12A,H12B,H12C), C96(H96A,H96B,H96C), C122(H12D,H12E,H12F), C89(H89A,H89B,
 H89C), C100(H10A,H10B,H10C), C126(H12G,H12H,H12I), C107(H10D,H10E,H10F),
 C38(H38A,H38B,H38C), C95(H95A,H95B,H95C), C49(H49A,H49B,H49C), C37(H37A,H37B,
 H37C), C68(H68A,H68B,H68C), C130(H13A,H13B,H13C), C101(H10G,H10H,H10I),
 C24(H24A,H24B,H24C), C131(H13D,H13E,H13F), C35(H35A,H35B,H35C), C138(H13G,H13H,
 H13I), C125(H12J,H12K,H12L), C108(H10J,H10K,H10L), C137(H13J,H13K,H13L),
 C34(H34A,H34B,H34C), C26(H26A,H26B,H26C), C4S(H4SA,H4SB,H4SC), C1S(H1SA,H1SB,
 H1SC), C26A(H26D,H26E,H26F)
;
_shelx_res_checksum              6107
_shelx_hkl_checksum              28
_olex2_submission_original_sample_id JFig967
_olex2_submission_special_instructions 'No special instructions were received'