# Supplementary Material (ESI) for Dalton Transactions
# This journal is (c) The Royal Society of Chemistry 2009

data_global
_journal_name_full               'Dalton Trans.'

_journal_coden_Cambridge         0222

_publ_contact_author_name        'Zhenfeng Xi'
_publ_contact_author_email       ZFXI@PKU.EDU.CN

_publ_section_title              
;
Hydride-Induced Cleavage of C-O Bond in Pyran
Ring of 2-Pyranylidene Carbene Complexes Followed by Ring Closure
of Unsaturated Acylmetalates and Reductive Elimination: Mechanism
and Synthetic Application
;
loop_
_publ_author_name
'Zhenfeng Xi'
'Chen Lin'
'Lantao Liu'
'Hui Sun'
'Qifeng Wang'
;
Wenxiong Zhang
;

# Attachment '4c.cif'

data_wqf2a
_database_code_depnum_ccdc_archive 'CCDC 734642'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C20 H25 I O2'
_chemical_formula_weight         424.30

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
I I -0.4742 1.8119 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Triclinic
_symmetry_space_group_name_H-M   P-1

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   7.5377(15)
_cell_length_b                   11.101(2)
_cell_length_c                   11.695(2)
_cell_angle_alpha                87.68(3)
_cell_angle_beta                 75.05(3)
_cell_angle_gamma                74.76(3)
_cell_volume                     911.8(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    123(2)
_cell_measurement_reflns_used    5338
_cell_measurement_theta_min      2.58
_cell_measurement_theta_max      27.48

_exptl_crystal_description       ?
_exptl_crystal_colour            ?
_exptl_crystal_size_max          0.40
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.545
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             428
_exptl_absorpt_coefficient_mu    1.764
_exptl_absorpt_correction_type   Empirical
_exptl_absorpt_correction_T_min  0.5389
_exptl_absorpt_correction_T_max  0.8434
_exptl_absorpt_process_details   
;
HIGASHI, T. (1995). Abscor-Empirical
Absorption Correction based on Fourier
Series Approximation.
Rigaku Corporation,Tokyo,Japan.
;

_diffrn_ambient_temperature      123(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Rigaku RAXIS RAPID IP'
_diffrn_measurement_method       \W
_diffrn_detector_area_resol_mean 10.00
_diffrn_standards_number         0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_decay_%        0
_diffrn_reflns_number            5338
_diffrn_reflns_av_R_equivalents  0.0566
_diffrn_reflns_av_sigmaI/netI    0.0509
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         2.58
_diffrn_reflns_theta_max         27.48
_reflns_number_total             3471
_reflns_number_gt                2748
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Rapid-AUTO (Rigaku,2000)'
_computing_cell_refinement       Rapid-AUTO
_computing_data_reduction        'CrystalStructure (Rigaku/MSC,2000)'
_computing_structure_solution    SHELXS-97,(Sheldrick,1997)
_computing_structure_refinement  SHELXL-97,(Sheldrick,1997)
_computing_molecular_graphics    'Siemens SHELXTL V4.2,(Sheldrick,1990)'
_computing_publication_material  SHELXL-97,(Sheldrick,1997)

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.1083P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3471
_refine_ls_number_parameters     216
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0675
_refine_ls_R_factor_gt           0.0555
_refine_ls_wR_factor_ref         0.1549
_refine_ls_wR_factor_gt          0.1489
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_restrained_S_all      1.031
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.6013(7) 0.2873(5) 0.3031(5) 0.0272(10) Uani 1 1 d . . .
C2 C 0.7793(7) 0.2019(5) 0.3325(5) 0.0274(11) Uani 1 1 d . . .
C3 C 0.7973(7) 0.0800(5) 0.2726(5) 0.0285(11) Uani 1 1 d . . .
C4 C 0.6545(7) 0.0824(5) 0.2250(4) 0.0242(10) Uani 1 1 d . . .
C5 C 0.5103(7) 0.2098(4) 0.2401(5) 0.0247(10) Uani 1 1 d . . .
C6 C 0.7648(8) 0.1913(5) 0.4664(5) 0.0306(11) Uani 1 1 d . . .
H6A H 0.6512 0.1617 0.5045 0.037 Uiso 1 1 calc R . .
H6B H 0.8777 0.1272 0.4776 0.037 Uiso 1 1 calc R . .
C7 C 0.7517(11) 0.3112(6) 0.5292(6) 0.0466(16) Uani 1 1 d . . .
H7A H 0.8594 0.3444 0.4894 0.070 Uiso 1 1 calc R . .
H7B H 0.7550 0.2941 0.6117 0.070 Uiso 1 1 calc R . .
H7C H 0.6324 0.3725 0.5273 0.070 Uiso 1 1 calc R . .
C8 C 0.9742(7) -0.0279(5) 0.2605(5) 0.0301(11) Uani 1 1 d . . .
H8A H 0.9393 -0.1080 0.2615 0.036 Uiso 1 1 calc R . .
H8B H 1.0287 -0.0254 0.3286 0.036 Uiso 1 1 calc R . .
C9 C 1.1232(8) -0.0208(6) 0.1451(5) 0.0364(13) Uani 1 1 d . . .
H9A H 1.0694 -0.0236 0.0777 0.055 Uiso 1 1 calc R . .
H9B H 1.2353 -0.0917 0.1386 0.055 Uiso 1 1 calc R . .
H9C H 1.1604 0.0574 0.1450 0.055 Uiso 1 1 calc R . .
C10 C 0.6285(7) -0.0259(5) 0.1618(5) 0.0298(11) Uani 1 1 d . . .
H10A H 0.7536 -0.0724 0.1119 0.036 Uiso 1 1 calc R . .
H10B H 0.5447 0.0073 0.1088 0.036 Uiso 1 1 calc R . .
C11 C 0.5430(9) -0.1156(5) 0.2466(6) 0.0367(13) Uani 1 1 d . . .
H11A H 0.6258 -0.1494 0.2989 0.055 Uiso 1 1 calc R . .
H11B H 0.5312 -0.1841 0.2013 0.055 Uiso 1 1 calc R . .
H11C H 0.4170 -0.0709 0.2942 0.055 Uiso 1 1 calc R . .
C12 C 0.3112(7) 0.2092(5) 0.3196(5) 0.0326(12) Uani 1 1 d . . .
H12A H 0.2251 0.2939 0.3211 0.039 Uiso 1 1 calc R . .
H12B H 0.2602 0.1513 0.2831 0.039 Uiso 1 1 calc R . .
C13 C 0.3072(8) 0.1710(6) 0.4475(6) 0.0391(13) Uani 1 1 d . . .
H13A H 0.3993 0.0901 0.4473 0.059 Uiso 1 1 calc R . .
H13B H 0.1794 0.1644 0.4887 0.059 Uiso 1 1 calc R . .
H13C H 0.3403 0.2341 0.4882 0.059 Uiso 1 1 calc R . .
C14 C 0.4858(7) 0.2620(5) 0.1192(5) 0.0275(11) Uani 1 1 d . . .
C15 C 0.6376(7) 0.3048(5) 0.0323(5) 0.0274(11) Uani 1 1 d . . .
C16 C 0.5925(8) 0.3664(5) -0.0680(5) 0.0289(11) Uani 1 1 d . . .
H16 H 0.4676 0.3793 -0.0776 0.035 Uiso 1 1 calc R . .
C17 C 0.7254(8) 0.4086(5) -0.1525(5) 0.0320(12) Uani 1 1 d . . .
H17 H 0.6931 0.4484 -0.2205 0.038 Uiso 1 1 calc R . .
C18 C 0.9077(8) 0.3923(5) -0.1373(5) 0.0303(11) Uani 1 1 d . . .
C19 C 0.9564(8) 0.3322(5) -0.0383(5) 0.0315(11) Uani 1 1 d . . .
H19 H 1.0809 0.3204 -0.0284 0.038 Uiso 1 1 calc R . .
C20 C 0.8220(8) 0.2900(5) 0.0447(5) 0.0321(12) Uani 1 1 d . . .
H20 H 0.8552 0.2498 0.1124 0.039 Uiso 1 1 calc R . .
I1 I 1.11208(5) 0.45964(3) -0.26075(3) 0.03981(18) Uani 1 1 d . . .
O1 O 0.5368(6) 0.3972(4) 0.3277(4) 0.0353(9) Uani 1 1 d . . .
O2 O 0.3401(6) 0.2603(4) 0.0904(4) 0.0435(11) Uani 1 1 d . . .
H2 H 0.883(8) 0.239(6) 0.290(6) 0.031(16) Uiso 1 1 d . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
C1 0.031(3) 0.028(3) 0.021(2) -0.0005(19) -0.010(2) -0.001(2)
C2 0.024(2) 0.026(2) 0.031(3) 0.006(2) -0.010(2) -0.003(2)
C3 0.028(3) 0.028(2) 0.025(3) 0.000(2) -0.009(2) 0.002(2)
C4 0.024(2) 0.023(2) 0.022(2) 0.0012(19) -0.0040(19) -0.0024(19)
C5 0.025(2) 0.023(2) 0.027(3) -0.0010(19) -0.012(2) -0.0019(19)
C6 0.031(3) 0.038(3) 0.024(3) 0.003(2) -0.011(2) -0.007(2)
C7 0.063(4) 0.042(3) 0.035(4) -0.006(3) -0.020(3) -0.005(3)
C8 0.027(2) 0.028(3) 0.032(3) 0.000(2) -0.010(2) 0.002(2)
C9 0.028(3) 0.044(3) 0.031(3) -0.006(2) -0.009(2) 0.003(2)
C10 0.028(2) 0.029(3) 0.029(3) -0.001(2) -0.009(2) 0.000(2)
C11 0.041(3) 0.031(3) 0.039(3) 0.006(2) -0.013(3) -0.008(2)
C12 0.024(2) 0.035(3) 0.034(3) 0.000(2) -0.008(2) 0.001(2)
C13 0.027(3) 0.049(3) 0.039(3) 0.003(3) -0.004(2) -0.010(3)
C14 0.034(3) 0.024(2) 0.026(3) 0.003(2) -0.016(2) -0.004(2)
C15 0.033(3) 0.025(2) 0.023(3) -0.0001(19) -0.010(2) -0.001(2)
C16 0.035(3) 0.024(2) 0.026(3) 0.003(2) -0.013(2) -0.002(2)
C17 0.045(3) 0.023(2) 0.026(3) 0.000(2) -0.015(2) 0.002(2)
C18 0.040(3) 0.023(2) 0.025(3) -0.001(2) -0.009(2) -0.003(2)
C19 0.034(3) 0.035(3) 0.025(3) 0.003(2) -0.011(2) -0.007(2)
C20 0.035(3) 0.033(3) 0.030(3) 0.009(2) -0.015(2) -0.007(2)
I1 0.0455(3) 0.0311(2) 0.0344(3) 0.00546(15) -0.00339(17) -0.00314(16)
O1 0.039(2) 0.0283(19) 0.037(2) -0.0018(16) -0.0153(18) 0.0002(17)
O2 0.040(2) 0.051(3) 0.049(3) 0.017(2) -0.027(2) -0.015(2)

_geom_special_details            
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 O1 1.205(6) . ?
C1 C2 1.537(6) . ?
C1 C5 1.541(7) . ?
C2 C3 1.507(8) . ?
C2 C6 1.543(7) . ?
C2 H2 0.99(6) . ?
C3 C4 1.328(7) . ?
C3 C8 1.520(7) . ?
C4 C10 1.517(7) . ?
C4 C5 1.525(6) . ?
C5 C14 1.543(7) . ?
C5 C12 1.550(8) . ?
C6 C7 1.514(8) . ?
C6 H6A 0.9900 . ?
C6 H6B 0.9900 . ?
C7 H7A 0.9800 . ?
C7 H7B 0.9800 . ?
C7 H7C 0.9800 . ?
C8 C9 1.532(8) . ?
C8 H8A 0.9900 . ?
C8 H8B 0.9900 . ?
C9 H9A 0.9800 . ?
C9 H9B 0.9800 . ?
C9 H9C 0.9800 . ?
C10 C11 1.523(8) . ?
C10 H10A 0.9900 . ?
C10 H10B 0.9900 . ?
C11 H11A 0.9800 . ?
C11 H11B 0.9800 . ?
C11 H11C 0.9800 . ?
C12 C13 1.533(8) . ?
C12 H12A 0.9900 . ?
C12 H12B 0.9900 . ?
C13 H13A 0.9800 . ?
C13 H13B 0.9800 . ?
C13 H13C 0.9800 . ?
C14 O2 1.234(6) . ?
C14 C15 1.488(8) . ?
C15 C20 1.401(7) . ?
C15 C16 1.406(7) . ?
C16 C17 1.377(8) . ?
C16 H16 0.9500 . ?
C17 C18 1.395(8) . ?
C17 H17 0.9500 . ?
C18 C19 1.396(7) . ?
C18 I1 2.094(6) . ?
C19 C20 1.376(8) . ?
C19 H19 0.9500 . ?
C20 H20 0.9500 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 C1 C2 126.3(5) . . ?
O1 C1 C5 124.2(4) . . ?
C2 C1 C5 109.5(4) . . ?
C3 C2 C1 102.2(4) . . ?
C3 C2 C6 113.5(4) . . ?
C1 C2 C6 113.9(4) . . ?
C3 C2 H2 110(4) . . ?
C1 C2 H2 104(3) . . ?
C6 C2 H2 113(4) . . ?
C4 C3 C2 113.4(4) . . ?
C4 C3 C8 125.3(5) . . ?
C2 C3 C8 121.0(5) . . ?
C3 C4 C10 126.1(4) . . ?
C3 C4 C5 112.6(5) . . ?
C10 C4 C5 121.3(4) . . ?
C4 C5 C1 101.9(4) . . ?
C4 C5 C14 111.1(4) . . ?
C1 C5 C14 112.9(4) . . ?
C4 C5 C12 113.8(4) . . ?
C1 C5 C12 109.0(4) . . ?
C14 C5 C12 108.2(4) . . ?
C7 C6 C2 115.1(5) . . ?
C7 C6 H6A 108.5 . . ?
C2 C6 H6A 108.5 . . ?
C7 C6 H6B 108.5 . . ?
C2 C6 H6B 108.5 . . ?
H6A C6 H6B 107.5 . . ?
C6 C7 H7A 109.5 . . ?
C6 C7 H7B 109.5 . . ?
H7A C7 H7B 109.5 . . ?
C6 C7 H7C 109.5 . . ?
H7A C7 H7C 109.5 . . ?
H7B C7 H7C 109.5 . . ?
C3 C8 C9 110.8(4) . . ?
C3 C8 H8A 109.5 . . ?
C9 C8 H8A 109.5 . . ?
C3 C8 H8B 109.5 . . ?
C9 C8 H8B 109.5 . . ?
H8A C8 H8B 108.1 . . ?
C8 C9 H9A 109.5 . . ?
C8 C9 H9B 109.5 . . ?
H9A C9 H9B 109.5 . . ?
C8 C9 H9C 109.5 . . ?
H9A C9 H9C 109.5 . . ?
H9B C9 H9C 109.5 . . ?
C4 C10 C11 112.9(5) . . ?
C4 C10 H10A 109.0 . . ?
C11 C10 H10A 109.0 . . ?
C4 C10 H10B 109.0 . . ?
C11 C10 H10B 109.0 . . ?
H10A C10 H10B 107.8 . . ?
C10 C11 H11A 109.5 . . ?
C10 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
C10 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
C13 C12 C5 115.0(4) . . ?
C13 C12 H12A 108.5 . . ?
C5 C12 H12A 108.5 . . ?
C13 C12 H12B 108.5 . . ?
C5 C12 H12B 108.5 . . ?
H12A C12 H12B 107.5 . . ?
C12 C13 H13A 109.5 . . ?
C12 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
C12 C13 H13C 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
O2 C14 C15 118.8(5) . . ?
O2 C14 C5 118.6(5) . . ?
C15 C14 C5 122.5(4) . . ?
C20 C15 C16 117.6(5) . . ?
C20 C15 C14 124.4(5) . . ?
C16 C15 C14 118.0(4) . . ?
C17 C16 C15 121.5(5) . . ?
C17 C16 H16 119.3 . . ?
C15 C16 H16 119.3 . . ?
C16 C17 C18 119.4(5) . . ?
C16 C17 H17 120.3 . . ?
C18 C17 H17 120.3 . . ?
C17 C18 C19 120.4(5) . . ?
C17 C18 I1 120.9(4) . . ?
C19 C18 I1 118.7(4) . . ?
C20 C19 C18 119.3(5) . . ?
C20 C19 H19 120.4 . . ?
C18 C19 H19 120.4 . . ?
C19 C20 C15 121.8(5) . . ?
C19 C20 H20 119.1 . . ?
C15 C20 H20 119.1 . . ?

_diffrn_measured_fraction_theta_max 0.831
_diffrn_reflns_theta_full        27.48
_diffrn_measured_fraction_theta_full 0.831
_refine_diff_density_max         1.095
_refine_diff_density_min         -1.464
_refine_diff_density_rms         0.148