Accelerating the Insertion Reactions of (NHC)Cu-H via Remote Ligand Functionalization
Speelman, Amy L.; Tran, Ba; Erickson, Jeremy D.; Vasiliu, Monica; Dixon, David A.; Bullock, R. Morris; Chemical Science  (2021) –; doi:10.1039/D1SC01911B

data_1564274
_publ_section_title
;
 Accelerating the Insertion Reactions of (NHC)Cu-H via Remote Ligand
 Functionalization
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC01911B
_journal_year                    2021
_chemical_formula_moiety
'C142 H122 Cu2 N4, 0.125[C4H8O], 0.125[C5H12]'
_chemical_formula_sum            'C142 H122 Cu2 N4'
_chemical_formula_weight         2011.51
_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'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2021-02-10
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6257)
;
_audit_update_record
;
2021-02-10 deposited with the CCDC.	2021-07-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 111.097(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   27.2994(17)
_cell_length_b                   30.050(2)
_cell_length_c                   33.605(2)
_cell_measurement_reflns_used    9966
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      32.62
_cell_measurement_theta_min      2.35
_cell_volume                     25720(3)
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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  0.0840
_diffrn_reflns_av_unetI/netI     0.0435
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       41
_diffrn_reflns_limit_h_min       -41
_diffrn_reflns_limit_k_max       45
_diffrn_reflns_limit_k_min       -45
_diffrn_reflns_limit_l_max       50
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_number            925690
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.651
_diffrn_reflns_theta_min         1.737
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.378
_exptl_absorpt_correction_T_max  0.8880
_exptl_absorpt_correction_T_min  0.8363
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0848 before and 0.0546 after correction. The Ratio of minimum to maximum transmission is 0.9418. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.039
_exptl_crystal_description       block
_exptl_crystal_F_000             8480
_exptl_crystal_size_max          0.314
_exptl_crystal_size_mid          0.198
_exptl_crystal_size_min          0.13
_refine_diff_density_max         2.362
_refine_diff_density_min         -0.944
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2725
_refine_ls_number_reflns         94041
_refine_ls_number_restraints     2418
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0943
_refine_ls_R_factor_gt           0.0670
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0858P)^2^+17.0246P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1695
_refine_ls_wR_factor_ref         0.1843
_reflns_Friedel_coverage         0.000
_reflns_number_gt                66199
_reflns_number_total             94041
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01911b3.cif
_cod_data_source_block           jdebt07_a
_cod_database_code               1564274
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.953
_shelx_estimated_absorpt_t_min   0.891
_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. Restrained distances
 C115-C114 \\sim C115-C118
 with sigma of 0.02
 C111-C112 \\sim C111-C116
 with sigma of 0.02
 C113-C112 \\sim C117-C116
 with sigma of 0.02
 C113-C114 \\sim C117-C118
 with sigma of 0.02
 C113-C133 \\sim C117-C135
 with sigma of 0.02
 C115-C113 \\sim C115-C117
 with sigma of 0.04
 C111-C113 \\sim C111-C117
 with sigma of 0.04
 C112-C114 \\sim C116-C118
 with sigma of 0.04
 C112-C133 \\sim C116-C135
 with sigma of 0.04
 C114-C133 \\sim C118-C135
 with sigma of 0.04
 C206-C208 \\sim C206-C207
 with sigma of 0.02
 C57-C59 \\sim C57-C58
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
: with sigma of 0.1 and sigma for terminal atoms of 0.2
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: H57A(0.5) H57B(0.5) H57C(0.5) H57D(0.5) C59(0.33333) H59A(0.33333)
 H59B(0.33333) H59C(0.33333) C112(0.9) H112(0.9) C113(0.9) C114(0.9) H114(0.9)
 C133(0.9) H13A(0.9) H13B(0.9) C134(0.9) H13C(0.9) H13D(0.9) H13E(0.9)
 C58(0.66667) H58A(0.66667) H58B(0.66667) H58C(0.66667) C116(0.1) H116(0.1)
 C117(0.1) C118(0.1) H118(0.1) C135(0.1) H13F(0.1) H13G(0.1) C136(0.1)
 H13H(0.1) H13I(0.1) H13J(0.1) H20A(0.4) H20B(0.4) H20C(0.6) H20D(0.6)
 C208(0.4) H20E(0.4) H20F(0.4) H20G(0.4) C207(0.6) H20H(0.6) H20I(0.6) H20J(0.6)
6.a Ternary CH refined with riding coordinates:
 C10(H10), C25(H25), C44(H44), C60(H60), C82(H82), C97(H97), C119(H119),
 C137(H137), C159(H159), C174(H174), C193(H193), C209(H209), C231(H231),
 C246(H246), C265(H265), C280(H280)
6.b Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C57(H57A,H57B), C57(H57C,H57D), C95(H95A,H95B), C133(H13A,
 H13B), C135(H13F,H13G), C172(H17A,H17B), C206(H20A,H20B), C206(H20C,H20D),
 C244(H24D,H24E), C278(H27A,H27B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C8(H8), C12(H12), C13(H13), C14(H14), C15(H15),
 C16(H16), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C27(H27), C28(H28),
  C29(H29), C30(H30), C31(H31), C33(H33), C34(H34), C35(H35), C36(H36),
 C37(H37), C40(H40), C42(H42), C46(H46), C47(H47), C48(H48), C49(H49), C50(H50),
  C52(H52), C53(H53), C54(H54), C55(H55), C56(H56), C62(H62), C63(H63),
 C64(H64), C65(H65), C66(H66), C68(H68), C69(H69), C70(H70), C71(H71), C72(H72),
  C74(H74), C75(H75), C78(H78), C80(H80), C84(H84), C85(H85), C86(H86),
 C87(H87), C88(H88), C90(H90), C91(H91), C92(H92), C93(H93), C94(H94), C99(H99),
  C100(H100), C101(H101), C102(H102), C103(H103), C105(H105), C106(H106),
 C107(H107), C108(H108), C109(H109), C121(H121), C122(H122), C123(H123),
 C124(H124), C125(H125), C127(H127), C128(H128), C129(H129), C130(H130),
 C131(H131), C139(H139), C140(H140), C141(H141), C142(H142), C143(H143),
 C145(H145), C146(H146), C147(H147), C148(H148), C149(H149), C112(H112),
 C114(H114), C116(H116), C118(H118), C151(H151), C152(H152), C155(H155),
 C157(H157), C161(H161), C162(H162), C163(H163), C164(H164), C165(H165),
 C167(H167), C168(H168), C169(H169), C170(H170), C171(H171), C176(H176),
 C177(H177), C178(H178), C179(H179), C180(H180), C182(H182), C183(H183),
 C184(H184), C185(H185), C186(H186), C189(H189), C191(H191), C195(H195),
 C196(H196), C197(H197), C198(H198), C199(H199), C201(H201), C202(H202),
 C203(H203), C204(H204), C205(H205), C211(H211), C212(H212), C213(H213),
 C214(H214), C215(H215), C217(H217), C218(H218), C219(H219), C220(H220),
 C221(H221), C223(H223), C224(H224), C227(H227), C229(H229), C233(H233),
 C234(H234), C235(H235), C236(H236), C237(H237), C239(H239), C240(H240),
 C241(H241), C242(H242), C243(H243), C248(H248), C249(H249), C250(H250),
 C251(H251), C252(H252), C254(H254), C255(H255), C256(H256), C257(H257),
 C258(H258), C261(H261), C263(H263), C267(H267), C268(H268), C269(H269),
 C270(H270), C271(H271), C273(H273), C274(H274), C275(H275), C276(H276),
 C277(H277), C282(H282), C283(H283), C284(H284), C285(H285), C286(H286),
 C288(H288), C289(H289), C290(H290), C291(H291), C292(H292)
6.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C96(H96A,H96B,H96C), C59(H59A,H59B,H59C), C134(H13C,H13D,
 H13E), C58(H58A,H58B,H58C), C136(H13H,H13I,H13J), C173(H17C,H17D,H17E),
 C245(H24F,H24G,H24H), C279(H27C,H27D,H27E), C208(H20E,H20F,H20G), C207(H20H,
 H20I,H20J)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2