Supporting Information

© Wiley-VCH 2008

69451 Weinheim, Germany

S-1

Design and Formation of a Large, Tetrahedral Supramolecular

Cluster Using 1,1′-Binaphthyl Ligands

Shannon M. Biros, Robert M. Yeh and Kenneth N. Raymond*

Contribution from the Department of Chemistry, University of California,

Berkeley, California 94720-1460.

SUPPORTING INFORMATION

Experimental Section. General Experimental. Dichloromethane, tetrahydrofuran, and diethyl ether were

passed through columns of activated alumina as described by Grubbs and coworkers.1

Deuterated solvents were used as purchased from Cambridge Isotope Laboratories. All

other chemicals were used as obtained from Sigma-Aldrich or Acros Organics and used

without further purification unless otherwise noted. 1H and 13C{1H} NMR spectral data

were recorded on either a Brüker AV-300, AVQ-400, AVB-400, AV-500 or DRX-500,

as noted. Chemical shifts are expressed as parts per million (δ) relative to SiMe4 (TMS, δ

= 0), and referenced internally with respect to the protio solvent impurity. Fast atom

bombardment low resolution (FABLR), high resolution electrospray ionization

quadrupole time-of-flight (HR ESI-QTOF) mass spectra were obtained at the University

of California, Berkeley, Microanalytical Facility. Elemental analyses were performed at

the University of California, Berkeley, Microanalytical Facility on a Perkin-Elmer Series

II CHNO/S analyzer. Molecular modeling (molecular mechanics calculations) was

carried out using the MM3 forcefield as employed by the CAChe 6.1 program from

Fujitsu, Inc.

S-2

NH2

Br

1-amino-5-bromonaphthalene (4). This is a modification of a literature preparation.2

(1) Bromination. A round bottom flask was filled with 1-nitronaphthalene (25.0 g, 0.145

mol) and fresh acid-washed fine iron powder (0.30 g). The organic solid was melted and

maintained in the liquid phase by raising the temperature to 85 °C. Bromine (23 g, 0.14

mol) was added dropwise over a period of 2 h to the hot liquid 1-nitronaphthalene. After

an additional h of heating, the dark mixture was cooled to room temperature. The solid

was dissolved in ethanol at reflux, filtered hot through a plug of celite to remove residual

iron powder, and crystallized by cooling in an ice bath for several h. The isolated solid

(5-bromo-1-nitronaphthalene) was recrystallized once from hot acetone as yellow

crystalline needles and dried under a stream of air overnight (14 g, 40 % yield). m.p.

found120-122 °C. lit. 122.5 °C. 1H NMR (400 MHz, CDCl3) δ 8.61 (1H); 8.47 (1H);

8.23 (1H); 7.94 (1H); 7.67 (1H); 7.55 (1H).

(2) Reduction. A round bottom flask was filled with water (200 mL) and fresh iron

powder (8.0 g, 0.15 mol). The suspension was heated to reflux and glacial acetic acid

(0.5 mL) was carefully added. 5-bromo-1-nitronaphthalene (10 g, 0.04 mol) was added

in small portions to the vigorously stirred hot suspension. More iron powder (4.0 g) was

added and the mixture was stirred for 1h at reflux. The biphasic reaction mixture

(organic / aqueous) was cooled to room temperature, diluted with water (300 mL) and

CH2Cl2 (200 mL) and filtered through a plug of celite to remove residual iron powder.

The aqueous layer was placed in a separatory funnel and sufficient 1N NaOH was added

to raise the pH to about 9 at which point a large amount of precipitate formed. The

organic phase was added to the separatory funnel and the precipitate was extracted into

the organic layer. The organic layer was dried with sodium sulfate and evaporated to

dryness to yield a brown microcrystalline powder (3.7 g, 40 %). 1H NMR (400 MHz,

CDCl3) δ 7.81 (2H), 7.74 (1H); 7.42 (1H), 7.31 (1H), 6.85 (1H), 4.20 (2H). This

literature compound was used without further characterization.

S-3

NH

Br

O

OMe

OMe

1-bromo-5-(2',3′-dimethoxybenzamido)naphthalene (6). A Schlenk flask was charged

with 1-amino-5-bromonaphthalene (6.0 g, 27 mmol), 2,3-dimethoxybenzoic acid chloride

(6, 5.5 g, 28 mmol), NEt3 (4.3 mL, 30 mmol) and anhydrous CH2Cl2 (200 mL). The

solution was filtered after stirring for 12 h at room temperature. The filtrate was washed

with 1 M NaOH (3 x 100 mL) and 1 M HCl (3 x 100 mL). Upon drying with sodium

sulfate, the CH2Cl2 solution was evaporated to yield a crude product. The solid was

dissolved in a small volume of ethanol at reflux and allowed to cool slowly to room

temperature. The product was isolated as large, off-white crystals. A second crop of

product was isolated from a reduced volume of the ethanol. (Total yield: 9.0 g, 86 %). 1H

NMR (500 MHz, CDCl3) δ 10.65 (bs, 1H), 8.51 (d, J = 7.5Hz, 1H), 8.13 (d, J = 8.7 Hz,

1H), 8.03 (d, J = 8.4 Hz, 1H), 7.88 (dd, J = 8.1, 1.4 Hz, 1H), 7.84 (d, J = 7.3 Hz, 1H),

7.66 (dd, J = 8.7, 8.1 Hz, 1H), 7.38 (dd, J = 8.6, 7.5 Hz, 1H), 7.28 (dd, J = 8.5, 8.1 Hz,

1H), 7.16 (dd, J = 8.2, 1.4 Hz, 1H), 4.09 (s, 3H), 3,99 (s, 3H); FAB MS m/z (%) 386 (50)

[M]+; Calcd. (Anal.) for C19H16BrNO3: C, 59.08 (59.09); H, 4.18 (4.28), N; 3.63 (3.49).

NHO

OMe

OMe

HN O

MeO

MeO 5,5′-(2′′,3′′-dimethoxybenzamido)-1,1′-binaphthalene (7). A dry Schlenk flask was

charged with 1-bromo-5-(2′,3′-dimethoxybenzamido)naphthalene (4.0 g, 10 mmol), bis-

S-4

pinacolatodiborane (1.3 g, 5.0 mmol, 0.5 equivalent with respect to the aryl bromide),

PdCl2(dppf)·CH2Cl2 (0.25 g, 3 mol %), Pd(PPh3)4 (0.25 g, 2 mol %), and an excess of

anhydrous K3PO4 (3.0 g) and anhydrous K2CO3 (2.0 g) under a dinitrogen atmosphere.

Degassed DMF (100 mL) was added to the solid. Under vigorous stirring, degassed

water (2 mL) was added to DMF solution to aid the dissolution of the base. The mixture

was stirred for 2 h at 90 °C and 20 h at 80 °C. Water (500 – 800 mL) was added to the

solution after it had cooled to room temperature to precipitate the product. The large

amount of precipitate was isolated by filtration through a medium glass frit. The solid on

the frit was washed repeatedly with water to remove residual DMF and base. After air-

drying, the solid was dissolved in CH2Cl2 : ethyl acetate (50:1) and passed through a

silica gel plug (4 cm) to remove dark palladium impurities. Repeated crystallization (3x)

from hot ethanol yielded off-white microcrystalline product (1.6 g, 95 %). 1H NMR (500

MHz, CDCl3) δ 10.74 (s, 2H), 8.43 (d, J = 7.1 Hz, 2H), 8.18 (d J = 8.7 Hz, 2H), 7.92 (dd,

J = 7.9, 1.5 Hz, 2H), 7.67 (dd, J = 8.7, 6.9 Hz, 2H), 7.54 (dd, J = 6.8, 0.8 Hz, 2H), 7.35

(dd, J = 8.7, 7.8 Hz, 2H), 7.30 (dd, J = 8.5, 8.1 Hz, 2H), 7.22 (apparent d, J = 8.7 Hz,

2H), 7.19 (dd, J = 8.2, 1.4 Hz, 2H), 4.15 (s, 6H), 4.02 (s, 6H); FAB MS m/z (%) 613 (50)

[M]+; Calcd. (Anal.) for C38H32N2O6: C, 74.49 (74.20); H, 5.26 (5.37); N, 4.57 (5.68).

NHO

OH

OH

HN O

HO

HO

5,5’-(2′′,3′′-dihydroxybenzamido)-1,1′-binaphthalene (8). A round bottom flask was

charged with 5,5′-(2′′,3′′-dimethoxybenzamido)-1,1′-binaphthalene (1.6 g, 2.6 mmol),

anhydrous CH2Cl2 (150 mL), and BBr3 (7.4 mL, 74 mmol, 30 equivalents). The yellow

suspension was stirred for 5 days. Water was added very slowly to the ice cooled yellow

S-5

suspension which contained a large excess of unreacted BBr3. After vigorous bubbling

had subsided, the slurry was filtered. The solid was washed with chloroform and hot

ethyl acetate until the filtrate was colorless. The air dried solid was dissolved in hot

methanol (200-300 mL) and kept at reflux for 3 h. Hot water (5 mL) was added to the

solution and the solution was heated to reflux for an additional 8 h. The solution was

removed from heat and poured into a beaker of hot water (300 mL, 100 °C) and allowed

to cool to room temperature. The off-white precipitate was isolated by filtration and

dried under vacuum. (1.1 g, 76 %). 1H NMR (500 MHz, DMSO-d6) δ 11.94 (s, 2H),

10.94 (s, 2H), 9.51 (bs, 2H), 8.16 (d, J = 8.6 Hz, 2H), 7.83 (d, J = 7.3 Hz, 2H), 7.74 (dd, J

= 8.9, 6.9 Hz, 2H), 7.65 (dd, J = 7.9, 1.2 Hz, 2H), 7.58 (dd, J = 6.9, 0.8 Hz, 2H), 7.41 (dd,

J = 8.7, 7.5 Hz, 2H), 7.05 (dd, J = 7.6, 1.4 Hz, 2H), 6.86 (dd, 8.2, 7.9 Hz, 2H); FAB-MS:

m/z 556 [M]+; Calcd. (Anal.) for C34H24N2O6·1.5 H2O : C, 69.98 (69.55); H, 4.66 (4.33);

N, 4.80 (4.69).

Pr4N+

HN

O

O

O

NH

O

O

O

[(6Pr4N)(Pr4N+ ⊂ BINAP Ga4L6.)(5K)]. A 100 mL round bottom schlenk flask was

charged with 75 mg BINAP H4L (8, 0.135 mmol) and 300 mg Bu4NBr (1.12 mmol). The

solids were suspended in ca. 20 mL methanol, and the mixture was degassed by bubbling

through N2 gas for ~15 minutes. A solution of 1N KOH/MeOH was added slowly (540

μL, 0.540 mmol) and was again degassed for ~10 minutes at which time all of the solids

had dissolved. In one portion, 33 mg Ga(acac)3 (0.090 mmol) was added, and the

reaction was heated to 65 °C and stirred for 22 hours under an atmosphere of nitrogen.

The reaction was allowed to cool to room temperature, and the volatiles were removed

under reduced pressure. The crude product was triturated with ca. 10 mL acetone and

filtered under a stream of nitrogen using a Büchner funnel. The resulting solid was

S-6

further washed with acetone (2 x 10 mL) to give 140 mg of product as an olive green

powder that was stored under an inert atmosphere. 1H NMR: (500 MHz, CD3OD) δ

14.10 (s, 12H), 8.16 (m, 12H), 7.66 (m, 12H), 7.46-7.08 (m, 48H), 6.82 (m, 12H), 6.49

(m, 12H), 3.10 (m, 48H), 1.62 (m, 48H), 0.94 (t, J = 7.3Hz, 72H), 0.51 (m, bm, 8H), -

1.00 (bm, 8H), -2.36 (t, J = 7.2H, 6H), -2.55 (t, J = 7.2H, 6H).

Figure S-1. 1H NMR spectrum (CD3OD, 500 MHz) of [(6Pr4N)(Pr4N ⊂ BINAP Ga4L6)(5K)] complex; : host; : external, ion-paired guest; : bound guest; X: solvent impurity.

Bu4N+

HN

O

O

O

NH

O

O

O

[(6Bu4N)(Bu4N ⊂ BINAP Ga4L6)(5K)]. A 100 mL round bottom schlenk flask was

charged with 75 mg BINAP H4L (8, 0.135 mmol) and 73 mg Bu4NBr (0.225 mmol). The

solids were suspended in ca. 15 mL methanol, and the mixture was degassed by bubbling

S-7

through N2 gas for ~15 minutes. A solution of 1N KOH/MeOH was added slowly (540

μL, 0.540 mmol) and was again degassed for ~10 minutes at which time all of the solids

had dissolved. In one portion, 33 mg Ga(acac)3 (0.090 mmol) was added, and the

reaction was heated to 65 °C and stirred for 22 hours under an atmosphere of nitrogen.

The reaction was allowed to cool to room temperature, and the volatiles were removed

under reduced pressure. The crude product was triturated with ca. 10 mL acetone and

filtered under a stream of nitrogen using a Büchner funnel. The resulting solid was

further washed with acetone (2 x 10 mL) to give 100 mg of product as an olive green

powder that was stored under an inert atmosphere. 1H NMR: (500 MHz, CD3OD) δ 14.07

(s, 12H), 7.77 (d, J = 7.7 Hz, 12H), 7.39 (dd, J = 8.0, 10.1 Hz, 12H), 7.34 (d, J = 7.9 Hz,

12H), 7.26-7.18 (m, 24H), 7.13 (dd, J = 8.0, 9.1 Hz, 12H), 6.83 (d, J = 7.3 Hz, 12H), 6.50

(dd, J = 7.8, 9.0 Hz, 12H), 3.16 (m, 48H), 1.59 (m, 48H), 1.36 (m, 48H), 0.97 (t, J = 7.3

Hz, 72H), 0.54 (bm, 8H), -1.14 (bm, 4H), -1.27 (bm, 4H), -1.45 (t, J = 7.2Hz, 12H), -1.96

(bm, 4H), -2.42 (bm, 4H); MS: (HR ESI-QTOF) M5- expected ([Ga4L6]12-+2Bu4N++5K+):

854.778; found: 854.779.

Figure S-2. 1H NMR spectrum (CD3OD, 500 MHz) of [(6Bu4N)(Bu4N ⊂ BINAP Ga4L6)(5K)] complex; : host; : external, ion-paired guest; : bound guest; X: solvent impurity.

S-8

Figure S-3. HR-ESI-QTOF mass spectrum of Bu4N ⊂ BINAP Ga4L6 complex: the observed spectrum is shown on the bottom along with the predicted isotope patterns for the host-guest complex in the 5- charge state.

Pentyl4N+

HN

O

O

O

NH

O

O

O

[(6n-Pentyl4N)(n-Pentyl4N ⊂ BINAP Ga4L6)(5K)]. A 100 mL round bottom schlenk

flask was charged with 75 mg BINAP H4L (8, 0.135 mmol) and 85 mg n-pentyl4NBr

(0.225 mmol). The solids were suspended in ca. 25 mL methanol, and the mixture was

degassed by bubbling through N2 gas for ~15 minutes. A solution of 1N KOH/MeOH

was added slowly (540 μL, 0.540 mmol) and was again degassed for ~10 minutes at

which time all of the solids had dissolved. In one portion, 33 mg Ga(acac)3 (0.090 mmol)

was added, and the reaction was heated to 65 °C and stirred for 22 hours under an

S-9

atmosphere of nitrogen. The reaction was allowed to cool to room temperature, and the

volatiles were removed under reduced pressure. The crude product was triturated with

ca. 10 mL acetone and filtered under a stream of nitrogen using a Büchner funnel. The

resulting solid was further washed with acetone (2 x 10 mL) to give 126 mg of product as

an olive green powder that was stored under an inert atmosphere. 1H NMR: (500 MHz,

CD3OD) δ 13.93 (s, 12H), 7.98 (d, J = 8.7 Hz, 12H), 7.78 (d, 7.1Hz, 12H), 7.30 (m,

12H), 7.18 (m, 12H), 7.02 (dd, J = 7.7, 8.4 Hz, 12 H), 6.78 (m, 12H), 6.45 (dd, 7.8,

7.9Hz, 12H), 3.10 (bm, 48H), 1.55 (bm, 48H), 1.33 (bm, 48H), 1.24 (bm, 48H), 0.86 (t, J

= 6.9H, 72H), 0.48 (bm, 4H), 0.30 (bm, 4H), 0.01 (t, J = 6.9 Hz, 12H), -0.74 (bm, 4H), -

0.85 (bm, 4H), -1.61 (bm, 4H), -2.30 (bm, 8H), -2.42 (bm, 4H); MS: (ESI-QTOF) M5-

expected ([Ga4L6]12-+2n-pentyl4N++5K+): 877.203; found: 877.232.

Figure S-4. 1H NMR spectrum (CD3OD, 500 MHz) of [(6 n-pentyl4N)(n-pentyl4N ⊂ BINAP Ga4L6)(6K+)] complex; : host; : external, ion-paired guest; : bound guest; X: solvent impurity.

S-10

Figure S-5. HR-ESI-QTOF mass spectrum of n-Pentyl4N⊂BINAP Ga4L6 complex: the observed spectrum is shown on the bottom along with the predicted isotope patterns for the host-guest complex in the 5- charge state.

HN

O

O

O

NH

O

O

O

Ph4P+

[(12Ph4P)(Ph4P ⊂ BINAP Ga4L6)]. A 100 mL round bottom schlenk flask was charged

with 100 mg BINAP H4L (8, 0.177 mmol), 44 mg Ga(acac)3 (0.12 mmol) and 332 mg

Ph4PCl (0.885 mmol, 5 eq.). The solids were suspended in ca. 20 mL methanol, and the

mixture was degassed by bubbling through N2 gas for ~15 minutes. A solution of 0.5N

KOH/MeOH was added slowly (1.4 mL, 0.70 mmol, 4eq./H4L) and was again degassed

for ~10 minutes. The reaction flask was equipped with a reflux condenser, heated to 65

°C and stirred for 22 hours under an atmosphere of nitrogen. The reaction was allowed to

cool to room temperature, and the volatiles were removed under reduced pressure. The

crude product was triturated with ca. 20 mL acetone and filtered under a stream of

nitrogen using a Büchner funnel. The resulting yellow solid was further washed with

S-11

acetone (2 x 10 mL) to give 240 mg of product as an orange-yellow powder that was

stored under an inert atmosphere. 1H NMR: (CD3OD, 500 MHz) δ 14.07 (bs, 12H), 8.09

(d, J = 8.5 Hz, 12H), 7.86-7.75 (m, 48H), 7.69-7.58 (m, 108H), 7.58-7.48 (m, 96H), 7.30

(dd, J = 8.1, 1.4 Hz, 12H), 7.01 (m, 24H), 6.88 (d, J = 7.2 Hz, 12H), 6.85 (d, J = 8.5 Hz,

12H), 6.79 (dd, J = 7.3, 1.4 Hz, 12H), 6.43 (dd, J = 9.2, 7.9 Hz, 12H), 5.77 (t, J = 8.1 Hz,

4H), 4.79 (m, 8H, solvent obscured), 4.05 (m, 8H); MS: (HR ESI-QTOF) M5- expected

([Ga4L6]12-+2Ph4P++4K++1H+): 885.926; found: 885.922.

Figure S-6. 1H NMR spectrum (CD3OD, 500 MHz) of [(12Ph4P+)(Ph4P ⊂ BINAP Ga4L6)] complex; : host; : external, ion-paired guest; : bound guest; X: solvent impurity.

S-12

Figure S-7. 1H NMR spectrum (DMSO-d6, 500 MHz) of [(12Ph4P)(Ph4P ⊂ BINAP Ga4L6)] complex; : host; : external, ion-paired guest; : bound guest; X: solvent impurity.

Figure S-8. HR-ESI-QTOF mass spectrum of Ph4P ⊂ BINAP Ga4L6 complex: the observed spectrum is shown on the bottom along with the predicted isotope patterns for the host-guest complex in the 5- charge state.

S-13

HN

O

O

O

NH

O

O

O

Ph3PrP+

Ph3PrP+⊂BINAP Ga4L6. This complex was generated and characterized in-situ. An

NMR tube was charged with 5 mg ligand 8 (0.009 mmol, 6 eq.) and 2.4 mg Ph3BuPBr

(0.006 mmol, 4 eq.). The solids were suspended in 700 μL CD3OD, and 72 μL 0.5N

KOH/MeOH (0.036 mmol, 24 eq.) was added by syringe. The tube was shaken, and

Ga(acac)3 (300 μL of 22 mg/3.0 mL CD3OD; 0.006 mmol, 2.2 mg, 4 eq.) was added.

The NMR tube was immediately flame sealed under static vacuum and the tube heated to

65 °C overnight in an oil bath. After cooling to room temperature, the following spectra

were obtained: MS: (HR ESI-QTOF) M5- expected ([Ga4L6]12-+Ph3PrP++6K+): 828.10;

found: 827.90.

S-14

Figure S-9. 1H NMR spectrum (DMSO-d6, 500 MHz) of [(Ph3PrP ⊂ BINAP Ga4L6)(11K)] complex; : host; : free guest; : bound guest; X: solvent impurity.

Figure S-10. HR-ESI-QTOF mass spectrum of [Ph3PrP ⊂ BINAP Ga4L6] complex: the observed spectrum is shown on the bottom along with the predicted isotope patterns for the host-guest complex in the 5- charge state. The peak to the immediate left of the identified peak results from H+/K+ exchange in the gas phase. (This sample was exposed to CD3OD, so there is some H/D exchange at the amide functions. The exact molecular formula is listed in the figure.)

S-15

HN

O

O

O

NH

O

O

O

Ph3BuP+

Ph3BuP+⊂BINAP Ga4L6. This complex was generated and characterized in-situ. An

NMR tube was charged with 5 mg ligand 8 (0.009 mmol, 6 eq.) and 2.3 mg Ph3BuPBr

(0.006 mmol, 4 eq.). The solids were suspended in 700 μL CD3OD, and 72 μL 0.5N

KOH/MeOH (0.036 mmol, 24 eq.) was added by syringe. The tube was shaken, and

Ga(acac)3 (300 μL of 22 mg/3.0 mL CD3OD; 0.006 mmol, 2.2 mg, 4 eq.) was added.

The NMR tube was immediately flame sealed under static vacuum and the tube was

heated to 65 °C overnight in an oil bath. After cooling to room temperature, the

following spectra were obtained: MS: (HR ESI-QTOF) M5- expected ([Ga4L6]12-

+2Ph3BuP++5K+): 867.14; found: 867.15.

Figure S-11. 1H NMR spectrum (DMSO-d6, 500 MHz) of [(Ph3BuP ⊂ BINAP Ga4L6)(11K)] complex; : host; : free guest; : bound guest; X: solvent impurity.

S-16

Figure S-12. HR-ESI-QTOF mass spectrum of [Ph3BuP⊂BINAP Ga4L6]complex: the observed spectrum is shown on the bottom along with the predicted isotope patterns for the host-guest complex in the 5- charge state. The peak to the immediate left of the identified peak results from H+/K+ exchange in the gas phase. (This sample was exposed to CD3OD, so there is some H/D exchange at the amide functions. The exact molecular formula is listed in the figure.)

Literature cited.

(1) Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Organometallics 1996, 15, 1518-1520.

(2) Klemm, L. H.; Sprague, J. W.; Mak, E. Y. K. Journal of Organic Chemistry 1957, 22, 161-166.