Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2002 data_dn37 _database_code_CSD 190254 _audit_creation_method Xtal3.6 _audit_creation_date 02-01-04 _audit_update_record ? _journal_coden_Cambridge 182 loop_ _publ_author_name 'Kingsley Cavell' 'Alison M. Magill' 'David J. Nielson' 'Brian W. Skelton' 'Allan H. White' 'Brian F. Yates' _publ_contact_author_name 'Prof Kingsley Cavell' _publ_contact_author_address ; Chemistry Cardiff University PO Box 912 Cardiff Wales CF10 3TB UNITED KINGDOM ; _publ_contact_author_email 'CAVELLKJ@CARDIFF.AC.UK' _publ_requested_journal 'Chemical Communications' _publ_section_title ; Experimental and computational study of a reductive elimination mechanism in a methyl-Pd(II)-CNC carbene complex. ; _publ_section_references ; Sheldrick, G M. (1996). SADABS. Program for Empirical Absorption Correction of Area Detector Data. University of Gottingen, Germany. Siemens (1995). SMART and SAINT. Area-Detector Control and Integration Software. Siemens Analytical X-ray Systems Inc., Madison, Wisconsin, USA. Hall, S.R., King, G.S.D., and Stewart., J.M. (1995). The Xtal 3.5 User's Manual. University of Western Australia, Lamb: Perth. ; _publ_section_figure_captions ; ? #<< figure captions ; _chemical_formula_sum 'C14 H16 B1 F4 N5 Pd1' _chemical_formula_moiety ? _chemical_formula_weight 447.54 _chemical_melting_point ? _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P_1_21/c_1 _symmetry_space_group_name_Hall -p_2ybc loop_ _symmetry_equiv_pos_as_xyz +x,+y,+z -x,1/2+y,1/2-z -x,-y,-z +x,1/2-y,1/2+z _cell_length_a 7.5226(6) _cell_length_b 20.093(2) _cell_length_c 11.0576(9) _cell_angle_alpha 90.00000 _cell_angle_beta 104.141(2) _cell_angle_gamma 90.00000 _cell_volume 1620.7(2) _cell_formula_units_Z 4 _exptl_crystal_density_diffrn 1.834 _exptl_crystal_density_meas ? _exptl_crystal_density_method ? _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength .71073 _cell_measurement_reflns_used 7536 _cell_measurement_theta_min 2.0 _cell_measurement_theta_max 24.3 _cell_measurement_temperature 150 _exptl_absorpt_coefficient_mu 1.195 _exptl_crystal_description needle _exptl_crystal_size_max .6 _exptl_crystal_size_mid .08 _exptl_crystal_size_min .07 _exptl_crystal_size_rad ? _exptl_crystal_colour colourless _diffrn_measurement_device_type ; Bruker SMART CCD diffractometer ; _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; SADABS; Sheldrick, 1996 ; _exptl_absorpt_correction_T_min .64 _exptl_absorpt_correction_T_max .84 _diffrn_reflns_number 28189 _reflns_number_total 4309 _reflns_Friedel_coverage 0 _reflns_number_gt 3781 _reflns_threshold_expression 'F > 4.00 sig(F )' _diffrn_reflns_theta_max 28.99 _diffrn_reflns_theta_full ? _diffrn_measured_fraction_theta_max ? _diffrn_measured_fraction_theta_full ? _diffrn_reflns_av_R_equivalents .045 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 27 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 15 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _refine_ls_structure_factor_coef F _refine_ls_R_factor_gt .048 _refine_ls_wR_factor_ref .076 _refine_ls_goodness_of_fit_ref 1.244 _refine_ls_number_reflns 3781 _refine_ls_number_parameters 226 _refine_ls_weighting_scheme calc _refine_ls_weighting_details ? _refine_ls_hydrogen_treatment noref _refine_ls_shift/su_max .006 _refine_diff_density_min -.863 _refine_diff_density_max 1.925 _refine_ls_extinction_method ? _refine_ls_extinction_coef ? _refine_ls_abs_structure_details ? _refine_ls_abs_structure_Flack ? # 3. Information for the "methods" section #----------------------------------------- _computing_data_collection 'Siemens SMART (Siemens, 1995)' _computing_cell_refinement 'Siemens SAINT (Siemens, 1995)' _computing_data_reduction 'xtal ADDREF SORTRF' _computing_structure_solution xtal _computing_structure_refinement 'xtal CRYLSQ' _computing_molecular_graphics xtal _computing_publication_material 'xtal BONDLA CIFIO' # 4. Supplementary data for validation and tables #------------------------------------------------ loop_ _atom_type_symbol _atom_type_description _atom_type_oxidation_number _atom_type_number_in_cell _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C ? 0 56 .002 .002 'Int Tables Vol IV Tables 2.2B and 2.3.1' H ? 0 64 0 0 'Int Tables Vol IV Tables 2.2B and 2.3.1' B ? 0 4 0 .001 'Int Tables Vol IV Tables 2.2B and 2.3.1' F ? 0 16 .014 .01 'Int Tables Vol IV Tables 2.2B and 2.3.1' N ? 0 20 .004 .003 'Int Tables Vol IV Tables 2.2B and 2.3.1' Pd ? 0 4 -1.177 1.007 'Int Tables Vol IV Tables 2.2B and 2.3.1' loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_calc_flag _atom_site_calc_attached_atom _atom_site_occupancy _atom_site_disorder_assembly _atom_site_disorder_group Pd .26786(4) .084171(16) .49192(3) .02451(18) Uani ? ? 1.00000 ? ? C0 .2709(6) .1881(2) .5069(4) .032(2) Uani ? ? 1.00000 ? ? N1 .2578(4) -.0159(2) .4727(3) .0241(15) Uani ? ? 1.00000 ? ? C2 .2911(6) -.0429(2) .3704(4) .0271(18) Uani ? ? 1.00000 ? ? N21 .3323(5) .00623(18) .2923(3) .0263(15) Uani ? ? 1.00000 ? ? C22 .3296(6) .0720(2) .3240(4) .0261(18) Uani ? ? 1.00000 ? ? N23 .3713(5) .1038(2) .2281(4) .0319(17) Uani ? ? 1.00000 ? ? C231 .3821(9) .1763(3) .2149(6) .048(3) Uani ? ? 1.00000 ? ? C24 .4009(7) .0599(3) .1389(4) .037(2) Uani ? ? 1.00000 ? ? C25 .3742(6) -.0021(3) .1774(4) .033(2) Uani ? ? 1.00000 ? ? C3 .2836(6) -.1110(2) .3520(5) .034(2) Uani ? ? 1.00000 ? ? C4 .2383(7) -.1500(2) .4447(6) .039(2) Uani ? ? 1.00000 ? ? C2' .2169(5) -.0535(2) .5624(4) .0276(18) Uani ? ? 1.00000 ? ? N21' .1852(5) -.0127(2) .6583(4) .0295(16) Uani ? ? 1.00000 ? ? C22' .2058(6) .0554(2) .6538(4) .031(2) Uani ? ? 1.00000 ? ? N23' .1698(6) .0764(2) .7598(4) .0335(19) Uani ? ? 1.00000 ? ? C231' .1776(7) .1467(3) .7995(5) .043(3) Uani ? ? 1.00000 ? ? C24' .1279(7) .0238(3) .8294(5) .040(2) Uani ? ? 1.00000 ? ? C25' .1390(6) -.0327(3) .7666(4) .034(2) Uani ? ? 1.00000 ? ? C3' .2025(7) -.1218(2) .5509(5) .035(2) Uani ? ? 1.00000 ? ? B -.2042(9) .3369(3) .5011(5) .036(3) Uani ? ? 1.00000 ? ? F1 -.1768(7) .31301(18) .6224(3) .066(2) Uani ? ? 1.00000 ? ? F2 -.1779(6) .28724(17) .4219(3) .062(2) Uani ? ? 1.00000 ? ? F3 -.0839(5) .38957(17) .4991(3) .0507(18) Uani ? ? 1.00000 ? ? F4 -.3824(5) .3600(2) .4627(4) .062(2) Uani ? ? 1.00000 ? ? H0a .21901 .20056 .57348 .04500 Uiso ? ? 1.00000 ? ? H0b .19807 .20630 .43107 .04500 Uiso ? ? 1.00000 ? ? H0c .39309 .20442 .51983 .04500 Uiso ? ? 1.00000 ? ? H231a .40941 .19663 .29611 .07100 Uiso ? ? 1.00000 ? ? H231b .26938 .19324 .16763 .07100 Uiso ? ? 1.00000 ? ? H231c .47749 .18766 .17507 .07100 Uiso ? ? 1.00000 ? ? H24 .43463 .07154 .06376 .04600 Uiso ? ? 1.00000 ? ? H25 .38230 -.04308 .13507 .04200 Uiso ? ? 1.00000 ? ? H3 .30907 -.13036 .27943 .04300 Uiso ? ? 1.00000 ? ? H4 .23056 -.19709 .43448 .04800 Uiso ? ? 1.00000 ? ? H231'a .17858 .17533 .73063 .06500 Uiso ? ? 1.00000 ? ? H231'b .28509 .15484 .86367 .06500 Uiso ? ? 1.00000 ? ? H231'c .07326 .15732 .83010 .06500 Uiso ? ? 1.00000 ? ? H24' .09791 .02694 .90843 .05000 Uiso ? ? 1.00000 ? ? H25' .11839 -.07694 .79108 .04500 Uiso ? ? 1.00000 ? ? H3' .16945 -.14847 .61336 .04400 Uiso ? ? 1.00000 ? ? loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_12 _atom_site_aniso_U_13 _atom_site_aniso_U_23 Pd .0243(2) .0217(2) .0268(2) -.00100(11) .00482(13) .00064(11) C0 .036(2) .019(2) .045(3) -.0071(16) .019(2) -.0123(17) N1 .0204(15) .0243(17) .0228(16) -.0019(12) -.0038(13) .0019(13) C2 .0245(19) .024(2) .031(2) -.0025(15) .0019(16) -.0028(16) N21 .0247(16) .0283(18) .0235(17) .0022(13) .0012(13) -.0002(14) C22 .0237(19) .027(2) .025(2) .0017(15) .0019(16) .0045(16) N23 .0307(19) .036(2) .0265(19) .0024(16) .0028(15) .0090(16) C231 .056(3) .040(3) .051(3) -.001(2) .019(3) .012(2) C24 .036(2) .050(3) .024(2) .004(2) .0066(19) .007(2) C25 .027(2) .043(3) .024(2) .0004(18) .0002(17) -.0034(18) C3 .028(2) .026(2) .043(3) -.0000(17) -.0003(19) -.006(2) C4 .037(2) .024(2) .054(3) -.0018(18) .005(2) .000(2) C2' .0179(17) .028(2) .033(2) -.0020(15) -.0003(16) .0076(17) N21' .0216(16) .038(2) .0268(18) -.0023(15) .0015(14) .0074(16) C22' .024(2) .037(2) .029(2) -.0042(17) .0034(17) -.0039(18) N23' .0245(18) .049(2) .0257(19) -.0047(16) .0035(15) -.0032(16) C231' .036(3) .061(4) .033(2) -.009(2) .008(2) -.019(2) C24' .028(2) .062(3) .031(2) -.003(2) .0070(19) .006(2) C25' .024(2) .048(3) .028(2) -.0034(18) .0002(17) .012(2) C3' .032(2) .029(2) .038(2) -.0073(18) .001(2) .008(2) B .054(3) .027(3) .030(3) .006(2) .014(2) .005(2) F1 .121(4) .044(2) .0353(18) -.004(2) .024(2) .0077(15) F2 .112(3) .0346(17) .052(2) -.0009(19) .041(2) -.0062(15) F3 .065(2) .0379(17) .058(2) -.0075(16) .0302(17) -.0014(15) F4 .055(2) .064(2) .069(3) -.0003(18) .0185(19) .010(2) # 5. Molecular Geometry #---------------------- loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag #<< enter YES for value to be published Pd C0 . . 2.094(5) ? Pd N1 . . 2.021(4) ? Pd C22 . . 2.036(5) ? Pd C22' . . 2.041(5) ? C0 H0a . . .948 ? C0 H0b . . .955 ? C0 H0c . . .954 ? N1 C2 . . 1.332(6) ? N1 C2' . . 1.341(6) ? C2 N21 . . 1.395(6) ? C2 C3 . . 1.384(6) ? N21 C22 . . 1.369(6) ? N21 C25 . . 1.392(6) ? C22 N23 . . 1.339(7) ? N23 C231 . . 1.469(7) ? N23 C24 . . 1.381(7) ? C231 H231a . . .962 ? C231 H231b . . .944 ? C231 H231c . . .957 ? C24 C25 . . 1.346(8) ? C24 H24 . . .956 ? C25 H25 . . .957 ? C3 C4 . . 1.396(8) ? C3 H3 . . .953 ? C4 C3' . . 1.388(8) ? C4 H4 . . .953 ? C2' N21' . . 1.406(6) ? C2' C3' . . 1.381(7) ? N21' C22' . . 1.379(6) ? N21' C25' . . 1.386(7) ? C22' N23' . . 1.334(7) ? N23' C231' . . 1.475(8) ? N23' C24' . . 1.390(8) ? C231' H231'a . . .956 ? C231' H231'b . . .951 ? C231' H231'c . . .952 ? C24' C25' . . 1.344(8) ? C24' H24' . . .956 ? C25' H25' . . .952 ? C3' H3' . . .953 ? B F1 . . 1.391(7) ? B F2 . . 1.373(7) ? B F3 . . 1.397(7) ? B F4 . . 1.383(7) ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_2 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag #<< enter YES for value to be published C0 Pd N1 . . . 178.14(15) ? C0 Pd C22 . . . 101.0(2) ? C0 Pd C22' . . . 102.3(2) ? N1 Pd C22 . . . 78.21(17) ? N1 Pd C22' . . . 78.45(18) ? C22 Pd C22' . . . 156.65(19) ? Pd C0 H0a . . . 109.1 ? Pd C0 H0b . . . 108.7 ? Pd C0 H0c . . . 110.3 ? H0a C0 H0b . . . 108.9 ? H0a C0 H0c . . . 110.9 ? H0b C0 H0c . . . 108.9 ? Pd N1 C2 . . . 119.0(3) ? Pd N1 C2' . . . 119.5(3) ? C2 N1 C2' . . . 121.5(4) ? N1 C2 N21 . . . 110.7(4) ? N1 C2 C3 . . . 121.2(5) ? N21 C2 C3 . . . 128.1(5) ? C2 N21 C22 . . . 120.4(4) ? C2 N21 C25 . . . 127.9(4) ? C22 N21 C25 . . . 111.7(4) ? Pd C22 N21 . . . 111.7(3) ? Pd C22 N23 . . . 144.5(3) ? N21 C22 N23 . . . 103.7(4) ? C22 N23 C231 . . . 125.6(5) ? C22 N23 C24 . . . 111.7(4) ? C231 N23 C24 . . . 122.7(5) ? N23 C231 H231a . . . 109.4 ? N23 C231 H231b . . . 110.4 ? N23 C231 H231c . . . 110.3 ? H231a C231 H231b . . . 108.8 ? H231a C231 H231c . . . 108.4 ? H231b C231 H231c . . . 109.4 ? N23 C24 C25 . . . 107.6(5) ? N23 C24 H24 . . . 126.0 ? C25 C24 H24 . . . 126.4 ? N21 C25 C24 . . . 105.2(4) ? N21 C25 H25 . . . 127.2 ? C24 C25 H25 . . . 127.5 ? C2 C3 C4 . . . 117.1(5) ? C2 C3 H3 . . . 121.2 ? C4 C3 H3 . . . 121.7 ? C3 C4 C3' . . . 121.7(5) ? C3 C4 H4 . . . 119.2 ? C3' C4 H4 . . . 119.1(6) ? N1 C2' N21' . . . 110.0(4) ? N1 C2' C3' . . . 121.3(5) ? N21' C2' C3' . . . 128.6(5) ? C2' N21' C22' . . . 120.7(4) ? C2' N21' C25' . . . 127.4(4) ? C22' N21' C25' . . . 111.9(4) ? Pd C22' N21' . . . 111.3(3) ? Pd C22' N23' . . . 145.0(4) ? N21' C22' N23' . . . 103.6(4) ? C22' N23' C231' . . . 124.2(5) ? C22' N23' C24' . . . 111.6(4) ? C231' N23' C24' . . . 124.2(5) ? N23' C231' H231'a . . . 110.3 ? N23' C231' H231'b . . . 110.6 ? N23' C231' H231'c . . . 110.2 ? H231'a C231' H231'b . . . 108.7 ? H231'a C231' H231'c . . . 108.4 ? H231'b C231' H231'c . . . 108.6 ? N23' C24' C25' . . . 107.8(5) ? N23' C24' H24' . . . 126.3 ? C25' C24' H24' . . . 125.9 ? N21' C25' C24' . . . 105.2(5) ? N21' C25' H25' . . . 127.5 ? C24' C25' H25' . . . 127.3 ? C4 C3' C2' . . . 117.1(5) ? C4 C3' H3' . . . 121.5 ? C2' C3' H3' . . . 121.4 ? F1 B F2 . . . 110.7(4) ? F1 B F3 . . . 109.4(4) ? F1 B F4 . . . 108.4(6) ? F2 B F3 . . . 110.2(5) ? F2 B F4 . . . 109.1(4) ? F3 B F4 . . . 108.9(4) ? _chemical_compound_source ? _chemical_name_systematic ? _chemical_name_common ? _chemical_formula_analytical ? _chemical_formula_structural ? _exptl_crystal_F_000 888 loop_ _diffrn_standard_refln_index_h _diffrn_standard_refln_index_k _diffrn_standard_refln_index_l ? ? ? loop_ _diffrn_attenuator_code _diffrn_attenuator_scale ? ? _reflns_limit_h_min 0 _reflns_limit_h_max 10 _reflns_limit_k_min 0 _reflns_limit_k_max 27 _reflns_limit_l_min -15 _reflns_limit_l_max 14 _reflns_number_observed ? _reflns_d_resolution_high .733 _reflns_d_resolution_low 10.026 _diffrn_reflns_av_sigmaI/netI .034 _diffrn_reflns_theta_min 2.03 _diffrn_reflns_reduction_process ? _diffrn_ambient_temperature 150 _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_radiation_detector 'CCD area detector' _refine_ls_extinction_expression ? _refine_ls_matrix_type full _refine_ls_number_restraints 0 _refine_ls_number_constraints 0 _refine_ls_R_factor_all .056 _refine_ls_wR_factor_all .08 _refine_ls_goodness_of_fit_all 1.225 _refine_ls_shift/su_mean .001 #-end-end-end-end-end-end-end-end-end-end-end-end-end-end-end-end-end-end