Manganese germylene hydride complexes: reactivity with carbon dioxide, benzophenone, and diisopropylcarbodiimide.
Price, Jeffrey S.; Emslie, David J. H.; Dalton transactions (Cambridge, England : 2003) 54 (2025) 14821–14837; doi:10.1039/d5dt01701g

data_7719476
_publ_section_title
;
 Manganese germylene hydride complexes: reactivity with carbon dioxide,
 benzophenone, and diisopropylcarbodiimide.
;
_journal_issue                   39
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              14821
_journal_page_last               14837
_journal_paper_doi               10.1039/d5dt01701g
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C21 H52 Ge Mn N P4'
_chemical_formula_sum            'C21 H52 Ge Mn N P4'
_chemical_formula_weight         570.04
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-08-12
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-07-16 deposited with the CCDC.	2025-09-02 downloaded from the CCDC.
;
_cell_angle_alpha                75.45(3)
_cell_angle_beta                 87.950(17)
_cell_angle_gamma                80.212(10)
_cell_formula_units_Z            4
_cell_length_a                   10.372(5)
_cell_length_b                   16.975(4)
_cell_length_c                   17.653(6)
_cell_measurement_reflns_used    3182
_cell_measurement_temperature    100
_cell_measurement_theta_max      25.214
_cell_measurement_theta_min      2.329
_cell_volume                     2964.5(19)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_details
;
466 frames, detector distance = 100.0 mm
;
_diffrn_measurement_device       '2-circle goniometer'
_diffrn_measurement_device_type  'STOE IPDS II'
_diffrn_measurement_method       'rotation method'
_diffrn_radiation_collimation    '0.5 mm diameter, monocapillary'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0284
_diffrn_reflns_av_unetI/netI     0.0523
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            38759
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.634
_diffrn_reflns_theta_min         1.935
_diffrn_source_current           40.0
_diffrn_source_power             2.0
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.664
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.6687
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0328 before and 0.0214 after correction.
The Ratio of minimum to maximum transmission is 0.8965.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.277
_exptl_crystal_description       block
_exptl_crystal_F_000             1208
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.25
_refine_diff_density_max         1.100
_refine_diff_density_min         -0.934
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     684
_refine_ls_number_reflns         16617
_refine_ls_number_restraints     904
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0623
_refine_ls_R_factor_gt           0.0452
_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^)+(0.0368P)^2^+3.2487P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1070
_refine_ls_wR_factor_ref         0.1135
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13019
_reflns_number_total             16617
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01701g3.cif
_cod_data_source_block           MnGeH2nBu_CNtBu_cis
_cod_depositor_comments
'Adding full bibliography for 7719468--7719476.cif.'
_cod_original_cell_volume        2964.4(18)
_cod_database_code               7719476
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.681
_shelx_estimated_absorpt_t_min   0.594
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C5A-C3A \\sim C3A-C4A \\sim C4A-C5A \\sim C4C-C5C \\sim C5C-C3C \\sim C3C-C4C
\\sim C5-C3 \\sim C3-C4 
 C4-C5
 with sigma of 0.002
 C2A-C5A \\sim C2A-C3A \\sim C2A-C4A \\sim C2A-C5C \\sim C2A-C4C \\sim C2A-C3C
\\sim C2-C5 \\sim C2-C3 
 C2-C4
 with sigma of 0.002
 Mn1-P1 \\sim Mn1-P1B \\sim Mn1-P3 \\sim Mn1-P3B \\sim Mn1A-P1A \\sim Mn1A-P1C
\\sim Mn1A-P3A \\sim Mn1A-P3C
 with sigma of 0.005
 Mn1-P2 \\sim Mn1-P2B \\sim Mn1A-P2A \\sim Mn1A-P4C
 with sigma of 0.005
 Mn1-P4 \\sim Mn1-P4B \\sim Mn1A-P4A \\sim Mn1A-P2C
 with sigma of 0.005
 P4-C19 \\sim P4B-C19B \\sim P3-C18 \\sim P1B-C18B \\sim P2-C13 \\sim P2B-C12B
\\sim P1-C12 \\sim P3B-C13B
 \\sim P1A-C12A \\sim P2A-C13A \\sim P3A-C18A \\sim P4A-C19A \\sim P1C-C12C
\\sim P2C-C13C \\sim P3C-C18C 
 P4C-C19C
 with sigma of 0.005
 C10-C11 \\sim C14-C15 \\sim C16-C17 \\sim C20-C21 \\sim C16B-C17B \\sim
C10B-C11B \\sim C14B-C15B 
 C20B-C21B \\sim C10A-C11A \\sim C14A-C15A \\sim C16A-C17A \\sim C20A-C21A
\\sim C10C-C11C \\sim C14C-
 C15C \\sim C16C-C17C \\sim C20C-C21C
 with sigma of 0.005
 C12-C13 \\sim C18-C19 \\sim C12A-C13A \\sim C18A-C19A \\sim C12B-C13B \\sim
C18B-C19B \\sim C12C-C13C
 \\sim C18C-C19C
 with sigma of 0.005
 C12-C10 \\sim C12-C11 \\sim C13-C14 \\sim C13-C15 \\sim C18-C16 \\sim C18-C17
\\sim C19-C20 \\sim C19-C21
 \\sim C12A-C10A \\sim C12A-C11A \\sim C13A-C14A \\sim C13A-C15A \\sim
C18A-C16A \\sim C18A-C17A \\sim C19A-
 C20A \\sim C19A-C21A \\sim C12B-C10B \\sim C12B-C11B \\sim C13B-C14B \\sim
C13B-C15B \\sim C18B-C16B 
 C18B-C17B \\sim C19B-C20B \\sim C19B-C21B \\sim C12C-C10C \\sim C12C-C11C
\\sim C13C-C14C \\sim C13C-
 C15C \\sim C18C-C16C \\sim C18C-C17C \\sim C19C-C20C \\sim C19C-C21C
 with sigma of 0.005
 C6A-C7A \\sim C7A-C8A \\sim C6C-C7C \\sim C7C-C8C \\sim C6-C7 \\sim C7-C8
 with sigma of 0.005
 C8A-C9A \\sim C8C-C9C \\sim C8-C9
 with sigma of 0.005
 Ge1A-C6A \\sim Ge1A-C6C
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(C5A) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.01
Uanis(C5A) = Uanis(C5C)
Uanis(C4C) = Uanis(C4A)
Uanis(C3A) = Uanis(C3C)
Uanis(P1) = Uanis(P1B)
Uanis(P2B) = Uanis(P2)
Uanis(P3) = Uanis(P3B)
Uanis(P4B) = Uanis(P4)
Uanis(P4A) = Uanis(P2C)
Uanis(P2A) = Uanis(P4C)
Uanis(P1A) = Uanis(P1C)
Uanis(P3A) = Uanis(P3C)
Uanis(C20) = Uanis(C21B)
Uanis(C20B) = Uanis(C21)
Uanis(C15) = Uanis(C11B)
Uanis(C14) = Uanis(C10B)
Uanis(C16) = Uanis(C15B)
Uanis(C16B) = Uanis(C10)
Uanis(C14B) = Uanis(C11)
Uanis(C17) = Uanis(C17B)
Uanis(C19) = Uanis(C19B)
Uanis(C18B) = Uanis(C18)
Uanis(C13) = Uanis(C12B)
Uanis(C12) = Uanis(C13B)
Uanis(C21C) = Uanis(C14A)
Uanis(C20C) = Uanis(C15A)
Uanis(C14C) = Uanis(C21A)
Uanis(C20A) = Uanis(C15C)
Uanis(C16A) = Uanis(C16C)
Uanis(C10A) = Uanis(C10C)
Uanis(C11A) = Uanis(C17C)
Uanis(C17A) = Uanis(C11C)
Uanis(C13C) = Uanis(C19A)
Uanis(C12C) = Uanis(C18A)
Uanis(C13A) = Uanis(C19C)
Uanis(C12A) = Uanis(C18C)
Uanis(C7C) = Uanis(C7A)
Uanis(C8C) = Uanis(C8A)
Uanis(C9A) = Uanis(C9C)
Uanis(C6A) = Uanis(C6C)
4. Rigid body (RIGU) restrains
 C2A, C5A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(P1C)=Sof(P2C)=Sof(P3C)=Sof(P4C)=Sof(C10C)=Sof(H10D)=Sof(H10E)=Sof(H10F)=
 Sof(C11C)=Sof(H11D)=Sof(H11E)=Sof(H11F)=Sof(C12C)=Sof(H12C)=Sof(H12D)=
 Sof(C13C)=Sof(H13C)=Sof(H13D)=Sof(C14C)=Sof(H14D)=Sof(H14E)=Sof(H14F)=
 Sof(C15C)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16C)=Sof(H16D)=Sof(H16E)=
 Sof(H16F)=Sof(C17C)=Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(C18C)=Sof(H18C)=
 Sof(H18D)=Sof(C19C)=Sof(H19C)=Sof(H19D)=Sof(C20C)=Sof(H20D)=Sof(H20E)=
 Sof(H20F)=Sof(C21C)=Sof(H21D)=Sof(H21E)=Sof(H21F)=1-FVAR(1)
 Sof(P1A)=Sof(P2A)=Sof(P3A)=Sof(P4A)=Sof(C10A)=Sof(H10A)=Sof(H10B)=Sof(H10C)=
 Sof(C11A)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C12A)=Sof(H12A)=Sof(H12B)=
 Sof(C13A)=Sof(H13A)=Sof(H13B)=Sof(C14A)=Sof(H14A)=Sof(H14B)=Sof(H14C)=
 Sof(C15A)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16A)=Sof(H16A)=Sof(H16B)=
 Sof(H16C)=Sof(C17A)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18A)=Sof(H18A)=
 Sof(H18B)=Sof(C19A)=Sof(H19A)=Sof(H19B)=Sof(C20A)=Sof(H20A)=Sof(H20B)=
 Sof(H20C)=Sof(C21A)=Sof(H21A)=Sof(H21B)=Sof(H21C)=FVAR(1)
 Sof(P1B)=Sof(P2B)=Sof(P3B)=Sof(P4B)=Sof(C10B)=Sof(H10J)=Sof(H10K)=Sof(H10L)=
 Sof(C11B)=Sof(H11J)=Sof(H11K)=Sof(H11L)=Sof(C12B)=Sof(H12G)=Sof(H12H)=
 Sof(C13B)=Sof(H13G)=Sof(H13H)=Sof(C14B)=Sof(H14J)=Sof(H14K)=Sof(H14L)=
 Sof(C15B)=Sof(H15J)=Sof(H15K)=Sof(H15L)=Sof(C16B)=Sof(H16J)=Sof(H16K)=
 Sof(H16L)=Sof(C17B)=Sof(H17J)=Sof(H17K)=Sof(H17L)=Sof(C18B)=Sof(H18G)=
 Sof(H18H)=Sof(C19B)=Sof(H19G)=Sof(H19H)=Sof(C20B)=Sof(H20J)=Sof(H20K)=
 Sof(H20L)=Sof(C21B)=Sof(H21J)=Sof(H21K)=Sof(H21L)=1-FVAR(2)
 Sof(P1)=Sof(P2)=Sof(P3)=Sof(P4)=Sof(C10)=Sof(H10G)=Sof(H10H)=Sof(H10I)=
 Sof(C11)=Sof(H11G)=Sof(H11H)=Sof(H11I)=Sof(C12)=Sof(H12E)=Sof(H12F)=Sof(C13)=
 Sof(H13E)=Sof(H13F)=Sof(C14)=Sof(H14G)=Sof(H14H)=Sof(H14I)=Sof(C15)=Sof(H15G)=
 Sof(H15H)=Sof(H15I)=Sof(C16)=Sof(H16G)=Sof(H16H)=Sof(H16I)=Sof(C17)=Sof(H17G)=
 Sof(H17H)=Sof(H17I)=Sof(C18)=Sof(H18E)=Sof(H18F)=Sof(C19)=Sof(H19E)=Sof(H19F)=
 Sof(C20)=Sof(H20G)=Sof(H20H)=Sof(H20I)=Sof(C21)=Sof(H21G)=Sof(H21H)=Sof(H21I)=
 FVAR(2)
 Sof(C3C)=Sof(H3CA)=Sof(H3CB)=Sof(H3CC)=Sof(C4C)=Sof(H4CA)=Sof(H4CB)=Sof(H4CC)=
 Sof(C5C)=Sof(H5CA)=Sof(H5CB)=Sof(H5CC)=1-FVAR(3)
 Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=
 Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=FVAR(3)
 Sof(C6C)=Sof(H6CA)=Sof(H6CB)=Sof(C7C)=Sof(H7CA)=Sof(H7CB)=Sof(C8C)=Sof(H8CA)=
 Sof(H8CB)=Sof(C9C)=Sof(H9CA)=Sof(H9CB)=Sof(H9CC)=1-FVAR(4)
 Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(C8A)=Sof(H8AA)=
 Sof(H8AB)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=FVAR(4)
6.a Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C12(H12E,H12F), C12B(H12G,H12H),
 C13(H13E,H13F), C13B(H13G,H13H), C18(H18E,H18F), C18B(H18G,H18H), C19(H19E,
 H19F), C19B(H19G,H19H), C6A(H6AA,H6AB), C6C(H6CA,H6CB), C7A(H7AA,H7AB),
 C7C(H7CA,H7CB), C8A(H8AA,H8AB), C8C(H8CA,H8CB), C12A(H12A,H12B), C12C(H12C,
 H12D), C13A(H13A,H13B), C13C(H13C,H13D), C18A(H18A,H18B), C18C(H18C,H18D),
 C19A(H19A,H19B), C19C(H19C,H19D)
6.b Me refined with riding coordinates:
 C3A(H3AA,H3AB,H3AC), C4C(H4CA,H4CB,H4CC)
6.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C9(H9A,H9B,H9C), C10(H10G,
 H10H,H10I), C10B(H10J,H10K,H10L), C11(H11G,H11H,H11I), C11B(H11J,H11K,H11L),
 C14(H14G,H14H,H14I), C14B(H14J,H14K,H14L), C15(H15G,H15H,H15I), C15B(H15J,H15K,
 H15L), C16(H16G,H16H,H16I), C16B(H16J,H16K,H16L), C17(H17G,H17H,H17I),
 C17B(H17J,H17K,H17L), C20(H20G,H20H,H20I), C20B(H20J,H20K,H20L), C21(H21G,H21H,
 H21I), C21B(H21J,H21K,H21L), C3C(H3CA,H3CB,H3CC), C4A(H4AA,H4AB,H4AC),
 C5A(H5AA,H5AB,H5AC), C5C(H5CA,H5CB,H5CC), C9A(H9AA,H9AB,H9AC), C9C(H9CA,H9CB,
 H9CC), C10A(H10A,H10B,H10C), C10C(H10D,H10E,H10F), C11A(H11A,H11B,H11C),
 C11C(H11D,H11E,H11F), C14A(H14A,H14B,H14C), C14C(H14D,H14E,H14F), C15A(H15A,
 H15B,H15C), C15C(H15D,H15E,H15F), C16A(H16A,H16B,H16C), C16C(H16D,H16E,H16F),
 C17A(H17A,H17B,H17C), C17C(H17D,H17E,H17F), C20A(H20A,H20B,H20C), C20C(H20D,
 H20E,H20F), C21A(H21A,H21B,H21C), C21C(H21D,H21E,H21F)
;
_shelx_res_checksum              31152
_olex2_submission_special_instructions 'No special instructions were received'