Reactions of Osmium Hydrido Alkenylcarbyne with Allenoates: Insertion and [3 + 2] Annulation
Zhou, Xiaoxi; He, Xiehua; Lin, Jianfeng; Zhuo, Qingde; Chen, Zhixin; Zhang, Hong; Wang, Jianbo; Xia, Haiping; Organometallics 34 (2015) 1742–; doi:10.1021/acs.organomet.5b00242

data_4087541
_publ_section_title
;
 Reactions of Osmium Hydrido Alkenylcarbyne with Allenoates: Insertion and
 [3 + 2] Annulation
;
_journal_issue                   9
_journal_name_full               Organometallics
_journal_page_first              1742
_journal_paper_doi               10.1021/acs.organomet.5b00242
_journal_volume                  34
_journal_year                    2015
_chemical_formula_moiety         'C73 H65 B2 F8 O4 Os P3,C1 Cl2 H2'
_chemical_formula_sum            'C74 H67 B2 Cl2 F8 O4 Os P3'
_chemical_formula_weight         1547.93
_chemical_name_systematic        triclinic
_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     heavy
_audit_creation_date             2014-11-30
_audit_creation_method
;
Olex2 1.2
(compiled 2014.11.25 svn.r3098 for OlexSys, GUI svn.r4951)
;
_cell_angle_alpha                78.5660(10)
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_cell_angle_gamma                61.9190(10)
_cell_formula_units_Z            2
_cell_length_a                   13.0016(4)
_cell_length_b                   13.3826(9)
_cell_length_c                   22.8476(6)
_cell_measurement_temperature    153
_cell_measurement_theta_max      55.07
_cell_measurement_theta_min      6.01
_cell_volume                     3427.9(3)
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      153
_diffrn_measured_fraction_theta_full 0.971
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'multiwire proportional'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1213
_diffrn_reflns_av_unetI/netI     0.0971
_diffrn_reflns_Laue_measured_fraction_full 0.971
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            44509
_diffrn_reflns_point_group_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         3.004
_exptl_absorpt_coefficient_mu    2.079
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.1913
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            'dull reddish red'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.500
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_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
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_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.104
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1113
_refine_ls_number_reflns         12045
_refine_ls_number_restraints     204
_refine_ls_restrained_S_all      1.103
_refine_ls_R_factor_all          0.0958
_refine_ls_R_factor_gt           0.0698
_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^)+(0.0992P)^2^+0.1602P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1576
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_reflns_Friedel_coverage         0.000
_reflns_number_gt                9125
_reflns_number_total             12045
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00242_si_003.cif
_cod_data_source_block           complex_5
_cod_database_code               4087541
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C251) \\sim Ueq, Uanis(C222) \\sim Ueq, Uanis(C253) \\sim Ueq,
Uanis(C254) \\sim Ueq, Uanis(C255) \\sim Ueq, Uanis(C256) \\sim Ueq,
Uanis(C256) \\sim Ueq, Uanis(C225) \\sim Ueq, Uanis(C222) \\sim Ueq,
Uanis(C251) \\sim Ueq, Uanis(C254) \\sim Ueq, Uanis(C253) \\sim Ueq: with sigma
of 0.05 and sigma for terminal atoms of 0.04
Uanis(B2) \\sim Ueq, Uanis(F7) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C333) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.04
Uanis(F5) \\sim Ueq, Uanis(Cl2) \\sim Ueq: with sigma of 0.05 and sigma for
terminal atoms of 0.04
Uanis(C346) \\sim Ueq, Uanis(C335) \\sim Ueq, Uanis(C344) \\sim Ueq,
Uanis(C343) \\sim Ueq, Uanis(C342) \\sim Ueq, Uanis(C341) \\sim Ueq,
Uanis(C342) \\sim Ueq, Uanis(C343) \\sim Ueq, Uanis(C346) \\sim Ueq,
Uanis(C335) \\sim Ueq, Uanis(C344) \\sim Ueq: with sigma of 0.05 and sigma for
terminal atoms of 0.04
Uanis(C331) \\sim Ueq, Uanis(C341) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C216) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C244) \\sim Ueq, Uanis(C243) \\sim Ueq, Uanis(C242) \\sim Ueq,
Uanis(C241) \\sim Ueq, Uanis(C246) \\sim Ueq, Uanis(C243) \\sim Ueq,
Uanis(C242) \\sim Ueq, Uanis(C241) \\sim Ueq, Uanis(C213) \\sim Ueq,
Uanis(C244) \\sim Ueq, Uanis(C245) \\sim Ueq, Uanis(C246) \\sim Ueq: with sigma
of 0.05 and sigma for terminal atoms of 0.04
Uanis(F3) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C231) \\sim Ueq, Uanis(C261) \\sim Ueq, Uanis(C236) \\sim Ueq,
Uanis(C266) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.02
Uanis(C2S) \\sim Ueq, Uanis(Cl5) \\sim Ueq, Uanis(C2S) \\sim Ueq, Uanis(Cl5)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.04
3. Others
 Fixed Sof: B2(0.5) C1S(0.5) H1SA(0.25) H1SB(0.25) H1SC(0.25) H1SD(0.25)
 C264(0.5) H264(0.5) C215(0.5) H215(0.5) C214(0.5) H214(0.5) C213(0.5)
 H213(0.5) C212(0.5) H212(0.5) C211(0.5) C216(0.5) H216(0.5) C255(0.5)
 H255(0.5) C332(0.5) H332(0.5) C232(0.5) H232(0.5) C231(0.5) C236(0.5)
 H236(0.5) C235(0.5) H235(0.5) C234(0.5) H234(0.5) C233(0.5) H233(0.5)
 C253(0.5) H253(0.5) C252(0.5) H252(0.5) C251(0.5) C221(0.5) C222(0.5)
 H222(0.5) C256(0.5) H256(0.5) C223(0.5) H223(0.5) C254(0.5) H254(0.5)
 C224(0.5) H224(0.5) C225(0.5) H225(0.5) C226(0.5) H226(0.5) C246(0.5)
 H246(0.5) C241(0.5) C242(0.5) H242(0.5) C243(0.5) H243(0.5) C244(0.5)
 H244(0.5) C245(0.5) H245(0.5) C261(0.5) C262(0.5) H262(0.5) C263(0.5)
 H263(0.5) C265(0.5) H265(0.5) C266(0.5) H266(0.5) C334(0.5) H334(0.5)
 C336(0.5) H336(0.5) C341(0.5) C342(0.5) H342(0.5) C343(0.5) H343(0.5)
 C344(0.5) H344(0.5) C345(0.5) H345(0.5) C346(0.5) H346(0.5) C335(0.5)
 H335(0.5) C2S(0.5) C333(0.5) H333(0.5) C331(0.5) F6(0.5) F8(0.5) F7(0.5)
 Cl6(0.5) Cl3(0.5) Cl1(0.25) Cl2(0.25) Cl4(0.25) Cl5(0.25) B3(0.5) F10(0.5)
 F9(0.5)
4.a Ternary CH refined with riding coordinates:
 C2S(H2S)
4.b Secondary CH2 refined with riding coordinates:
 C1S(H1SA,H1SB), C1S(H1SC,H1SD), C16(H16A,H16B), C18(H18A,H18B), C14(H14A,H14B)
4.c Aromatic/amide H refined with riding coordinates:
 C264(H264), C9(H9), C8(H8), C7(H7), C6(H6), C3(H3), C215(H215), C214(H214),
 C213(H213), C212(H212), C216(H216), C255(H255), C332(H332), C232(H232),
 C236(H236), C235(H235), C234(H234), C233(H233), C253(H253), C252(H252),
 C132(H132), C133(H133), C134(H134), C135(H135), C136(H136), C122(H122),
 C123(H123), C124(H124), C125(H125), C126(H126), C112(H112), C113(H113),
 C114(H114), C115(H115), C116(H116), C222(H222), C256(H256), C223(H223),
 C254(H254), C224(H224), C225(H225), C226(H226), C246(H246), C242(H242),
 C243(H243), C244(H244), C245(H245), C262(H262), C263(H263), C265(H265),
 C266(H266), C316(H316), C315(H315), C314(H314), C313(H313), C334(H334),
 C312(H312), C326(H326), C325(H325), C324(H324), C323(H323), C322(H322),
 C336(H336), C342(H342), C343(H343), C344(H344), C345(H345), C346(H346),
 C335(H335), C333(H333)
4.d Fitted hexagon refined as free rotating group:
 C215(C214,C213,C212,C211,C216), C232(C231,C236,C235,C234,C233), C246(C241,
 C242,C243,C244,C245)
4.e Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C15(H15A,H15B,H15C)
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_shelx_res_checksum              40426
_shelx_hkl_checksum              5119
_olex2_submission_special_instructions 'No special instructions were received'