Metallation of sensitive fluoroarenes using a potassium TMP-zincate supported by a silyl(bis)amido ligand
Mastropierro, Pasquale; Kennedy, Alan R.; Hevia, Eva; Chemical Communications  (2022) –; doi:10.1039/D2CC00979J

data_7129962
_publ_section_title
;
 Metallation of sensitive fluoroarenes using a potassium TMP-zincate
 supported by a silyl(bis)amido ligand
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC00979J
_journal_year                    2022
_chemical_formula_moiety         'C45 H62 N3 Si Zn, 1(C24 H48 Na O6)'
_chemical_formula_sum            'C69 H110 N3 Na O6 Si Zn'
_chemical_formula_weight         1194.04
_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   geom
_audit_creation_date             2022-03-01
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-03-04 deposited with the CCDC.	2022-03-08 downloaded from the CCDC.
;
_cell_angle_alpha                87.6370(10)
_cell_angle_beta                 82.6610(10)
_cell_angle_gamma                88.9470(10)
_cell_formula_units_Z            8
_cell_length_a                   10.47530(10)
_cell_length_b                   35.3408(5)
_cell_length_c                   37.5660(5)
_cell_measurement_reflns_used    37720
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      73.1710
_cell_measurement_theta_min      3.7300
_cell_volume                     13780.3(3)
_computing_cell_refinement       CrysalisPro
_computing_data_collection       CrysalisPro
_computing_data_reduction        CrysalisPro
_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, 2018)'
_computing_structure_solution    SHELXS
_diffrn_ambient_temperature      123(2)
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_device_type  'Oxford Diffraction Gemini S'
_diffrn_measurement_method       'omega scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0380
_diffrn_reflns_av_unetI/netI     0.0441
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       43
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            125953
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        70.000
_diffrn_reflns_theta_max         73.190
_diffrn_reflns_theta_min         4.961
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    1.104
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.23972
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.151
_exptl_crystal_description       block
_exptl_crystal_F_000             5184
_exptl_crystal_size_max          0.9
_exptl_crystal_size_mid          0.6
_exptl_crystal_size_min          0.6
_refine_diff_density_max         1.308
_refine_diff_density_min         -0.525
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3056
_refine_ls_number_reflns         54223
_refine_ls_number_restraints     423
_refine_ls_restrained_S_all      2.143
_refine_ls_R_factor_all          0.0738
_refine_ls_R_factor_gt           0.0615
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1007P)^2^+9.0123P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1656
_refine_ls_wR_factor_ref         0.1776
_reflns_Friedel_coverage         0.000
_reflns_number_gt                44552
_reflns_number_total             54223
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc00979j2.cif
_cod_data_source_block           pm322-c
_cod_database_code               7129962
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Shared sites
{C202, C902}
2. Restrained distances
 C139-C140 = C140-C141 = C141-C142 = C939-C940 = C940-C941 = C941-C942
 1.53 with sigma of 0.01
 O13-C139 = O13-C142 = O13-C939 = O13-C942
 1.43 with sigma of 0.01
 C149-C148 = C147-C148 = C149-C948 = C147-C948
 1.53 with sigma of 0.01
 O5-C62 = O5-C65 = O5-C962 = O5-C965 = O12-C90 = O12-C93
 1.43 with sigma of 0.01
 C62-C63 = C63-C64 = C64-C65 = C962-C963 = C963-C964 = C964-C965
 1.53 with sigma of 0.01
 C90-C91 = C91-C92 = C92-C93 = C990-C991 = C991-C992 = C992-C993
 1.53 with sigma of 0.01
 O15-C159 = O9-C81 = O12-C990 = O12-C993
 1.43 with sigma of 0.01
 C82-C83 = C83-C84 = C81-C80 = C159-C160 = C981-C80 = C959-C160
 1.53 with sigma of 0.01
 C82-C983 = C983-C84 = C981-C80 = C959-C160
 1.53 with sigma of 0.01
 N3-C37 = N3-C41 = N9-C199 = N9-C203 = N9-C903
 1.48 with sigma of 0.01
 C37-C44 = C37-C45 = C37-C38 = C38-C39 = C39A-C40A = C41-C43A = C41-C42A
 1.53 with sigma of 0.01
 C37-C44A = C37-C45A = C37-C38A = C38A-C39A = C39-C40 = C41-C43 = C41-C42
 1.53 with sigma of 0.01
 C40-C41 = C40A-C41 = C199-C200 = C199-C206 = C199-C207 = C200-C201
 1.53 with sigma of 0.01
 C201-C202 = C202-C203 = C203-C204 = C203-C205 = C199-C906 = C199-C907
 1.53 with sigma of 0.01
 C199-C900 = C900-C901 = C901-C902 = C902-C903 = C903-C904 = C903-C905
 1.53 with sigma of 0.01
 C906-C907
 2.45 with sigma of 0.02
 C905-C904
 2.45 with sigma of 0.02
3. Rigid bond restraints
 O13, C139, C140, C141, C142
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O15, C147, C148, C149, C150
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O5, C62, C63, C64, C65
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O12, C90, C91, C92, C93
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N3, C37, C41, C38, C39, C40, C42, C43, C44, C45
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N9, C199, C200, C201, C202, C203, C204, C205, C206, C207
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O12, C91, C93, C90, C92
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
O13 \\sim C139 \\sim C140 \\sim C141 \\sim C142: within 1.7A with sigma of 0.02
and sigma for terminal atoms of 0.02 within 1.7A
O15 \\sim C147 \\sim C148 \\sim C149 \\sim C150: within 1.7A with sigma of 0.02
and sigma for terminal atoms of 0.02 within 1.7A
O5 \\sim C62 \\sim C63 \\sim C64 \\sim C65: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.01 within 1.7A
O12 \\sim C90 \\sim C91 \\sim C92 \\sim C93: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.01 within 1.7A
N3 \\sim C37 \\sim C41 \\sim C38 \\sim C39 \\sim C40 \\sim C42 \\sim C43 \\sim
C44 \\sim C45: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.01 within 1.7A
N9 \\sim C199 \\sim C200 \\sim C201 \\sim C202 \\sim C203 \\sim C204 \\sim C205
\\sim C206 \\sim C207: within 1.7A with sigma of 0.02 and sigma for terminal
atoms of 0.02 within 1.7A
O12 \\sim C91 \\sim C93 \\sim C90 \\sim C92: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.02 within 1.7A
Uanis(C44) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(C90) = Uanis(C990)
Uanis(C91) = Uanis(C991)
Uanis(C92) = Uanis(C992)
Uanis(C93) = Uanis(C993)
Uanis(C139) = Uanis(C939)
Uanis(C140) = Uanis(C940)
Uanis(C141) = Uanis(C941)
Uanis(C81) = Uanis(C981)
Uanis(C83) = Uanis(C983)
Uanis(C159) = Uanis(C959)
Uanis(C142) = Uanis(C942)
Uanis(C148) = Uanis(C948)
Uanis(C62) = Uanis(C962)
Uanis(C63) = Uanis(C963)
Uanis(C64) = Uanis(C964)
Uanis(C65) = Uanis(C965)
Uanis(C38) = Uanis(C38A)
Uanis(C39) = Uanis(C39A)
Uanis(C40) = Uanis(C40A)
Uanis(C42) = Uanis(C42A)
Uanis(C43) = Uanis(C43A)
Uanis(C45) = Uanis(C45A)
Uanis(C206) = Uanis(C906)
Uanis(C207) = Uanis(C907)
Uanis(C200) = Uanis(C900)
Uanis(C201) = Uanis(C901)
Uanis(C202) = Uanis(C902)
Uanis(C203) = Uanis(C903)
Uanis(C904) = Uanis(C204)
Uanis(C205) = Uanis(C905)
5. Others
 Sof(C939)=Sof(H93C)=Sof(H93D)=Sof(C941)=Sof(H94A)=Sof(H94B)=Sof(C942)=
 Sof(H94C)=Sof(H94D)=Sof(C940)=Sof(H94E)=Sof(H94F)=1-FVAR(1)
 Sof(C139)=Sof(H13S)=Sof(H13T)=Sof(C140)=Sof(H14A)=Sof(H14B)=Sof(C141)=
 Sof(H14C)=Sof(H14D)=Sof(C142)=Sof(H1ZE)=Sof(H1ZF)=FVAR(1)
 Sof(C948)=Sof(H94G)=Sof(H94H)=Sof(C959)=Sof(H95A)=Sof(H95B)=1-FVAR(2)
 Sof(C148)=Sof(H14G)=Sof(H14H)=Sof(C159)=Sof(H15S)=Sof(H15T)=FVAR(2)
 Sof(C962)=Sof(H96A)=Sof(H96B)=Sof(C965)=Sof(H96C)=Sof(H96D)=Sof(C964)=
 Sof(H96E)=Sof(H96F)=Sof(C963)=Sof(H96G)=Sof(H96H)=1-FVAR(3)
 Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(C64)=Sof(H64A)=
 Sof(H64B)=Sof(C65)=Sof(H65A)=Sof(H65B)=FVAR(3)
 Sof(C991)=Sof(H99A)=Sof(H99B)=Sof(C993)=Sof(H99C)=Sof(H99D)=Sof(C990)=
 Sof(H99E)=Sof(H99F)=Sof(C992)=Sof(H99G)=Sof(H99H)=1-FVAR(4)
 Sof(C91)=Sof(H91A)=Sof(H91B)=Sof(C93)=Sof(H93A)=Sof(H93B)=Sof(C90)=Sof(H90A)=
 Sof(H90B)=Sof(C92)=Sof(H92A)=Sof(H92B)=FVAR(4)
 Sof(C901)=Sof(H90C)=Sof(H90D)=Sof(C907)=Sof(H90E)=Sof(H90F)=Sof(H90G)=
 Sof(C900)=Sof(H90H)=Sof(H90I)=Sof(C902)=Sof(H90J)=Sof(H90K)=Sof(C906)=
 Sof(H90L)=Sof(H90M)=Sof(H90N)=Sof(C903)=Sof(C904)=Sof(H2GG)=Sof(H2HH)=
 Sof(H2II)=Sof(C905)=Sof(H2JJ)=Sof(H2KK)=Sof(H2LL)=1-FVAR(5)
 Sof(C200)=Sof(H20A)=Sof(H20B)=Sof(C201)=Sof(H20C)=Sof(H20D)=Sof(C202)=
 Sof(H20E)=Sof(H20F)=Sof(C203)=Sof(C204)=Sof(H20G)=Sof(H20H)=Sof(H20I)=
 Sof(C205)=Sof(H20J)=Sof(H20K)=Sof(H20L)=Sof(C206)=Sof(H20M)=Sof(H20N)=
 Sof(H20O)=Sof(C207)=Sof(H20P)=Sof(H20Q)=Sof(H20R)=FVAR(5)
 Sof(C981)=Sof(H98A)=Sof(H98B)=1-FVAR(6)
 Sof(C81)=Sof(H81A)=Sof(H81B)=FVAR(6)
 Sof(C983)=Sof(H98C)=Sof(H98D)=1-FVAR(7)
 Sof(C83)=Sof(H83A)=Sof(H83B)=FVAR(7)
 Sof(C44A)=Sof(H44D)=Sof(H44E)=Sof(H44F)=Sof(C39A)=Sof(H39C)=Sof(H39D)=
 Sof(C45A)=Sof(H45D)=Sof(H45E)=Sof(H45F)=Sof(C43A)=Sof(H43D)=Sof(H43E)=
 Sof(H43F)=Sof(C38A)=Sof(H38C)=Sof(H38D)=Sof(C40A)=Sof(H40C)=Sof(H40D)=
 Sof(C42A)=Sof(H42D)=Sof(H42E)=Sof(H42F)=1-FVAR(8)
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(C40)=Sof(H40A)=
 Sof(H40B)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C43)=Sof(H43A)=Sof(H43B)=
 Sof(H43C)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=Sof(C45)=Sof(H45A)=Sof(H45B)=
 Sof(H45C)=FVAR(8)
6.a Ternary CH refined with riding coordinates:
 C19(H19), C22(H22), C31(H31), C34(H34), C112(H112), C115(H115), C124(H124),
 C127(H127), C181(H181), C184(H184), C193(H193), C196(H196), C248(H248),
 C251(H251), C260(H260), C263(H263)
6.b Secondary CH2 refined with riding coordinates:
 C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B), C46(H46A,H46B), C47(H47A,
 H47B), C48(H48A,H48B), C49(H49A,H49B), C049(H04A,H04B), C50(H50A,H50B),
 C51(H51A,H51B), C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B),
  C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B), C59(H59A,H59B), C60(H60A,
 H60B), C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B), C64(H64A,H64B),
 C65(H65A,H65B), C66(H66A,H66B), C67(H67A,H67B), C68(H68A,H68B), C69(H69A,H69B),
  C70(H70A,H70B), C71(H71A,H71B), C72(H72A,H72B), C73(H73A,H73B), C74(H74A,
 H74B), C75(H75A,H75B), C76(H76A,H76B), C77(H77A,H77B), C78(H78A,H78B),
 C79(H79A,H79B), C80(H80A,H80B), C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B),
  C84(H84A,H84B), C85(H85A,H85B), C86(H86A,H86B), C87(H87A,H87B), C88(H88A,
 H88B), C89(H89A,H89B), C131(H13F,H13G), C132(H13K,H13L), C133(H13A,H13B),
 C139(H13S,H13T), C140(H14A,H14B), C141(H14C,H14D), C142(H1ZE,H1ZF), C143(H14E,
 H14F), C144(H14I,H14J), C145(H1ZA,H1ZB), C146(H1ZC,H1ZD), C147(H14M,H14N),
 C148(H14G,H14H), C149(H14K,H14L), C150(H15G,H15H), C151(H15E,H15F), C152(H15M,
 H15N), C153(H15Q,H15R), C154(H15C,H15D), C155(H15A,H15B), C156(H15I,H15J),
 C157(H15K,H15L), C158(H15O,H15P), C159(H15S,H15T), C160(H16A,H16B), C161(H16E,
 H16F), C162(H16C,H16D), C200(H20A,H20B), C201(H20C,H20D), C202(H20E,H20F),
 C208(H20X,H20Y), C209(H20V,H20W), C210(H21D,H21E), C211(H21P,H21Q), C212(H21T,
 H21U), C213(H21J,H21K), C214(H21N,H21O), C215(H21H,H21I), C216(H21R,H21S),
 C217(H21V,H21W), C218(H21F,H21G), C219(H21L,H21M), C220(H22O,H22P), C221(H22M,
 H22N), C222(H22A,H22B), C223(H22I,H22J), C224(H22C,H22D), C225(H22K,H22L),
 C226(H22E,H22F), C227(H22G,H22H), C228(H22S,H22T), C229(H22Q,H22R), C230(H23D,
 H23E), C269(H26D,H26E), C270(H27C,H27D), C271(H27A,H27B), C939(H93C,H93D),
 C941(H94A,H94B), C942(H94C,H94D), C940(H94E,H94F), C948(H94G,H94H), C962(H96A,
 H96B), C965(H96C,H96D), C964(H96E,H96F), C963(H96G,H96H), C91(H91A,H91B),
 C93(H93A,H93B), C90(H90A,H90B), C92(H92A,H92B), C959(H95A,H95B), C981(H98A,
 H98B), C983(H98C,H98D), C39A(H39C,H39D), C38A(H38C,H38D), C40A(H40C,H40D),
 C901(H90C,H90D), C900(H90H,H90I), C902(H90J,H90K), C991(H99A,H99B), C993(H99C,
 H99D), C990(H99E,H99F), C992(H99G,H99H)
6.c Me refined with riding coordinates:
 C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,
 H45C), C204(H20G,H20H,H20I), C205(H20J,H20K,H20L), C206(H20M,H20N,H20O),
 C207(H20P,H20Q,H20R), C44A(H44D,H44E,H44F), C45A(H45D,H45E,H45F), C43A(H43D,
 H43E,H43F), C42A(H42D,H42E,H42F), C907(H90E,H90F,H90G), C906(H90L,H90M,H90N),
 C904(H2GG,H2HH,H2II), C905(H2JJ,H2KK,H2LL)
6.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C02G(H02G), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10),
 C11(H11), C12(H12), C15(H15), C16(H16), C17(H17), C27(H27), C28(H28), C29(H29),
  C95(H95), C96(H96), C97(H97), C98(H98), C99(H99), C101(H101), C102(H102),
 C103(H103), C104(H104), C105(H105), C108(H108), C109(H109), C110(H110),
 C120(H120), C121(H121), C122(H122), C164(H164), C165(H165), C166(H166),
 C167(H167), C168(H168), C170(H170), C172(H172), C173(H173), C174(H174),
 C177(H177), C178(H178), C179(H179), C189(H189), C190(H190), C191(H191),
 C232(H232), C233(H233), C234(H234), C235(H235), C237(H237), C238(H238),
 C239(H239), C240(H240), C241(H241), C244(H244), C245(H245), C246(H246),
 C256(H256), C257(H257), C258(H258), C275(H275)
6.e Idealised Me refined as rotating group:
 C20(H20S,H20T,H20U), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24D,H24E,
 H24F), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C36(H36A,
 H36B,H36C), C113(H11J,H11K,H11L), C114(H11G,H11H,H11I), C116(H11A,H11B,H11C),
 C117(H11D,H11E,H11F), C125(H12A,H12B,H12C), C126(H12D,H12E,H12F), C128(H12J,
 H12K,H12L), C129(H12G,H12H,H12I), C135(H13C,H13D,H13E), C136(H13P,H13Q,H13R),
 C137(H13M,H13N,H13O), C138(H13H,H13I,H13J), C182(H18G,H18H,H18I), C183(H18A,
 H18B,H18C), C185(H18D,H18E,H18F), C186(H18J,H18K,H18L), C194(H19A,H19B,H19C),
 C195(H19D,H19E,H19F), C197(H19J,H19K,H19L), C198(H19G,H19H,H19I), C249(H24A,
 H24B,H24C), C250(H25G,H25H,H25I), C252(H25D,H25E,H25F), C253(H25A,H25B,H25C),
 C261(H26R,H26S,H26T), C262(H26O,H26P,H26Q), C264(H26F,H26G,H26H), C265(H26I,
 H26J,H26K), C267(H26A,H26B,H26C), C268(H26L,H26M,H26N), C273(H27H,H27I,H27J),
 C274(H27E,H27F,H27G)
;
_shelx_res_checksum              50185
_shelx_hkl_checksum              84530
_olex2_submission_special_instructions 'No special instructions were received'