Supporting Information
© Wiley-VCH 2006
69451 Weinheim, Germany
Evidence for Substrate *Binding by the Lanthanide Centers in
Li3(THF)n(BINOLate)3Ln: Solution and Solid-State Characterization of 7- and 8Coordinate Li3(sol)n(BINOLate)3Ln(S)m Adducts**
Alfred J. Wooten, Patrick J. Carroll, and Patrick J. Walsh*
P. Roy and Diana T. Vagelos Laboratories, University of Pennsylvania,
Department of Chemistry, 231 South 34th Street, Philadelphia, Pennsylvania
19104-6323.
E-mail: [email protected]
Experimental Procedures………………………………………………………….S2-S3
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H and 13C NMR of Li3(THF)4(BINOLate)3La(THF) (7)………………………...S4
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H and 13C NMR of Li3(THF)4(BINOLate)3Eu(THF) (6)……...……...…….……S5
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H and 13C NMR of Li3(Py)5(BINOLate)3La(Py)2 (8)………………..…...………S6
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H and 13C NMR of Li3(DMEDA)3(BINOLate)3Eu (3)………………..…….……S7
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H and 13C NMR of Li3(DMEDA)3(BINOLate)3La (4)………………..…….……S8
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H NMR of Cyclohexenone………………………………………………....…….S9
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H NMR of Cyclohexenone with Li3(THF)6(BINOLate)3Eu (1)………………….S9
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H NMR of Cyclohexenone with Li3(DMEDA)3(BINOLate)3Eu (3)……………..S10
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H NMR of Cyclohexenone with Li3(THF)6(BINOLate)3Pr (5).………………….S10
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H NMR of N,N-Dimethylformamide (DMF)…….…………………….……...…S11
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H NMR of DMF with Li3(THF)6(BINOLate)3Eu (1)……..…………… .……….S11
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H NMR of DMF with Li3(DMEDA)3(BINOLate)3Eu (3)………...……………...S12
ORTEP plot of Li3(THF)4(BINOLate)3Eu(THF) (6)………..……………...……..S12
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Experimental Section
General Methods: All reactions and manipulations were carried out under an
inert atmosphere in a Vacuum Atmospheres drybox with attached MO-40 Dritrain, or by
using standard Schlenk or vacuum line techniques with oven-dried glassware.
Dichloromethane, toluene, and hexanes (UV grade, alkene-free) were dried through
alumina columns under nitrogen. Diethyl ether and tetrahydrofuran were pre-dried
through alumina columns and further dried using sodium/benzophenone ketyl. Pentane
(HPLC grade) was dried using sodium/benzophenone ketyl. Solutions were degassed as
follows: they were cooled to -196 °C, evacuated under high vacuum, and thawed. This
sequence was repeated three times in each case. Unless otherwise specified, all reagents
were purchased from Aldrich Chemical Co., Acros, or Strem Chemicals, and all solvents
were purchased from Fischer Scientific. Deuterated solvents were purchased from
Cambridge Isotopes. [D8]THF was vacuum transferred from sodium/benzophenone
ketyl. N,N’ dimethylethylene diamine (DMEDA) was dried from KOH, heated on an oil
bath, and collected via fractional distillation under nitrogen. The 1H and 13C{1H} NMR
spectra were obtained on a Bruker DMX-300 or on a Bruker AM-500 Fourier transform
NMR spectrometer at 300 and 75 MHz or 500 and 125 MHz, respectively. Chemical
shifts are recorded in units of parts per million downfield from tetramethylsilane and are
reported relative to the deuterated solvent residual proton resonance. All coupling
constants are reported in Hertz. The infrared spectra were obtained using a Perkin Elmer
1600 series spectrometer.
NMR Procedure to Determine Induced Chemical Shifts of Cyclohexenone:
The H spectra in this study were obtained on a Bruker DMX-300 Fourier transform
NMR spectrometer at 300 MHz. Mesitylene was used as an internal referencing standard
for all experiments and [D8]THF was used as the solvent. Induced chemical shifts of
cyclohexenone and N,N-Dimethylformamide (DMF) were obtained by incremental
addition of known weights of the solid lanthanide complex to a known solution
concentration of the substrate. The first shift reagent (SR) used with cyclohexenone and
DMF was Li3(THF)3(BINOLate)3Eu, at a molar ratio concentration [SR/Substrate] of
0.032 M/0.193 M and 0.032 M/0.258 M respectively. Second,
Li3(DMEDA)3(BINOLate)3Eu was used with cyclohexenone and DMF at a molar ratio
concentration of 0.037 M/0.186 M and 0.032 M/0.258 M, respectively. Finally,
Li3(THF)3(BINOLate)3Pr was used with cyclohexenone at a molar ratio concentration of
0.032 M/0.193 M. Each sample was allowed to equilibrate for 15 minutes before
acquisition of NMR data.
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Synthesis of Li3(THF)4(BINOLate)3Eu(THF) (6) and
Li3(THF)4(BINOLate)3La(THF) (7):
Under a nitrogen atmosphere, 30 mg of Li3(THF)3(BINOLate)3Eu (1 ) or
Li3(THF)3(BINOLate)3La (2) were added to a 4 mL vial and dissolved in 1.0 mL of
anhydrous THF. The vial was then placed inside of a 20 mL screw capped vial that was
half filled with dry pentane. After several days of pentane diffusion at room temperature,
pale X-ray quality crystals of compounds 6 and 7 were obtained. These crystals were
subjected to X-ray diffraction studies. NMR spectra of 6 and 7 in [D8]THF were
S2
identical to those of compounds 1 and 2, respectively. Crystals of 6 and 7 were not
amenable to elemental analysis due to desolvation.
Synthesis of Li3(Py)5(BINOLate)3La(Py)2 (8): Li3(THF)3(BINOLate)3La (2)
(30 mg) was added to a vial and dissolved in 1.0 mL of pyridine. This vial was then
placed inside of a 20 mL screw capped vial that was half filled with dry pentane. After
several days, pale crystals formed that were suitable for an X-ray diffraction study: 1H
NMR (500 MHz, [D8]THF, 25°C, TMS): d = 6.79 (m, 4H), 6.89 (m, 2H), 6.98 (d, J
(H,H) = 8.7 Hz, 2H), 7.22 (m, 7H), 7.58 (d, , J (H,H) = 8.8 Hz, 2H), 7.60 (d, , J (H,H) =
8.0 Hz, 2H), 7.65 (m, 3H), and 8.52 (m, 7H) ppm; 13C{1H} NMR (125 MHz, [D8]THF):
d = 119.1, 120.4, 124.4, 124.8, 126.8, 126.9, 128.1, 128.4, 128.5, 136.4, 136.7, 150.9,
and 163.5 ppm; Elemental analysis calcd (%) for C95H71Li3O6N7La (1566.35 g mol-1): C,
72.85; H, 4.57; N, 6.26; found: C, 72.98; H, 4.78; N, 6.12.
Synthesis of Li3(DMEDA)3(BINOLate)3Eu (3): Under nitrogen, DMEDA
(0.141 mL, 0.117 g, 1.33 mmol) was added to a 40 mL THF solution of
Li3(THF)3(BINOLate)3Eu (1) (0.500 g, 0.403 mmol). After stirring this solution at room
temperature for 4 h, all volatile materials were removed in vacuo. The remaining solid
was placed on a frit and washed with three 5 mL portions of diethyl ether, affording
0.440 g of the desired compound after drying under reduced pressure (85 % yield based
on Li3(THF)3(BINOLate)3Eu (1)): 1H NMR (300 MHz, [D8]THF, 25°C, TMS): d =
-9.16 (br s, 2H; NH), -3.82 (br s, 2H; N-CH2), -3.59 (br s, 2H; N-CH2), 0.366 (s, 6H; NCH3), -1.69 (d, 2H), 3.04 (t, 2H), 5.56 (t, 2H), 7.65 (d, 2H), 13.76 (br s, 2H), and 40.56
(br s, 2H) ppm; 13C{1H} NMR (75 MHz, [D8]THF): d = 33.2 (N-CH3), 43.8 (N-CH2),
85.99, 116.43, 116.86, 122.07, 122.58, 128.64, 130.49, 132.39, 134.54, and 180.40 ppm;
IR (KBr): n = 3342, 3299, 3043, 2985, 2952, 2875, 2856, 2803, 1612, 1589, 1554, 1501,
1463, 1423, 1342, 1283, 1248, 1175, 1138, 1096, 1069, 995, 959, 935, 898, 821, 746,
665, 642, 591, 574 cm-1; Elemental analysis calcd (%) for C72H72Li3O6N6Eu•THF
(1362.27 g mol-1): C, 67.01; H, 5.92; N, 6.17; found: C, 67.26; H, 6.35; N, 5.99.
Preparation of Li3(DMEDA)3(BINOLate)3La (4): Under nitrogen, DMEDA
(0.143 mL, 0.118 g, 1.34 mmol) was added to a 40 mL THF solution of
Li3(THF)3(BINOLate)3La (2) (0.500 g, 0.407 mmol). After stirring this solution at room
temperature for 4 h, all volatile materials were removed in vacuo. The remaining white
solid was placed on a frit and washed with three 5 mL portions of diethyl ether, affording
0.470 g of the desired compound after drying under reduced pressure (91% yield based
on Li3(THF)3(BINOLate)3La (2)): 1H NMR (300 MHz, [D8]THF, 25°C, TMS): d = 0.61
(br s, 2H; NH), 1.60 (s, 6H; N-CH3), 1.69 (br d, 2H; N-CH2), 1.96 (br d, 2H; N-CH2),
6.83 (d, 2H), 6.91 (m, 4H), 7.23 (d, 2H), and 7.67 (t, 4H) ppm; 13C{1H} NMR (75 MHz,
[D8]THF): d 36.1 (N-CH3), 50.7 (N-CH2), 119.4, 120.4, 125.0, 126.1, 127.2, 127.9,
128.2, 128.6, 136.6, and 163.8; IR (KBr): n = 3341, 3299, 3043, 2981,2952, 2890, 2855,
2802, 1612, 1588, 1553, 1499, 1463, 1422, 1342, 1283, 1247, 1177, 1140, 1096, 1069,
994, 959, 935, 882, 822, 746, 665, 632, 591, 574 cm-1; Elemental analysis calcd (%) for
C72H72Li3O6N6La (1277.11 g mol-1): C, 67.71; H, 5.68; N, 6.58. Found: C, 67.35; H,
5.67; N, 6.30.
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Figure S1. ORTEP plot of Li3(THF)4(BINOLate)3Eu(THF) with 30% probability
thermal ellipsoids.
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