Synthesis, structure, and catalytic activity of chiral silver(I) and copper(II) complexes with biaryl-based nitrogen-containing ligands

Article abstract of DOI:10.1016/j.ica.2010.11.023

A series of chiral Ag(I) and Cu(II) complexes have been prepared from the reaction between AgX (X = NO₃, PF₆, OTf) or CuX ₂ (X = Cl, ClO₄) and chiral biaryl-based N-ligands. The rigidity of the ligand plays an i

Full text of DOI:10.1016/j.ica.2010.11.023

Inorganica Chimica Acta 366 (2011) 320–336
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Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Synthesis, structure, and catalytic activity of chiral silver(I) and copper(II)
complexes with biaryl-based nitrogen-containing ligands
Haiyan Zhang a, Liang Chen a, Haibin Song b, Guofu Zi a,
⇑
a Department of Chemistry, Beijing Normal University, Beijing 100875, China
b State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China
a r t i c l e i n f o
a b s t r a c t
Article history:
A series of chiral Ag(I) and Cu(II) complexes have been prepared from the reaction between AgX (X = NO3,
PF6, OTf) or CuX2 (X = Cl, ClO4) and chiral biaryl-based N-ligands. The rigidity of the ligand plays an
important role in the Ag(I) complex formation. For example, treatment of chiral N3-ligands 1–3 with half
equiv of AgX (X = NO3, PF6, OTf) gives the chiral bis-ligated four-coordinated Ag(I) complexes, while
ligand 4 affords the two-coordinated Ag(I) complexes. Reaction of AgX with 1 equiv of chiral N4-ligands
5, 7, 8 and 10 gives the chiral, binuclear double helicate Ag(I) complexes, while chiral mono-nuclear
single helicate Ag(I) complexes are obtained with N4-ligands 6 and 9. Treatment of either N3-ligand 1
or N4-ligand 9 or 10 with 1 equiv of CuX2 (X = Cl, ClO4) gives the mono-ligated Cu(II) complexes. All
the complexes have been characterized by various spectroscopic techniques, and elemental analyses.
Seventeen of them have further been confirmed by X-ray diffraction analyses. The Cu(II) complexes do
not show catalytic activity for allylation reaction, in contrast to Ag(I) complexes, but they do exhibit cat-
alytic activity for Henry reaction (nitroaldol reaction) that Ag(I) complexes do not.
Received 5 October 2010
Accepted 15 November 2010
Available online 21 November 2010
Keywords:
Chiral N-ligands
Cu(II) complexes
Ag(I) complexes
Crystal structure
Asymmetric allylation reaction
Asymmetric Henry reaction
Ó 2010 Elsevier B.V. All rights reserved.
1. Introduction
coordinated by chiral C1-symmetric tridentate N3-ligands. In our
endeavor to further explore the BINAM chemistry, we have
In recent years, both the symmetric and nonsymmetric 2,20-
substituted-1,10-binaphthyls have been widely used as chiral
ligands in organic synthesis and asymmetric synthesis [1–12]. In
particular, 2,20-diamino-1,10-binaphthyl (BINAM) as its (R) or (S)
enantiomers have been modified to give variants which bear
appropriate structural and electronic features for intended specific
reactions, and its derivatives have exhibited good to excellent
enantioselectivities in a number of asymmetric transformations
[7–12]. In recent years, we have developed a series of bina-
phthyldiamine-based chiral nitrogen-containing ligands, and their
Ir(I), Rh(I), Ti(IV), Ag(I), Zr(IV) and lanthanide complexes are useful
catalysts for a range of transformations [13–29]. Further we dem-
onstrated that the binaphthyldiamine-based bis-ligated lanthanide
amides [(S)-2-Me2N–C20H12-20-(NCHC4H3N)]2LnN(SiMe3)2 with C1-
symmetric N3-ligand are more effective chiral catalysts for the
enantioselective hydroamination/cyclization reaction than those
[(R)-C20H12(NCHC4H3N)2]LnN(SiMe3)2(thf) (Ln = Sm, Y, Yb) with
C2-symmetric N4-ligands [15,17]. In our ongoing research, we are
now focusing on the preparation of the type of bis-ligated catalysts
recently extended our work to a new chiral C1-symmetric versatile
ligand, (R)-2-(pyridin-2-ylmethylimino)-20-(dimethylamino)-1,10-
binaphthyl (1), which contains three
r-donating nitrogen atoms
that can act in bidentate or tridentate fashion. Herein, we report
the synthesis and property of the new chiral ligand, its use in the
coordination chemistry of group 11 metals, and the applications
of the resulting complexes as catalysts for the asymmetric allylation
and Henry reaction (nitroaldol reaction). For better understanding
and comparison, the C1-symmetric N3-ligands (R)-2-(pyridin-2-
ylmethyleneamino)-20-(dimethylamino)-6,60-dimethyl-1,10-biphe-
nyl (2), (R)-2-(pyridin-2-ylmethylamino)-20-(dimethylamino)-6,
60-dimethyl-1,10-biphenyl (3) and (R)-2-(pyridin-2-ylamino)-20-
(dimethylamino)-6,60-dimethyl-1,10-biphenyl (4), and C2-symmetric
N4-ligands (R)-2,20-bis(pyridin-2-ylmethyleneamino)-1,10-binaph-
thyl (5), (R)-2,20-bis(pyridin-2-ylmethylamino)-1,10-binaphthyl
(6), (R)-5,506,607,708,80-octahydro-2,20-bis(2-(pyridin-2-ylmethyl-
ene)-1,10-binaphthyldimine (7), (R)-2,20-bis(pyridin-2-ylmethyle-
neamino)-6,60-dimethyl-1,10-biphenyl (8), (R)-2,20-bis(pyridin-2-
ylmethylamino)-6,60-dimethyl-1,10-biphenyl (9) and (S)-2,20-
bis(pyridin-2-ylamino)-6,60-dimethyl-1,10-biphenyl (10), which
are derived from (R)-2,20-diamino-1,10-binaphthyl, and (R) or (S)-
2,20-diamino-6,60-dimethyl-1,10-biphenyl, respectively, will also
be included in this contribution.
⇑
Corresponding author. Tel.: +86 10 5880 6051; fax: +86 10 5880 2075.
E-mail address: gzi@bnu.edu.cn (G. Zi).
0020-1693/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2010.11.023

H. Zhang et al. / Inorganica Chimica Acta 366 (2011) 320–336
321
1464 (s), 1434 (s), 1314 (s), 1023 (s), 967 (s), 785 (s). Anal. Calc.
for C22H23N3: C, 80.21; H, 7.04; N, 12.76. Found: C, 80.13; H,
6.93; N, 12.82%.
2. Experimental section
2.1. General methods
2.4. Preparation of (R)-5,506,607,708,80-octahydro-2,20-bis(2-(pyridin-
All chemicals were purchased from Aldrich Chemical Co. and
Beijing Chemical Co. used as received unless otherwise noted.
(R)-2,20-Diamino-1010-binaphthyl [27], (R)-5,50,6,60,7,708,80-octahy-
dro-2,20-diamino-1,10-binaphthyl [27], (R) or (S)-2,20-diamino-
6,60-dimethyl-1,10-biphenyl [24], (R)-2-amino-20-dimethylamino-1,
10-binaphthyl [24], (R)-2-amino-20-(dimethylamino)-6,60-dime-
thyl-1,10-biphenyl [24], (R)-2-(pyridin-2-ylmethylamino)-20-
(dimethylamino)-6,60-dimethyl-1,10-biphenyl (3) [24], (R)-2-(pyri-
din-2-ylamino)-20-(dimethylamino)-6,60-dimethyl-1,10-biphenyl (4)
2-ylmethylene)-1,10-binaphthyldimine (7)
This compound was prepared as a yellow solid from the reac-
tion of (R)-5,506,607,708,80-octahydro-1,10-binaphthyl (2.92 g,
10.0 mmol) with pyridine-2-carboxaldehyde (2.14 g, 20.0 mmol)
in the presence of 4 Å molecular sieves in dry toluene (50 mL) at
70 °C and washed with n-hexane by a similar procedure as in the
synthesis of 1. Yeild: 4.01 g (90%). M.p.: 66–68 °C. 1H NMR
(C6D6): d 8.79 (s, 2H, N@CH), 8.35 (d, J = 4.6 Hz, 2H, aryl), 7.89 (d,
J = 7.9 Hz, 2H, aryl), 6.94 (d, J = 8.2 Hz, 2H, aryl), 6.82 (m, 4H, aryl),
6.47 (m, 2H, aryl), 2.60 (m, 6H, CH2), 2.45 (m, 2H, CH2), 1.58 (m, 8H,
CH2). IR (KBr, cmꢀ1): v 3047 (w), 2922 (s), 1634 (s), 1583 (s), 1565
(s), 1471 (s), 1434 (s), 1261 (s), 1088 (s), 1026 (s), 806 (s). Anal.
Calc. for C30H30N4: C, 80.68; H, 6.77; N, 12.55. Found: C, 80.57; H,
6.64; N, 12.57%.
[25],
(R)-2,20-bis(pyridin-2-ylmethyleneamino)-1,10-binaphthyl
(5) [13,14], (R)-2,20-bis(pyridin-2-ylmethylamino)-1,10-binaphthyl
(6) [14], (R)-2,20-bis(pyridin-2-ylmethyleneamino)-6,60-dimethyl-
1,10-biphenyl (8) [25], (R)-2,20-bis(pyridin-2-ylmethylamino)-6,
60-dimethyl-1,10-biphenyl (9) [25] and (S)-2,20-bis(pyridin-2-yla-
mino)-6,60-dimethyl-1,10-biphenyl (10) [30] were prepared accord-
ing to literature methods. Infrared spectra were obtained from KBr
pellets on an Avatar 360 Fourier transform spectrometer. 1H NMR
spectra were recorded on a Bruker AV-400 spectrometer. All chem-
ical shifts are reported in d units with reference to the residual pro-
tons of the deuterated solvents. Melting points were measured on
an X-6 melting point apparatus and were uncorrected. Optical
rotations were measured on a Perkin–Elmer 343 polarimeter.
Enantiomeric excesses were determined by HPLC with a Chiralcel
OD-H column. Elemental analyses were performed on a Vario EL
elemental analyzer.
2.5. General procedure for the preparation of Ag(I) complexes 11–13
and 15–23
Preparation of [(1)2Ag](NO3) (11) is representative. A CH2Cl2
solution (20 mL) of 1 (0.80 g, 2.0 mmol) was added to a methanol
solution (5 mL) of AgNO3 (0.17 g, 1.0 mmol) with stirring at room
temperature. The solution was stirred for 5 h at room temperature
and filtered. The solution was reduced to 5 mL and cooled to
ꢀ20 °C, yielding yellow microcrystals, which were isolated by fil-
tration. Yield: 0.83 g (85%). M.p.: 200–202 °C (dec.). 1H NMR
(CDCl3): d 8.00 (m, 4H, aryl and N@CH), 7.85 (d, J = 4.3 Hz, 2H, aryl),
7.80 (d, J = 4.2 Hz, 2H, aryl), 7.64 (d, J = 2.0 Hz, 2H, aryl), 7.58 (d,
J = 3.8 Hz, 2H, aryl), 7.50 (m, 2H, aryl), 7.32 (t, J = 3.6 Hz, 2H, aryl),
7.16–6.98 (m, 14H, aryl), 6.90 (d, J = 4.2 Hz, 2H, aryl), 6.76 (d,
J = 4.2 Hz, 2H, aryl), 2.01 (s, 12H, NCH3). IR (KBr, cmꢀ1): v 3053
(w), 2934 (w), 1616 (m), 1588 (s), 1504 (s), 1384 (s), 1338 (s),
1302 (s), 992 (s), 819 (s). Anal. Calc. for C56H46N7AgO3: C, 69.14;
H, 4.77; N, 10.08. Found: C, 69.05; H, 4.64; N, 10.12%. Yellow crys-
tals 11ꢁCH3OH suitable for X-ray structural analysis were grown
from a methanol solution at room temperature.
2.2. Preparation of (R)-2-(pyridin-2-ylmethylimino)-20-
(dimethylamino)-1,10-binaphthyl (1)
Pyridine-2-carboxaldehyde (0.54 g, 5.0 mmol) was mixed with
(S)-2-amino-20-dimethylamino-1,10-binaphthyl (1.56 g, 5.0 mmol)
in dry toluene (25 mL). A few 4 Å molecular sieves were added,
and the solution was warmed to 70 °C and kept for two days at this
temperature. The solution was filtered and the solvent was re-
moved under reduced pressure. The resulting yellow solid was
recrystallization from an n-hexane solution to give 1 as yellow
crystals. Yield: 1.71 g (85%). M.p.: 116–118 °C. 1H NMR (C6D6): d
8.96 (s, 1H, CH@N), 8.47 (d, J = 4.3 Hz, 1H, aryl), 7.88 (d,
J = 8.8 Hz, 1H, aryl), 7.82 (m, 3H, aryl), 7.68 (d, J = 7.8 Hz, 1H, aryl),
7.57 (d, J = 8.2 Hz, 1H, aryl), 7.50 (m, 2H, aryl), 7.33 (m, 2H, aryl),
7.23 (t, J = 7.2 Hz, 1H, aryl), 7.16 (t, J = 7.7 Hz, 1H, aryl), 7.09 (t,
J = 7.7 Hz, 1H, aryl), 6.78 (t, J = 7.6 Hz, 1H, aryl), 6.55 (t, J = 6.0 Hz,
2.5.1. [(1)2Ag](PF6) (12)
Yield: 0.92 g (87%). Yellow crystals, m.p.: 250–252 °C (dec.). 1H
NMR (CDCl3): d 7.91 (m, 4H, aryl and N@CH), 7.85 (d, J = 4.2 Hz, 2H,
aryl), 7.80 (d, J = 4.1 Hz, 2H, aryl), 7.63 (d, J = 2.1 Hz, 2H, aryl), 7.54
(d, J = 3.8 Hz, 2H, aryl), 7.49 (m, 2H, aryl), 7.31 (t, J = 3.5 Hz, 2H,
aryl), 7.11–7.02 (m, 14H, aryl), 6.90 (d, J = 4.1 Hz, 2H, aryl), 6.76
(d, J = 4.1 Hz, 2H, aryl), 1.97 (s, 12H, NMe2). IR (KBr, cmꢀ1): v
3055 (w), 2931 (w), 1616 (m), 1589 (s), 1504 (s), 1437 (s), 1354
(s), 1302 (s), 1204 (s), 1142 (s), 993 (s), 843.0(s). Anal. Calc. for
1H, aryl), 2.47 (s, 6H, NMe2). IR (KBr, cmꢀ1):
m 3049 (w), 2932
(w), 1636 (s), 1615 (s), 1595 (s), 1504 (s), 2345 (s), 1141 (s), 992
(s), 818 (s), 751 (s). Anal. Calc. for C28H23N3: C, 83.76; H, 5.77; N,
10.47. Found: C, 83.72; H, 5.56; N, 10.42%.
C
56H46N6AgF6P: C, 63.70; H, 4.39; N, 7.96. Found: C, 63.91; H,
2.3. Preparation of (R)-2-(pyridin-2-ylmethyleneamino)-20-
(dimethylamino)-6,60-dimethyl-1,10-biphenyl (2)
4.44; N, 7.86%.
2.5.2. [(1)2Ag](OTf) (13)
This compound was prepared as a pale yellow oil from the reac-
tion of (R)-2-amino-20-(dimethylamino)-6,60-dimethyl-1,10-biphe-
nyl (2.40 g, 10.0 mmol) with pyridine-2-carboxaldehyde (1.07 g,
10.0 mmol) in the presence of 4 Å molecular sieves in dry toluene
(50 mL) at 70 °C and washed with n-hexane by a similar procedure
as in the synthesis of 1. Yield: 2.99 g (91%). 1H NMR (C6D6): d 8.80
(s, 1H, N@CH), 8.41 (d, J = 2.3 Hz, 1H, aryl), 7.82 (d, J = 4.0 Hz, 1H,
aryl), 7.19 (m, 1H, aryl), 7.10 (m, 2H, aryl), 6.92 (d, J = 3.7 Hz, 1H,
aryl), 6.87 (d, J = 4.0 Hz, 1H, aryl), 6.80 (m, 2H, aryl), 6.51 (m, 1H,
aryl), 2.43 (s, 6H, NCH3), 2.07 (s, 3H, CH3), 2.00 (s, 3H, CH3). IR
(KBr, cmꢀ1): v 3053 (m), 2975 (m), 2960 (m), 1626 (s), 1584 (s),
Yield: 0.87 g (82%). Yellow solid, m.p.: 192–194 °C (dec.). 1H
NMR (CDCl3): d 7.98 (m, 4H, aryl and N@CH), 7.86 (d, J = 4.3 Hz,
2H, aryl), 7.81 (d, J = 4.2 Hz, 2H, aryl), 7.63 (d, J = 2.0 Hz, 2H, aryl),
7.57 (d, J = 3.6 Hz, 2H, aryl), 7.52 (m, 2H, aryl), 7.33 (t, J = 3.6 Hz,
2H, aryl), 7.12–7.02 (m, 14H, aryl), 6.91 (d, J = 4.2 Hz, 2H, aryl),
6.76 (d, J = 4.2 Hz, 2H, aryl), 1.97 (s, 12H, NMe2). IR (KBr, cmꢀ1): v
3053 (w), 2934 (w), 1617 (m), 1588 (s), 1505 (s), 1436 (s), 1262
(s), 1154 (s), 1029 (s), 820 (s), 750 (s). Anal. Calc. for C57H46N6Ag-
F3O3S: C, 64.59; H, 4.37; N, 7.93. Found: C, 64.62; H, 4.43; N,
7.96%. Yellow crystals 13ꢁCH3OH suitable for X-ray structural anal-
ysis were grown from a methanol solution at room temperature.

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H. Zhang et al. / Inorganica Chimica Acta 366 (2011) 320–336
2.5.3. [(2)2Ag](NO3) (15)
(s), 759 (s). Anal. Calc. for C45H50N6AgF3O3S: C, 58.76; H, 5.48; N,
Yield: 0.70 g (84%). Yellow solid, m.p.: 212–214 oC (dec.). 1H
NMR (CDCl3): d 8.35 (s, 2H, N@CH), 7.98 (t, J = 7.6 Hz, 2H, aryl),
7.89 (d, J = 4.4 Hz, 2H, aryl), 7.75 (d, J = 7.6 Hz, 2H, aryl), 7.48 (t,
J = 6.1 Hz, 2H, aryl), 7.29 (t, J = 7.7 Hz, 2H, aryl), 7.20 (m, 2H, aryl),
7.01 (d, J = 7.8 Hz, 2H, aryl), 6.55 (m, 2H, aryl), 6.48 (m, 4H, aryl),
2.13 (s, 12H, NMe2), 1.95 (s, 6H, CH3), 1.69 (s, 6H, CH3). IR (KBr,
cmꢀ1): v 3041 (w), 2922 (w), 1622 (m), 1586 (s), 1452 (s), 1384
(s), 1330 (s), 1263 (s), 1026 (s), 966 (s), 792 (s), 744 (s). Anal. Calc.
for C44H46N7AgO3: C, 63.77; H, 5.59; N, 11.83. Found: C, 63.62; H,
5.43; N, 11.96%.
9.14. Found: C, 59.00; H, 5.43; N, 9.18%.
2.5.9. [(4)2Ag](NO3) (21)
Yield: 0.66 g (82%). White solid, m.p.: 180–182 °C (dec.). 1H
NMR (DMSO-d6): d 8.00 (d, J = 4.8 Hz, 2H, aryl), 7.62 (d, J = 8.0 Hz,
2H, aryl), 7.47 (t, J = 6.9 Hz, 2H, aryl), 7.22 (t, J = 7.8 Hz, 4H, aryl),
6.97 (m, 6H, aryl), 6.75 (d, J = 8.4 Hz, 2H, aryl), 6.70 (m, 4H, aryl
and NH), 2.38 (s, 12H, NMe2), 1.91 (s, 6H, CH3), 1.81 (s, 6H, CH3).
IR (KBr, cmꢀ1): v 3398 (m), 2943 (w), 1604 (s), 1582 (s), 1512 (s),
1464 (s), 1440 (s), 1384 (s), 769 (s). Anal. Calc. for C42H46N7AgO3:
C, 62.69; H, 5.76; N, 12.18. Found: C, 62.45; H, 5.83; N, 12.16%.
2.5.4. [(2)2Ag](PF6) (16)
Yield: 0.76 g (83%). Yellow crystals, m.p.: 180–182 °C (dec.). 1H
NMR (CDCl3): d 8.41 (s, 2H, N@CH), 7.94 (t, J = 7.4 Hz, 2H, aryl), 7.90
(d, J = 4.3 Hz, 2H, aryl), 7.78 (d, J = 7.8 Hz, 2H, aryl), 7.48 (t,
J = 6.0 Hz, 2H, aryl), 7.30 (t, J = 7.8 Hz, 2H, aryl), 7.20 (m, 2H, aryl),
7.01 (d, J = 7.8 Hz, 2H, aryl), 6.66 (m, 2H, aryl), 6.47 (m, 4H, aryl),
2.24 (s, 12H, NMe2), 1.90 (s, 6H, CH3), 1.66 (s, 6H, CH3). IR (KBr,
cmꢀ1): v 3059 (m), 2939 (m), 1628 (m), 1587 (s), 1454 (s), 1322
(s), 1134 (s), 793 (s). Anal. Calc. for C44H46N6AgF6P: C, 57.96; H,
5.09; N, 9.22. Found: C, 58.02; H, 5.13; N, 9.32%.
2.5.10. [(4)2Ag](PF6) (22)
Yield: 0.70 g (79%). White solid, m.p.: 250–252 °C (dec.). 1H
NMR (DMSO-d6): d 8.02 (d, J = 4.6 Hz, 2H, aryl), 7.63 (d, J = 8.1 Hz,
2H, aryl), 7.46 (t, J = 6.8 Hz, 2H, aryl), 7.23 (t, J = 7.8 Hz, 4H, aryl),
7.00 (m, 6H, aryl), 6.76 (d, J = 8.2 Hz, 2H, aryl), 6.68 (m, 4H, aryl
and NH), 2.36 (s, 12H, NMe2), 1.90 (s, 6H, CH3), 1.80 (s, 6H, CH3).
IR (KBr, cmꢀ1): v 3350 (m), 2940 (m), 1613 (s), 1508 (s), 1459 (s),
1298 (s), 1157 (s), 840 (s). Anal. Calc. for C42H46N6AgF6P: C,
56.83; H, 5.22; N, 9.47. Found: C, 56.76; H, 5.32; N, 9.42%. Colorless
crystals 22ꢁCH3OH suitable for X-ray structural analysis were
grown from a methanol solution at room temperature.
2.5.5. [(2)2Ag](OTf) (17)
Yield: 0.82 g (89%). Yellow solid, m.p.: 192–194 °C (dec.). 1H
NMR (CDCl3): d 8.64 (s, 2H, N@CH), 8.17 (t, J = 7.6 Hz, 2H, aryl),
8.04 (d, J = 4.6 Hz, 2H, aryl), 7.81 (d, J = 7.6 Hz, 2H, aryl), 7.64 (t,
J = 5.8 Hz, 2H, aryl), 7.40 (t, J = 7.7 Hz, 2H, aryl), 7.27 (m, 2H, aryl),
7.01 (d, J = 7.8 Hz, 2H, aryl), 6.56 (m, 2H, aryl), 6.45 (m, 4H, aryl),
2.09 (s, 12H, NMe2), 1.92 (s, 3H, CH3), 1.63 (s, 3H, CH3). IR (KBr,
cmꢀ1): v 3059 (w), 2938 (w), 1629 (m), 1587 (s), 1453 (s), 1270
(s), 1150 (s), 1031 (s), 792 (s). Anal. Calc. for C45H46N6AgF3O3S: C,
59.02; H, 5.06; N, 9.18. Found: C, 59.02; H, 5.23; N, 9.12%.
2.5.11. [(4)2Ag](OTf) (23)
Yield: 0.72 g (81%). White solid, m.p.: 196–198 °C (dec.). 1H
NMR (DMSO-d6): d 8.01 (d, J = 4.9 Hz, 2H, aryl), 7.65 (d, J = 8.0 Hz,
2H, aryl), 7.48 (t, J = 7.7 Hz, 2H, aryl), 7.23 (t, J = 7.8 Hz, 4H, aryl),
6.98 (m, 6H, aryl), 6.75 (d, J = 8.4 Hz, 2H, aryl), 6.68 (t, J = 6.3 Hz,
2H, aryl), 6.63 (s, 2H, NH), 2.39 (s, 12H, NMe2), 1.91 (s, 6H, CH3),
1.82 (s, 6H, CH3). IR (KBr, cmꢀ1): v 3398 (m), 2943 (w), 1605 (s),
1582 (s), 1509 (s), 1464 (s), 1440 (s), 1259 (s), 1033 (s), 769 (s).
Anal. Calc. for C43H46N6AgF3O3S: C, 57.91; H, 5.20; N, 9.42. Found:
C, 57.84; H, 5.23; N, 9.36%.
2.5.6. [(3)2Ag](NO3) (18)
Yield: 0.67 g (80%). White solid, m.p.: 178–180 °C (dec.). 1H
NMR (DMSO-d6): d 8.44 (d, J = 4.8 Hz, 2H, aryl), 7.73 (t, J = 7.6 Hz,
2H, aryl), 7.34 (d, J = 7.8 Hz, 2H, aryl), 7.22 (t, J = 7.8 Hz, 4H, aryl),
6.98 (m, 6H, aryl), 6.56 (d, J = 7.4 Hz, 2H, aryl), 6.36 (d, J = 8.1 Hz,
2H, aryl), 4.77 (br s, 2H, NH), 4.34 (s, 4H, CH2), 2.46 (s, 12H,
NMe2), 1.86 (s, 6H, CH3), 1.78 (s, 6H, CH3). IR (KBr, cmꢀ1): v 3369
(m), 2928 (m), 2856 (m), 1583 (s), 1509 (s), 1472 (s), 1383 (s),
1352 (s), 1323 (s), 1278 (s), 760 (s). Anal. Calc. for C44H50N7AgO3:
C, 63.46; H, 6.05; N, 11.77. Found: C, 63.45; H, 6.13; N, 11.76%.
2.6. Preparation of [(1)2Ag]2[Ag(NO3)3(OH2)] (14)
AgNO3 (34 mg, 0.2 mmol) was added to a methanol solution
(5 mL) of 11 (194 mg, 0.2 mmol) with stirring at room tempera-
ture. The solution was stirred for 2 h at room temperature and fil-
tered. The solution was reduced to 1 mL and cooled to ꢀ20 °C,
yielding yellow crystals, which were isolated by filtration. Yield:
183 mg (86%). M.p.: 168–170 °C (dec.). 1H NMR (CD3OD): d 7.99
(m, 8H, aryl and N@CH), 7.87 (d, J = 4.2 Hz, 4H, aryl), 7.82 (d,
J = 4.1 Hz, 4H, aryl), 7.63 (d, J = 1.9 Hz, 4H, aryl), 7.56 (d,
J = 3.5 Hz, 4H, aryl), 7.51 (m, 4H, aryl), 7.32 (t, J = 3.6 Hz, 4H, aryl),
7.15–7.01 (m, 28H, aryl), 6.90 (d, J = 4.3 Hz, 4H, aryl), 6.75 (d,
J = 4.3 Hz, 4H, aryl), 1.98 (s, 24H, NMe2); protons of H2O were not
observed. IR (KBr, cmꢀ1): m 3444 (br, m), 3054 (w), 2934 (w),
1616 (m), 1588 (s), 1504 (s), 1384 (s), 1301 (s), 1021 (s), 819 (s),
750 (s). Anal. Calc. for C112H94N15Ag3O10: C, 63.05; H, 4.44; N,
9.85. Found: C, 62.98; H, 4.52; N, 10.01%. This compound could also
be prepared in 87% yield (0.46 g) from the reaction of AgNO3
(0.17 g, 1.0 mmol) and 11 (0.40 g, 1.0 mmol) in a mixed solvent
of CH2Cl2 (20 mL) and methanol (5 mL).
2.5.7. [(3)2Ag](PF6) (19)
Yield: 0.76 g (83%). Colorless crystals, m.p.: 176–178 °C (dec.).
1H NMR (DMSO-d6): d 8.29 (d, J = 4.8 Hz, 2H, aryl), 7.65 (t,
J = 7.6 Hz, 2H, aryl), 7.32 (d, J = 7.9 Hz, 2H, aryl), 7.16 (t, J = 7.5 Hz,
4H, aryl), 6.90 (m, 6H, aryl), 6.58 (d, J = 7.5 Hz, 2H, aryl), 6.30 (d,
J = 8.1 Hz, 2H, aryl), 4.72 (br s, 2H, NH), 4.27 (s, 4H, CH2), 2.48 (s,
12H, NMe2), 1.86 (s, 6H, CH3), 1.76 (s, 6H, CH3). IR (KBr, cmꢀ1): v
3303 (m), 3060 (w), 2919 (m), 1598 (s), 1581 (s), 1456 (s), 1439
(s), 1303 (s), 1094 (s), 1024 (s), 840 (s), 756 (s). Anal. Calc. for
C44H50N6AgF6P: C, 57.71; H, 5.50; N, 9.18. Found: C, 58.02; H,
5.43; N, 9.12%.
2.7. General procedure for the preparation of Ag(I) complexes 24–41
2.5.8. [(3)2Ag](OTf) (20)
Yield: 0.72 g (78%). White solid, m.p.: 184–186 °C (dec.). 1H
NMR (DMSO-d6): d 8.51 (d, J = 4.6 Hz, 2H, aryl), 7.80 (t, J = 7.4 Hz,
2H, aryl), 7.42 (d, J = 7.8 Hz, 2H, aryl), 7.30 (t, J = 7.7 Hz, 4H, aryl),
7.05 (m, 6H, aryl), 6.63 (d, J = 7.4 Hz, 2H, aryl), 6.44 (d, J = 8.0 Hz,
2H, aryl), 4.85 (br, 2H, NH), 4.42 (s, 4H, CH2), 2.54 (s, 12H, NMe2),
1.94 (s, 6H, CH3), 1.85 (s, 6H, CH3). IR (KBr, cmꢀ1): v 3371 (m),
2921 (w), 1583 (s), 1471 (s), 1276 (s), 1252 (s), 1156 (s), 1029
Preparation of [Ag2(5)2][NO3]2 (24) is representative [14]. A
CH2Cl2 solution (20 mL) of 5 (0.46 g, 1.0 mmol) was added to a
methanol solution (5 ml) of AgNO3 (0.17 g, 1.0 mmol) with stirring
at room temperature. The solution was stirred for 5 h at room tem-
perature and filtered. The solution was reduced to 5 mL and cooled
to ꢀ20 °C, yielding pale yellow microcrystals, which were isolated
by filtration. Yield: 0.60 g (95%). M.p.: 327–329 °C (dec.). 1H NMR

H. Zhang et al. / Inorganica Chimica Acta 366 (2011) 320–336
323
(CD3OD): d 8.95 (d, J = 9.0 Hz, 4H, N@CH), 8.20 (m, 4H, aryl), 8.04
(d, J = 7.7 Hz, 4H, aryl), 7.58 (d, J = 8.1 Hz, 4H, aryl), 7.50 (d,
J = 8.8 Hz, 4H, aryl), 7.48 (m, 4H, aryl), 7.35 (t, J = 7.1 Hz, 4H, aryl),
7.19 (t, J = 7.5 Hz, 4H, aryl), 7.12 (d, J = 8.8 Hz, 4H, aryl), 6.82 (d,
J = 16.7 Hz, 2H, CH2), 4.51 (d, J = 16.7 Hz, 2H, CH2). IR (KBr, cmꢀ1):
v 3352 (m), 3049 (m), 2968 (m), 1618 (s), 1596 (s), 1509 (s),
1336 (s), 1283 (s), 1151 (s), 1028 (s), 807 (s). Anal. Calc. for
C33H26N4AgF3O3S: C, 54.78; H, 3.62; N, 7.74. Found: C, 54.72; H,
J = 8.6 Hz, 4H, aryl), 6.78 (d, J = 4.2 Hz, 4H, aryl). IR (KBr, cmꢀ1):
m
3.52; N, 7.73%.
3044 (w), 3000 (w), 2963 (w), 1622 (w), 1585 (w), 1384 (s), 1297
(w), 1150 (w), 1043 (w), 898 (w), 821 (w), 750 (w). Anal. Calc. for
2.7.6. [Ag2(7)2][NO3]2 (30)
C64H44N10Ag2O6: C, 60.77; H, 3.51; N, 11.07. Found: C, 60.52; H,
Yield: 0.58 g (91%). Yellow solid, m.p.: 216–218 oC (dec.). 1H
NMR (DMSO-d6): d 8.77 (d, J = 9.2 Hz, 4H, N@CH), 8.25 (m, 4H,
aryl), 8.07 (d, J = 7.7 Hz, 4H, aryl), 7.74 (d, J = 4.5 Hz, 8H, aryl),
6.95 (d, J = 8.2 Hz, 4H, aryl), 5.92 (d, J = 8.3 Hz, 4H, aryl), 2.47–
2.37 (m, 8H, CH2), 1.69–1.58 (m, 8H, CH2), 1.57–1.48 (m, 4H,
CH2), 1.40–1.29 (m, 12H, CH2). IR (KBr, cmꢀ1): v 3051 (w), 2925
(m), 1619 (m), 1586 (s), 1435 (s), 1383 (s), 1214 (s), 1046 (s),
1004 (s), 832 (s), 778 (s). Anal. Calc. for C64H60N10Ag2O6: C,
60.01; H, 4.72; N, 10.93. Found: C, 60.12; H, 4.82; N, 10.73%.
3.82; N, 10.83%.
2.7.1. [Ag2(5)2][PF6]2 (25) [31]
Yield: 0.66 g (92%). Yellow solid, m.p.: 306–608 °C (dec.). 1H
NMR (DMSO-d6):
d 8.99 (d, J = 9.1 Hz, 4H, N@CH), 8.23 (t,
J = 7.7 Hz, 4H, aryl), 8.06 (d, J = 7.7 Hz, 4H, aryl), 7.63 (d,
J = 8.9 Hz, 4H, aryl), 7.56 (d, J = 8.2 Hz, 4H, aryl), 7.50 (t, J = 6.0 Hz,
4H, aryl), 7.30 (t, J = 7.2 Hz, 4H, aryl), 7.12 (t, J = 7.8 Hz, 4H, aryl),
7.00 (d, J = 8.8 Hz, 4H, aryl), 6.69 (d, J = 8.6 Hz, 4H, aryl), 6.63 (d,
J = 4.3 Hz, 4H, aryl). IR (KBr, cmꢀ1): v 3055 (w), 1624 (m), 1587
(s), 1567 (m), 1438 (s), 1304 (s), 1269 (m), 1203 (m), 1006 (m),
842 (s). Anal. Calc. for C64H44N8Ag2F12P2: C, 53.73; H, 3.10; N,
7.83. Found: C, 53.72; H, 3.02; N, 7.63%.
2.7.7. [Ag2(7)2][PF6]2 (31)
Yield: 0.65 g (90%). Yellow crystals, m.p.: 266–268 °C (dec.). 1H
NMR (CDCl3): d 8.53 (d, J = 9.3 Hz, 4H, N@CH), 7.97 (d, J = 7.7 Hz,
4H, aryl), 7.91 (t, J = 7.6 Hz, 4H, aryl), 7.58 (d, J = 4.2 Hz, 4H, aryl),
7.29 (t, J = 5.6 Hz, 4H, aryl), 6.99 (d, J = 8.2 Hz, 4H, aryl), 5.92 (d,
J = 8.3 Hz, 4H, aryl), 2.76–2.56 (m, 4H, CH2), 2.45–2.37 (m, 4H,
CH2), 2.24–2.09 (m, 6H, CH2), 1.68–1.49 (m, 18H, CH2). IR (KBr,
cmꢀ1): v 2930 (m), 1620 (m), 1587 (s), 1460 (s), 1437 (s), 1304
(s), 1158 (m), 1006 (s), 841 (s). Anal. Calc. for C64H60N8Ag2F12P2:
C, 53.13; H, 4.18; N, 7.74. Found: C, 53.22; H, 4.02; N, 7.83.
2.7.2. [Ag2(5)2][OTf]2 (26)
Yeild: 0.65 g (90%). Yellow solid, m.p.: 316–318 °C (dec.). 1H
NMR (CDCl3): d 8.89 (d, J = 9.0 Hz, 4H, N@CH), 8.12 (d, J = 7.7 Hz,
4H, aryl), 8.00 (t, J = 7.7 Hz, 4H, aryl), 7.82 (d, J = 8.9 Hz, 4H, aryl),
7.35 (d, J = 8.1 Hz, 4H, aryl), 7.21 (m, 4H, aryl), 7.17 (m, 4H, aryl),
6.96 (t, J = 8.4 Hz, 4H, aryl), 6.87 (d, J = 8.9 Hz, 4H, aryl), 6.73 (d,
J = 4.24 Hz, 4H, aryl), 6.57 (d, J = 8.5 Hz, 4H, aryl). IR (KBr, cmꢀ1):
v 3053 (w), 1624 (m), 1587 (s), 1438 (s), 1276 (s), 1258 (s), 1155
(s), 1029 (s), 826 (s). Anal. Calc. for C66H44N8Ag2F6O6S2: C, 55.09;
H, 3.08; N, 7.79. Found: C, 55.02; H, 3.06; N, 7.83%. Yellow crystals
26ꢁ2CH3OH suitable for X-ray structural analysis were grown from
a methanol solution at room temperature.
2.7.8. [Ag2(7)2][OTf]2 (32)
Yield: 0.68 g (93%). Yellow solid, m.p.: 206–208 °C (dec.). 1H
NMR (DMSO-d6): d 8.75 (d, J = 9.2 Hz, 4H, N@CH), 8.23 (m, 4H,
aryl), 8.05 (d, J = 7.7 Hz, 4H, aryl), 7.72 (m, 8H, aryl), 6.94 (d,
J = 8.2 Hz, 4H, aryl), 5.91 (d, J = 8.3 Hz, 4H, aryl), 2.45–2.36 (m,
8H, CH2), 1.68–1.58 (m, 8H, CH2), 1.56–1.48 (m, 4H, CH2), 1.38–
1.27 (m, 12H, CH2). IR (KBr, cmꢀ1): v 2926 (m), 1619 (m), 1587
(s), 1437 (s), 1259 (s), 1153 (s), 1030 (s), 779 (s). Anal. Calc. for
2.7.3. [Ag(6)](NO3) (27) [14]
Yield: 0.57 g (90%). Colorless microcrystals, m.p.: 218–220 °C
(dec.). 1H NMR (CD3OD/CDCl3; 1:4): d 8.60 (d, J = 4.1 Hz, 2H, aryl),
8.01 (t, J = 7.6 Hz, 2H, aryl), 7.83 (t, J = 9.3 Hz, 4H, aryl), 7.63 (d,
J = 7.7 Hz, 2H, aryl), 7.48 (t, J = 6.2 Hz, 2H, aryl), 7.30 (t, J = 7.4 Hz,
2H, aryl), 7.23 (t, J = 7.0 Hz, 2H, aryl), 6.97 (d, J = 8.4 Hz, 2H, aryl),
6.89 (d, J = 8.9 Hz, 2H, aryl), 4.50 (d, J = 16.6 Hz, 2H, CH2), 4.46 (d,
J = 16.6 Hz, 2H, CH2); protons of NH were not observed. IR (KBr,
cmꢀ1): v 3385 (w), 3052 (w), 2896 (w), 1615 (s), 1596 (s), 1508
(s), 1491 (s), 1436 (s), 1383 (s), 1362 (s), 1338 (s), 1286 (s), 825
(s), 809 (s). Anal. Calc. for C32H26N5AgO3: C, 60.39; H, 4.12; N,
11.00. Found: C, 60.04; H, 4.33; N, 10.91%.
C66H60N8Ag2F6O6S2: C, 54.48; H, 4.16; N, 7.70. Found: C, 54.35; H,
4.06; N, 7.63%.
2.7.9. [Ag2(8)2][NO3]2 (33) [14]
Yield: 0.47 g (83%). Yellow solid, m.p.: 308–310 °C (dec.). 1H
NMR (CD3OD): d 8.78 (d, J = 9.0 Hz, 4H, N@CH), 8.20 (m, 4H, aryl),
8.05 (d, J = 7.7 Hz, 4H, aryl), 7.83 (d, J = 4.2 Hz, 4H, aryl), 7.65 (m,
4H, aryl), 6.97 (m, 8H, aryl), 6.36 (t, J = 7.8 Hz, 4H, aryl), 1.65 (s,
12H, CH3). IR (KBr, cmꢀ1): v 3051 (w), 2918 (w), 2844 (w), 1624
(w), 1587 (m), 1453 (w), 1384 (s), 1355 (s), 1304 (m), 1209 (w),
1150 (w), 1002 (w), 795 (m), 740 (m). Anal. Calc. for C52H44N10
Ag2O6: C, 55.73; H, 3.96; N, 12.50. Found: C, 55.57; H, 4.05; N,
12.38%.
2.7.4. [Ag(6)](PF6) (28)
Yield: 0.65 g (90%). White solid, m.p.: 213–215 °C (dec.). 1H
NMR (DMSO-d6): d 8.72 (d, J = 4.8 Hz, 2H, aryl), 8.06 (t, J = 7.6 Hz,
2H, aryl), 7.93 (d, J = 9.0 Hz, 2H, aryl), 7.88 (d, J = 7.7 Hz, 2H, aryl),
7.80 (d, J = 7.8 Hz, 2H, aryl), 7.52 (t, J = 6.0 Hz, 2H, aryl), 7.24 (m,
4H, aryl), 7.05 (d, J = 9.0 Hz, 2H, aryl), 6.79 (d, J = 8.0 Hz, 2H, aryl),
5.81 (br s, 2H, NH), 4.59 (d, J = 16.7 Hz, 2H, CH2), 4.52 (d,
J = 16.7 Hz, 2H, CH2). IR (KBr, cmꢀ1): v 3376 (m), 1616 (s), 1595
(s), 1509 (s), 1437 (s), 1284 (s), 840 (s). Anal. Calc. for
2.7.10. [Ag2(8)2][PF6]2 (34)
Yield: 0.55 g (85%). Yellow solid, m.p.: 278–280 °C (dec.). 1H
NMR (DMSO-d6):
d 8.84 (d, J = 9.1 Hz, 4H, N@CH), 8.24 (t,
J = 8.5 Hz, 4H, aryl), 8.08 (d, J = 7.7 Hz, 4H, aryl), 7.73 (d,
J = 4.1 Hz, 4H, aryl), 7.66 (t, J = 6.4 Hz, 4H, aryl), 7.05 (d, J = 7.9 Hz,
4H, aryl), 6.89 (d, J = 7.6 Hz, 4H, aryl), 6.19 (t, J = 7.8 Hz, 4H, aryl),
1.54 (s, 12H, CH3). IR (KBr, cmꢀ1): v 3051 (w), 2920 (w), 1623
(m), 1588 (s), 1451 (s), 1306 (s), 1213 (s), 1157 (s), 839 (s). Anal.
Calc. for C52H44N8Ag2F12P2: C, 48.54; H, 3.45; N, 8.71. Found: C,
48.79; H, 3.50; N, 8.69%.
C32H26N4AgF6P: C, 53.42; H, 3.64; N, 7.79. Found: C, 53.12; H,
3.63; N, 7.81%.
2.7.5. [Ag(6)](OTf) (29)
Yield: 0.68 g (94%). Colorless crystals, m.p.: 219–221 °C (dec.).
1H NMR (DMSO-d6): d 8.78 (d, J = 4.9 Hz, 2H, aryl), 8.15 (t,
J = 7.7 Hz, 2H, aryl), 7.93 (d, J = 9.0 Hz, 2H, aryl), 7.89 (m, 4H, aryl),
7.58 (t, J = 6.3 Hz, 2H, aryl), 7.25 (m, 4H, aryl), 7.01 (d, J = 9.0 Hz,
2H, aryl), 6.77 (d, J = 8.2 Hz, 2H, aryl), 5.91 (br s, 2H, NH), 4.59 (d,
2.7.11. [Ag2(8)2][OTf]2 (35)
Yield: 0.52 g (80%). Yellow crystals, m.p.: 280–282 °C (dec.). 1H
NMR (CDCl3): d 8.73 (d, J = 9.1 Hz, 4H, N@CH), 8.12 (d, J = 7.7 Hz,
4H, aryl), 8.00 (t, J = 7.7 Hz, 4H, aryl), 7.72 (d, J = 4.1 Hz, 4H, aryl),
7.42 (t, J = 6.1 Hz, 4H, aryl), 7.30 (d, J = 8.0 Hz, 4H, aryl), 6.69 (d,

324
H. Zhang et al. / Inorganica Chimica Acta 366 (2011) 320–336
J = 7.5 Hz, 4H, aryl), 6.12 (t, J = 7.8 Hz, 4H, aryl), 1.43 (s, 12H, CH3).
IR (KBr, cmꢀ1): v 3060 (w), 2917 (w), 1620 (m), 1588 (s), 1453 (s),
1259 (s), 1154 (s), 1030 (s), 796 (s). Anal. Calc. for C54H44N8Ag2-
F6O6S2: C, 50.09; H, 3.43; N, 8.65. Found: C, 49.82; H, 3.50; N,
8.68%. Yellow crystals 35ꢁ2CH3OH suitable for X-ray structural
2.7.17. [Ag2(10)2][OTf]2 (41)
Yield: 0.51 g (82%).White solid, m.p.: 228–230 °C (dec.). 1H NMR
(DMSO-d6): d 7.96 (d, J = 4.0 Hz, 4H, aryl), 7.56 (s, 4H, NH), 7.51 (t,
J = 7.7 Hz, 4H, aryl), 7.31 (d, J = 7.8 Hz, 4H, aryl), 7.22 (t, J = 7.6 Hz,
4H, aryl), 7.03 (d, J = 7.4 Hz, 4H, aryl), 6.70 (m, 8H, aryl), 1.84 (s,
12H, CH3). IR (KBr, cmꢀ1): v 3400 (m), 2921 (w), 1611 (s), 1569
(s), 1506 (s), 1483 (s), 1447 (s), 1279 (s), 1251 (s), 1157 (s), 1028
(s), 768 (s). Anal. Calc. for C50H44N8Ag2F6O6S2: C, 48.17; H, 3.56;
N, 8.99. Found: C, 47.92; H, 3.50; N, 8.88%.
analysis were grown from
temperature.
a methanol solution at room
2.7.12. [Ag(9)](NO3) (36)
Yield: 0.46 g (82%). White solid, m.p.: 148–150 °C (dec.). 1H
NMR (CDCl3): d 8.61 (d, J = 4.9 Hz, 2H, aryl), 7.82 (t, J = 7.4 Hz, 2H,
aryl), 7.44 (d, J = 7.9 Hz, 2H, aryl), 7.31 (t, J = 6.2 Hz, 2H, aryl),
7.01 (t, J = 7.8 Hz, 2H, aryl), 6.74 (d, J = 7.6 Hz, 2H, aryl), 6.20 (d,
J = 8.1 Hz, 2H, aryl), 4.52 (d, J = 16.4 Hz, 2H, CH2), 4.32 (d,
J = 16.4 Hz, 2H, CH2), 2.97 (br s, 2H, NH), 1.87 (s, 6H, CH3). IR
(KBr, cmꢀ1): v 3346 (m), 3062 (w), 2898 (m), 1601 (s), 1581 (s),
1468 (s), 1383 (s), 1333 (s), 1280 (s), 1100 (s), 774 (s). Anal. Calc.
for C26H26N5AgO3: C, 55.33; H, 4.64; N, 12.41. Found: C, 55.23; H,
4.54; N, 12.61%.
2.8. General procedure for the preparation of Cu(II) complexes 42–45
Preparation of (1)CuCl2ꢁH2O (42ꢁH2O) is representative.
A
CH2Cl2 solution (10 mL) of 1 (0.40 g, 1.0 mmol) was added to a
methanol solution (5 mL) of CuCl2ꢁ2H2O (0.17 g, 1.0 mmol) with
stirring at room temperature. The solution was stirred for 2 h at
room temperature and filtered. Then the solution was reduced to
5 ml and cooled to ꢀ20 °C, yielding green crystals 42ꢁH2O, which
were isolated by filtration. Yield: 0.49 g (89%). M.p.: 180–182 °C
(dec.). IR (KBr, cmꢀ1): v 3420 (s), 3049 (m), 1617 (s), 1595 (s),
1505 (s), 1476 (s), 1445 (s), 1348 (s), 1299 (s), 1205 (s), 1099 (s),
1057 (s), 935 (s), 815 (s), 752 (s). Anal. Calc. for C28H25N3Cl2CuO:
C, 60.71; H, 4.55; N, 7.59. Found: C, 60.59; H, 4.62; N, 7.63%.
2.7.13. [Ag(9)](PF6) (37)
Yield: 0.58 g (81%). Colorless crystals, m.p.: 196–198 °C (dec.).
1H NMR (CDCl3): d 8.57 (d, J = 4.8 Hz, 2H, aryl), 7.84 (t, J = 7.7 Hz,
2H, aryl), 7.46 (d, J = 7.8 Hz, 2H, aryl), 7.33 (t, J = 6.3 Hz, 2H, aryl),
7.01 (t, J = 7.8 Hz, 2H, aryl), 6.79 (d, J = 7.6 Hz, 2H, aryl), 6.16 (d,
J = 8.1 Hz, 2H, aryl), 4.77 (s, 2H, NH), 4.51 (d, J = 16.4 Hz, 2H,
CH2), 4.28 (d, J = 16.4 Hz, 2H, CH2), 1.88 (s, 6H, CH3). IR (KBr,
cmꢀ1): v 3385 (m), 2916 (w), 1582 (s), 1469 (s), 1321 (s), 1293
(s), 1133 (s), 838 (s). Anal. Calc. for C26H26N4AgPF6: C, 48.24; H,
4.05; N, 8.65. Found: C, 48.21; H, 4.14; N, 8.61%.
2.8.1. [(9)CuCl]Cl (43)
Yield: 0.42 g (80%). Green crystals, m.p.: 215–217 °C (dec.). IR
(KBr, cmꢀ1): v 3079 (m), 2898 (s), 1609 (s), 1577 (s), 1489 (s),
1467 (s), 1426 (s), 1291 (s), 1051 (s), 801 (s). Anal. Calc. for
C26H26N4Cl2Cu: C, 59.04; H, 4.95; N, 10.59. Found: C, 59.23; H,
4.82; N, 10.63%.
2.8.2. [(9)Cu(OHMe)](ClO4)2 (44)
Yield: 0.56 g (82%). Green crystals, m.p.: 278–280 °C (dec.). IR
(KBr, cmꢀ1): v 3246 (m), 3068 (w), 2960 (w), 1612 (s), 1577 (s),
1489 (s), 1460 (s), 1291 (s), 1090 (s), 905 (s), 758 (s). Anal. Calc.
for C27H30N4Cl2CuO9: C, 47.07; H, 4.39; N, 8.13. Found: C, 47.14;
H, 4.42; N, 8.21%.
2.7.14. [Ag(9)](OTf) (38)
Yield: 0.55 g (84%). White solid, m.p.: 278–280 °C (dec.). 1H
NMR (DMSO-d6): d 8.64 (d, J = 4.6 Hz, 2H, aryl), 8.04 (t, J = 7.7 Hz,
2H, aryl), 7.77 (d, J = 7.8 Hz, 2H, aryl), 7.48 (t, J = 6.2 Hz, 2H, aryl),
7.03 (t, J = 7.8 Hz, 2H, aryl), 6.77 (d, J = 7.5 Hz, 2H, aryl), 6.24 (d,
J = 8.1 Hz, 2H, aryl), 5.43 (s, 2H, NH), 4.48 (d, J = 16.4 Hz, 2H,
CH2), 4.33 (d, J = 16.4 Hz, 2H, CH2), 1.81 (s, 6H, CH3). IR (KBr,
cmꢀ1): v 3378 (m), 3063 (w), 2917 (w), 1602 (s), 1582 (s), 1468
(s), 1274 (s), 1252 (s), 1159 (s), 1029 (s), 776 (s). Anal. Calc. for
2.8.3. [2-(2-NHC5H5N)-20-(2-NHC5H4N)-6,60-Me2-(C6H3)2]CuCl3 (45)
Yield: 0.40 g (75%). Green crystals, m.p.: 200–202 °C (dec.). IR
(KBr, cmꢀ1): v 3240 (m), 3045 (w), 1611 (s), 1568 (s), 1518 (s),
1445 (s), 1325 (s), 1159 (s), 1017 (s), 773 (s). Anal. Calc. for
C27H26N4AgF3O3S: C, 49.78; H, 4.02; N, 8.60. Found: C, 49.49; H,
C24H23N4Cl3Cu: C, 53.64; H, 4.31; N, 10.43. Found: C, 53.43; H,
3.93; N, 8.33%.
4.32; N, 10.23%.
2.7.15. [Ag2(10)2][NO3]2 (39)
2.9. General procedure for asymmetric allylation of benzaldehyde
Yield: 0.43 g (81%). White solid, m.p.: 143–145 °C (dec.). 1H
NMR (DMSO-d6): d 7.96 (m, 4H, aryl), 7.56 (s, 4H, NH), 7.51 (t,
J = 7.4 Hz, 4H, aryl), 7.31 (d, J = 7.8 Hz, 4H, aryl), 7.22 (t, J = 7.6 Hz,
4H, aryl), 7.03 (d, J = 7.2 Hz, 4H, aryl), 6.72 (m, 8H, aryl), 1.84 (s,
12H, CH3). IR (KBr, cmꢀ1): v 3404 (m), 3061 (w), 2918 (w), 1609
(s), 1568 (s), 1508 (s), 1445 (s), 1384 (s), 1323 (s), 1295 (s), 1155
(s), 1033 (s), 768 (s). Anal. Calc. for C48H44N10Ag2O6: C, 53.75; H,
4.13; N, 13.06. Found: C, 53.57; H, 4.05; N, 13.08%.
Allylation of benzaldehyde catalyzed by complex [(1)2Ag](OTf)
(13) is representative. Under nitrogen atmosphere and in the dark.
Complex 13 (106 mg, 0.1 mmol) was dissolved in a mixed solvent
of THF (1 mL) and CH2Cl2 (1 mL). Benzaldehyde (51
lL, 0.5 mmol)
and allyltributyltin (186 L, 0.6 mmol) were added successively
l
to the solution at 20 °C, the mixture was stirred for 60 h at this
temperature, then treated with saturated KF solution, and ex-
tracted with diethyl ether (5 mL ꢂ 3). The combined organic layers
were dried over Na2SO4 and the solvent was removed in vacuum.
The residue was purified by column chromatography (hexane/
ethyl acetate = 10/1) to give 4-phenyl-4-hydroxy-1-butene
(60 mg, 82% yield) as a colorless oil. 1H NMR (CDCl3): d 7.40 (m,
4H, phenyl H), 7.33 (m, 1H, phenyl H), 5.85 (m, 1H, vinyl H), 5.18
(m, 2H, vinyl H), 4.74 (t, J = 6.0 Hz, 1H, CH), 2.55 (m, 2H, CH2),
2.46 (s, 1H, OH). These spectroscopic data are in agreement with
those reported in the literature [32]. Enantiomeric excess was
determined by HPLC with a Chiralcel OD-H column: hexane/iso-
propanol = 95/5, 0.7 mL/min, 254 nm, major enantiomer
2.7.16. [Ag2(10)2][PF6]2 (40)
Yield: 0.52 g (84%). White solid, m.p.: 296–298 °C (dec.). 1H
NMR (CDCl3): d 7.42 (t, J = 7.3 Hz, 6H, aryl), 7.28 (t, J = 7.7 Hz, 6H,
aryl), 7.18 (d, J = 7.8 Hz, 4H, aryl), 7.11 (d, J = 7.3 Hz, 6H, aryl),
6.65 (d, J = 8.5 Hz, 6H, aryl), 6.33 (s, 4H, NH), 1.97 (s, 12H, CH3).
IR (KBr, cmꢀ1): v 3363 (m), 3066 (w), 2923 (w), 1613 (s), 1568
(s), 1502 (s), 1446 (s), 1298 (s), 1159 (s), 844 (s). Anal. Calc. for
C48H44N8Ag2F12P2: C, 46.55; H, 3.58; N, 9.05. Found: C, 46.79; H,
3.50; N, 8.89%. Colorless crystals 40ꢁ2CH3OHꢁ2H2O suitable for
X-ray structural analysis were grown from a methanol solution
at room temperature.
tR = 10.64 min, minor enantiomer tR = 11.91 min. [a]
25 = +25.1
D

H. Zhang et al. / Inorganica Chimica Acta 366 (2011) 320–336
325
(c = 2.0, benzene) for 48% ee. The absolute stereochemistry was as-
signed as (R) by comparison of the optical rotation with the litera-
as a colorless oil. 1H NMR (CDCl3): d 7.30 (m, 5H, phenyl H), 5.34
(m, 1H, CH), 4.50 (m, 1H, CH2NO2), 4.40 (m, 1H, CH2NO2), 3.05 (s,
1H, OH). These spectroscopic data are in agreement with those re-
ported in the literature [33]. Enantiomeric excess was determined
by HPLC with a Chiralcel OD-H column: hexane/isopropanol = 85/
15, 0.8 mL/min, 215 nm, minor enantiomer tR = 12.69 min, major
ture [32], [
a]
25 = ꢀ50.5 (c = 1.1, benzene) for 96% ee, (S)-isomer.
D
2.10. General procedure for asymmetric Henry reactions
enantiomer tR = 14.97 min. [a]
21 = +13.6 (c = 2.0, CH2Cl2) for 32%
D
Henry reaction catalyzed by complex [(9)Cu(OHMe)](ClO4)2
(44) is representative. Under nitrogen atmosphere, 44 (69 mg,
ee. The absolute stereochemistry was assigned as (S) by compari-
son of the optical rotation with the literature [33], [
(c = 1.03, CH2Cl2) for 94% ee, (R)-isomer.
a
]
D
21 = ꢀ41.6
0.1 mmol) was dissolved in ethanol (2 mL). Benzaldehyde (51
0.5 mmol), nitromethane (540 L, 10.0 mmol), and triethylamine
(14 L, 0.1 mmol) were added successively to the solution at
lL,
l
l
ꢀ20 °C. After this solution was stirred for 72 h at ꢀ20 °C, the vola-
tile components were removed under reduced pressure, and the
residue was purified by column chromatography (hexane/ethyl
acetate = 10/1) to give 1-phenyl-2-nitroethanol (67 mg, 80% yield)
2.11. X-ray crystallography
Single-crystal X-ray diffraction measurements were carried out
on a Bruker SMART CCD diffractometer at 113(2) K using graphite
Table 1
Crystal data and experimental parameters for compounds 1, 11–14 and 16.
Compound
1
11ꢁCH3OH
12
13ꢁCH3OH
14
16
Formula
C
28H23N3
C57H50N7AgO4
1004.91
orthorhombic
P212121
26.375(1)
12.752(1)
15.099(1)
90
90
90
5078.6(3)
4
1.314
C56H46N6AgF6P
1055.83
orthorhombic
P212121
13.035(3)
13.337(3)
28.469(6)
90
C58H50N6AgF3O4S
1091.97
monoclinic
P21
13.268(1)
13.180(1)
14.992(1)
90
90.99(1)
90
2621.2(1)
2
C112H94N15Ag3O10
2133.63
triclinic
P1
12.832(6)
13.557(7)
15.211(8)
110.14(1)
91.73(1)
102.13(1)
2414(2)
1
C44H46N6AgF6P
911.71
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
401.49
tetragonal
P41
11.628(1)
11.628(1)
16.181(2)
90
90
90
2187.7(3)
4
1.219
orthorhombic
P212121
9.275(1)
20.142(2)
22.197(2)
90
90
90
4146.8(6)
4
1.460
a
(°)
b (°)
90
90
c
(°)
V (Å3)
4949.2(17)
4
1.417
Z
Dcalc (g/cm3)
1.384
1.468
Size (mm)
F(0 0 0)
0.20 ꢂ 0.10 ꢂ 0.08
0.26 ꢂ 0.20 ꢂ 0.18
0.24 ꢂ 0.20 ꢂ 0.18
0.30 ꢂ 0.18 ꢂ 0.10
0.12 ꢂ 0.08 ꢂ 0.06
0.22 ꢂ 0.14 ꢂ 0.12
848
2080
2160
1124
1092
1872
2h Range (°)
3.50–55.88
27780
5241 (0.0510)
4418
2.70–55.68
36990
11733 (0.0344)
11333
2.86–55.76
37586
11811 (0.0294)
11425
6.18–55.42
16262
11322 (0.0225)
9081
3.26–52.00
26767
17331 (0.0935)
12204
2.74–55.76
37812
9874 (0.0313)
8912
Number of reflections collected
Number of unique reflections [R(int)
Number of observed reflections
]
Absorbed corrections (Tmax, Tmin
R
)
0.99, 0.98
0.045
0.92, 0.89
0.054
0.91, 0.89
0.033
0.95, 0.87
0.043
0.96, 0.92
0.073
0.93, 0.88
0.033
Rw
0.091
0.159
0.075
0.109
0.154
0.072
wR2 (all data)
Goodness-of-fit (GOF)
0.097
0.98
0.161
1.14
0.076
1.07
0.119
1.01
0.167
1.14
0.084
1.12
Table 2
Crystal data and experimental parameters for compounds 19, 22, 26, 29, 31 and 35.
Compound
19
22ꢁCH3OH
26ꢁ2CH3OH
29
31
35ꢁ2CH3OH
Formula
C
44H48N6AgF6P
C43H48N6AgF6OP
917.71
C68H52N8Ag2F6O8S2 C33H26N4AgF3O3S
C32H30N4AgF6P
723.44
orthorhombic
P212121
17.462(1)
13.009(1)
16.573(1)
90
C56H52N8Ag2F6O8S2
1358.92
orthorhombic
P212121
16.449(1)
17.295(1)
20.499(1)
90
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
913.72
orthorhombic
P212121
9.459(1)
20.779(3)
21.622(3)
90
1503.04
trigonal
P31
723.51
orthorhombic
P212121
10.022(1)
10.287(1)
29.417(1)
90
orthorhombic
P212121
13.259(2)
13.521(2)
23.600(4)
90
14.535(1)
14.535(1)
27.423(2)
90
a
(°)
b (°)
90
90
90
90
90
90
c
(°)
90
90
120
5017.3(3)
3
90
3032.9(2)
4
90
3764.8(1)
4
90
5831.4(2)
4
V (Å3)
4249.5(10)
4
1.428
4230.9(11)
4
1.441
Z
Dcalc (g/cm3)
1.492
1.585
1.276
1.548
Size (mm)
F(0 0 0)
0.24 ꢂ 0.20 ꢂ 0.18 0.26 ꢂ 0.24 ꢂ 0.22 0.50 ꢂ 0.40 ꢂ 0.30
0.45 ꢂ 0.40 ꢂ 0.25 0.22 ꢂ 0.20 ꢂ 0.20 0.40 ꢂ 0.30 ꢂ 0.30
1880
1888
2280
1464
1464
2752
2h Range (°)
2.72–55.76
40732
10139 (0.0441)
9240
3.46–55.74
37669
9881 (0.0398)
9171
2.40–55.30
20925
14040 (0.0148)
12538
4.20–52.40
10755
5985 (0.0181)
4833
3.98–55.22
15986
8369 (0.0248)
5484
3.96–52.32
15695
10984 (0.0154)
9059
Number of reflections collected
Number of unique reflections [R(int)
Number of observed reflections
]
Absorbed corrections (Tmax, Tmin
R
)
0.90, 0.87
0.037
0.88, 0.86
0.036
0.81, 0.71
0.042
0.83, 0.72
0.033
0.88, 0.87
0.057
0.79, 0.73
0.043
Rw
0.083
0.076
0.116
0.075
0.164
0.108
wR2 (all data)
Goodness-of-fit (GOF)
0.084
1.08
0.077
1.03
0.122
1.04
0.080
1.03
0.177
1.00
0.116
1.02

326
H. Zhang et al. / Inorganica Chimica Acta 366 (2011) 320–336
monochromated Mo K
a radiation (k = 0.71073 Å). An empirical
3. Results and discussion
absorption correction was applied using the SADABS program [34].
All structures were solved by direct methods and refined by full-
matrix least squares on F2 using the SHELXL-97 program package
[35]. Most of the hydrogen atoms (excluding those of the solvated
H2O and CH3OH) were geometrically fixed using the riding model.
The crystal data and experimental data for 1, 11–14, 16, 19, 22, 26,
29, 31, 35, 37, 40 and 42–45 are summarized in Tables 1–3. Se-
lected bond lengths and bond angles are listed in Tables 4 and 5.
3.1. Synthesis and characterization of ligands 1, 2 and 7
Condensation of (R)-2-amino-20-(dimethylamino)-1,10-binaph-
thyl, (R)-2-amino-20-(dimethylamino)-6,60-dimethyl-1,10-biphenyl
or
(R)-5,50,6,60,7,708,80-octahydro-2,20-diamino-1,10-binaphthyl
with 1 or 2 equiv of 2-pyridine carboxaldehyde in toluene in
the presence of molecular sieves at 70 °C gives the Schiff base
Table 3
Crystal data and experimental parameters for compounds 37, 40 and 42–45.
Compound
37
40ꢁ2CH3OHꢁ2H2O
42ꢁH2O
43
44
45
Formula
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
C
26H26N4AgF6P
C50H56N8Ag2F12O4P2 C28H25N3Cl2CuO
C26H26N4Cl2Cu
528.95
monoclinic
P1211
10.511(1)
12.050(1)
10.539(1)
117.90(1)
1179.8(1)
2
C27H30N4Cl2CuO9
688.99
monoclinic
P1211
8.745(2)
13.139(3)
12.849(3)
107.11(1)
1411.1(6)
2
C24H23N4Cl3Cu
537.35
647.35
orthorhombic
P212121
9.535(1)
13.654(1)
19.920(2)
90
2593.5(4)
4
1.658
1338.71
monoclinic
P21
553.95
tetragonal
I4
orthorhombic
P212121
9.511(1)
15.733(1)
16.112(1)
90
2410.86(8)
4
1.480
12.722(2)
14.943(2)
16.682(2)
112.21(1)
2935.8(6)
2
20.758(2)
20.758(2)
12.990(1)
90
5597.3(7)
8
b (°)
V (Å3)
Z
Dcalc. (g/cm3)
1.514
1.315
1.489
1.622
Size (mm)
F(0 0 0)
0.26 ꢂ 0.24 ꢂ 0.20 0.27 ꢂ 0.21 ꢂ 0.18
0.20 ꢂ 0.12 ꢂ 0.10 0.20 ꢂ 0.04 ꢂ 0.02 0.22 ꢂ 0.14 ꢂ 0.04 0.25 ꢂ 0.15 ꢂ 0.15
1304
1352
2280
546
710
1100
2h Range (°)
3.62–55.76
26335
6169 (0.0382)
5862
6.92–50.70
11249
8538 (0.0169)
7413
3.70–55.66
34832
6633 (0.0516)
6154
4.38–55.78
14912
5571 (0.0375)
4298
4.54–55.78
17791
6624 (0.0354)
5559
3.62–55.12
9832
5517
Number of reflections collected
Number of unique reflections [R(int)
Number of observed reflections
]
3706
Absorbed corrections (Tmax, Tmin
R
)
0.84, 0.80
0.032
0.87, 0.81
0.045
0.91, 0.83
0.047
0.98, 0.80
0.025
0.96, 0.81
0.042
0.83, 0.74
0.048
Rw
0.073
0.125
0.116
0.054
0.089
0.105
wR2 (all data)
Goodness-of-fit (GOF)
0.075
1.04
0.133
1.01
0.118
1.09
0.056
0.96
0.094
1.01
0.119
1.01
Table 4
Selected bond distances (Å) and bond angles (°) for compounds 1, 11–14, 16, 19, 22, 26, 29, 31, 35, 37 and 40.
Compound
Ag–N (av.)
C@N
AgꢁꢁꢁAg
Torsions
Aryl–imine
Pyridyl–imine
Aryl–aryl
1
11
1.256(2)
1.281(6)
1.276(6)
1.266(3)
1.270(3)
1.271(5)
1.265(4)
1.273(10)
1.309(10)
1.276(3)
1.278(3)
40.9(2)
49.8(3)
50.4(3)
48.7(2)
48.5(2)
48.9(2)
47.8(2)
51.9(7)
37.7(7)
60.8(4)
47.7(4)
12.0(2)
0.2(3)
2.1(3)
1.3(2)
8.2(2)
0.6(3)
1.0(3)
3.0(4)
4.0(4)
0.4(2)
6.7(2)
71.5(2)
74.3(5)
79.0(3)
73.7(2)
74.2(2)
77.0(2)
75.7(2)
72.9(7)
73.8(7)
76.5(3)
72.5(3)
72.6(2)
67.5(2)
68.3(4)
72.1(4)
73.0(2)
80.4(2)
2.361(4)
2.354(2)
2.376(3)
2.364(7)
2.362(2)
2.380(2)
2.181(2)
2.358(4)
12
13
14
16
19
22
26
1.278(6)
1.256(5)
1.272(5)
1.268(5)
3.671(6)
42.2(2)
42.6(2)
42.4(2)
39.4(2)
3.2(5)
3.6(5)
0.2(2)
0.2(2)
29
31
2.421(3)
2.381(5)
80.4(3)
79.0(3)
79.0(3)
1.260(6)
1.260(6)
1.274(7)
1.274(7)
1.256(6)
1.266(6)
1.286(6)
1.291(6)
3.448(8)
3.597(6)
37.1(3)
37.1(3)
42.5(3)
42.5(3)
34.6(2)
39.2(2)
39.8(2)
32.5(2)
7.9(4)
2.7(4)
2.7(4)
7.9(4)
0.7(2)
9.3(2)
5.6(2)
4.0(2)
35
2.355(5)
78.8(2)
81.3(2)
37
40
2.460(2)
2.139(6)
85.6(2)
74.6(8)
76.9(7)
3.238(1)

H. Zhang et al. / Inorganica Chimica Acta 366 (2011) 320–336
327
ligands, (R)-2-(pyridin-2-ylmethyleneamino)-20-(dimethylamino)-
1,10-binaphthyl (1), (R)-2-(pyridin-2-ylmethyleneamino)-20-(di-
methylamino)-6,60-dimethyl-1,10-biphenyl (2) and (R)-5,506,60
7,708,80-octahydro-2,20-bis(2-(pyridin-2-ylmethyleneamino)-1,10-bi-
naphthyl (7), respectively, in good yields, (Schemes 1, 2 and 7).
Compounds 1, 2 and 7 are air-stable and very soluble in CH2Cl2,
CHCl3, toluene and benzene, but only slightly soluble in n-hexane.
Ligands 1, 2 and 7 have been fully characterized by various spec-
troscopic techniques and elemental analyses. The 1H NMR spectra
of 1 and 2 indicates that they are unsymmetrical on the NMR time-
scale, while that of 7 shows that it is symmetrical. The IR spectra of
1, 2 and 7 show a typical characteristic N@C absorption at about
1630 cmꢀ1. The solid-state structure of 1 has been further con-
firmed by single-crystal X-ray diffraction analysis.
The molecular structure of 1 shows that it crystallizes in a C1
symmetric distorted-tetrahedral geometry (Fig. 1). As expected,
the distance (1.256(2) Å) of C@N is in agreement with a C@N dou-
ble bond. The naphthalene unit is twisted with the imine group
(torsion angle is 40.9(2)°), and a more dramatic twisting is ob-
served between the naphthalene rings which are almost perpen-
dicular to each other (torsion angles is 71.5(2)°), which is smaller
than that (75.6(3)°) found in (S)-2-(pyrrol-2-ylmethyleneamino)-
20-(dimethylamino)-1,10-binaphthyl [17].
Table 5
Selected bond distances (Å) and bond angles (°) for compounds 42–45.
Compound
42
43
44
45
M–N (av.)
Cu–Cl
2.041(2)
2.227(1)
2.239(1)
2.070(2)
2.259(1)
2.017(3)
2.017(3)
2.266(1)
2.211(1)
2.220(1)
Cu–O
Torsion (aryl–aryl)
2.288(3)
73.9(2)
68.3(3)
71.9(2)
75.7(5)
3.2. Synthesis and characterization of Ag(I) complexes with C1-
symmetric ligands
Treatment of AgX (X = NO3, PF6, OTf) with 2 equiv of chiral N3-
ligands 1, 2, 3 and 4 in mixed solvents of MeOH and CH2Cl2 (1:4)
gives the chiral bis-ligated, ionic Ag(I) complexes [Ag(1)2]X
(X = NO3 (11), PF6 (12), OTf (13)), [Ag(2)2]X (X = NO3 (15), PF6
N
Me2N
N
[Ag(NO3)3(OH2)]
2
Ag
N
NMe2
N
AgNO3
CH2Cl2/MeOH
N
Me2N
14
N
Ag
X
O
N
N
N
NMe2
N
H
NH2
N
NMe2
C7H8/m.s.
NMe2
X = NO3 (15), PF6 (16), OTf (17)
0.5 AgX
1
CH2Cl2/MeOH
CH2Cl2/MeOH
0.5 AgX
O
N
N
H
N
Me2N
NH2
NMe2
N
NMe2
N
X
C7H8/m.s.
Ag
N
NMe2
N
C7H8/MeOH
N
2
NaBH4
H
N
X = NO3 (11), PF6 (12), OTf (13)
NMe2
CH2Cl2
AgNO3
CH2Cl2/MeOH
MeOH
0.5 AgX
3
Me2N
N
N
Me2N
N
H
N
X
Ag
[Ag(NO3)3(OH2)]
2
Ag
N
H
N
NMe2
N
NMe2
N
X = NO3 (18), PF6 (19), OTf (20)
14
Scheme 1. Synthesis of complexes 11–14.
Scheme 2. Synthesis of complexes 15–20.

328
H. Zhang et al. / Inorganica Chimica Acta 366 (2011) 320–336
The single-crystal structures of complexes 11–14 show that
they consist of well-separated, alternating layers of the complex
cation [Ag(1)2]+ and free anion NO3 with one solꢀvated methanol
ꢀ
ꢀ
molecule for 11, anion PF6 for 12, anion CF3SO3 with one sol-
vated methanol molecule for 13, and anion [Ag(NO3)3(OH2)]2ꢀ for
14, respectively, in the lattice. In the each complex ion [Ag(1)2]+,
the substituted Me2N groups are far away from the metal center,
and the Ag+ ion is
r-coordinated to four nitrogen atoms from
two ligands 1 in a distorted-tetrahedral geometry (Fig. 2a). The
average distance of Ag–N is ranged from 2.354(2) to 2.376(3) Å,
which are slightly longer than that found in [Ag{N,N0-bis(2-
pyridylmethylene)-2,20-(ethylenedioxy)bis(ethylamine)}][BF4]
(2.331(6) Å) [36]. The twisting as expressed by the torsion angles
between the naphthalene rings are ranged from 71.5(2) to 79.0°,
which are comparable to that found in 1 (75.6(3)°).
In the anion [Ag(NO3)3(OH2)]2ꢀ of 14, the three oxygen atoms of
ꢀ
NO3 and one oxygen atom of H2O are
r
-coordinated to the Ag+
cation in
a C3v geometry (Fig. 2b). The average distance
(2.463(8) Å) of Ag–O(NO3ꢀ) is shorter than that (2.629(9) Å) of
Fig. 1. Molecular structure of 1 (thermal ellipsoids drawn at the 35% probability
level).
-
Ag–O(OH2), and comparable to that (Ag–O(NO3 )) found in
{[Ag3(1,3,5-tri(pyraol-1-yl) benzene)2(NO3)2]NO3}n (2.515(5) Å)
[37].
(16), OTf (17)), [Ag(3)2]X (X = NO3 (18), PF6 (19), OTf (20)) and
[Ag(4)2]X (X = NO3 (21), PF6 (22), OTf (23)), respectively, in good
yields (Schemes 1–3). [Ag(1)2][NO3] (11) can further react with ex-
cess AgNO3 to give [Ag(1)2]2[Ag(NO3)3(OH2)] (14) in 86% yield, 14
can also be prepared in 87% yield by reaction of AgNO3 with 1
equiv of ligand 1 (Scheme 1). Complexes 11–23 are air-stable
and soluble in methanol, partially soluble in CH2Cl2, CHCl3 and ace-
tone, but insoluble in n-hexane, toluene, and benzene. They have
been fully characterized by various spectroscopic techniques and
elemental analyses. The 1H NMR chemical shifts data and coupling
constants for compounds 11, 12, 13 and 14, or 15, 16 and 17, or 18,
19 and 20, or 21, 22 and 23 in (CD3)2SO, CD3OD or CDCl3 solution
are identical, respectively, consistent with the formation of the
same cation in compounds 11, 12, 13 and 14, or 15, 16 and 17,
or 18, 19 and 20, or 21, 22 and 23, respectively. The infrared spec-
tra of these complexes exhibit peaks corresponding to aromatic
stretches in addition to weak imine stretches at about 1620 cmꢀ1
for 11–17, and N–H stretches at about 3370 cmꢀ1 for 18–23. The
solid-state structures of complexes 11–14, 16, 19, and 22 have
been further confirmed by single-crystal X-ray diffraction analyses.
The single-crystal structures of complexes 16 and 19 show that
they consist of well-separated, alternating layers of the free anion
PF6ꢀ and the complex cation [Ag(2)2]+ or [Ag(3)2]+, respectively, in
the lattice. In the each complex ion [Ag(2)2]+ or [Ag(3)2]+, the
substituted Me2N groups are far away from the metal center, and
the Ag+ ion is
r-coordinated to four nitrogen atoms from two
ligands 2 or 3 in a distorted-tetrahedral geometry (Figs. 3 and 4).
The average distance of Ag–N is 2.362(2) Å for 16 and 2.380(2) Å
N
Br
N
N
H
NH2
NMe2
Pd(dba)3, DPPP
tBuONa
NMe2
4
0.5 AgX
Fig. 2a. Molecular structure of the cation [Ag(1)2]+ in 11–14 (thermal ellipsoids
drawn at the 35% probability level).
CH2Cl2/MeOH
N
Me2N
HN
NH
Ag
X
NMe2
N
X = NO3 (21), PF6 (22), OTf (23)
Fig. 2b. Molecular structure of the anion [Ag(NO3)3(OH2)]2ꢀ in 14 (thermal
Scheme 3. Synthesis of complexes 21–23.
ellipsoids drawn at the 35% probability level).

H. Zhang et al. / Inorganica Chimica Acta 366 (2011) 320–336
329
for 19, respectively. The twisting as expressed by the torsion angles
between the phenyl rings are 76.5(3) and 72.5(3)° for 16, which are
comparable to those found in 19 (72.6(2) and 67.5(2)°).
The single-crystal structure of complex 22 shows that it consists
of well-separated, alternating layers of the free anion PF6ꢀ and the
complex cation [Ag(4)2]+ and one solvated methanol molecule in
the lattice. In the complex ion [Ag(4)2]+, the substituted Me2N
groups are far away from the metal center, and the Ag+ ion is
r-
coordinated to two nitrogen atoms from two ligands 4 in a linear
(174.2(1)°) geometry (Fig. 5). The average distance of Ag–N is
2.181(2) Å, which is shorter than those found in 16 (2.362(2) Å)
and 19 (2.380(2) Å). The twisting as expressed by the torsion an-
gles between the phenyl rings are 72.1(4) and 68.3(4)°, which are
close to those found in 19 (72.6(2) and 67.5(2)°).
3.3. Synthesis and characterization of Ag(I) complexes with C2-
symmetric ligands
Simultaneously, we have also prepared a series of chiral silver
complexes with C2-symmetric N4-ligands 5–10. Treatment of AgX
(X = NO3, PF6, OTf) with 1 equiv of chiral N4-ligands 5, 7, 8 and
10 in mixed solvents of MeOH and CH2Cl2 (1:4) gives the chiral
binuclear, ionic Ag(I) complexes [Ag2(5)2]X2 (X = NO3 (24), PF6
(25), OTf (26)), [Ag2(7)2]X2 (X = NO3 (30), PF6 (31), OTf (32)),
[Ag2(8)2]X2 (X = NO3 (33), PF6 (34), OTf (35)) and [Ag2(10)2]X2
(X = NO3 (39), PF6 (40), OTf (41)), respectively, in good yields
(Schemes 4–7). However, under similar reaction conditions, reac-
tion of AgX (X = NO3, PF6, OTf) with 1 equiv of chiral N4-ligands 6
and 9 does not give the binuclear complexes, instead, a series of
mono-nuclear ionic complexes [Ag(6)]X (X = NO3 (27), PF6 (28),
OTf (29)) and [Ag(9)]X (X = NO3 (36), PF6 (37), OTf (38)) have been
isolated, respectively, in good yields (Schemes 4 and 6). Complexes
Fig. 3. Molecular structure of the cation [Ag(2)2]+ in 16 (thermal ellipsoids drawn at
the 35% probability level).
N
N
Ag
Ag
N
N
N
N
X2
N
N
Fig. 4. Molecular structure of the cation [Ag(3)2]+ in 19 (thermal ellipsoids drawn at
the 35% probability level).
X = NO3 (24), PF6 (25), OTf (26)
AgX
CH2Cl2/MeOH
O
N
H
2
N
N
NH2
NH2
N
N
C7H8/m.s.
5
NaBH4
C7H8/MeOH
H
N
N
H
N
N
N
N
AgX
N
N
H
H
X
Ag
CH2Cl2/MeOH
X = NO3 (27), PF6 (28), OTf (29)
Scheme 4. Synthesis of complexes 24–29.
6
Fig. 5. Molecular structure of the cation [Ag(4)2]+ in 22 (thermal ellipsoids drawn at
the 35% probability level).

330
H. Zhang et al. / Inorganica Chimica Acta 366 (2011) 320–336
O
N
H
2
N
N
NH2
NH2
C7H8/m.s.
N
N
7
AgX
CH2Cl2/MeOH
N
N
Ag
Ag
N
N
N
N
X2
N
N
Fig. 6a. Molecular structure of the cation [Ag2(5)2]2+ in 26 (thermal ellipsoids
X = NO3 (30), PF6 (31), OTf (32)
drawn at the 35% probability level).
Scheme 5. Synthesis of complexes 30–32.
24–41 are air-stable and soluble in methanol, partially soluble in
CH2Cl2, CHCl3 and acetone, but insoluble in n-hexane, toluene,
and benzene. They have been fully characterized by various spec-
troscopic techniques and elemental analyses. The 1H NMR spectra
N
N
Ag
Ag
N
N
N
N
X2
N
N
X = NO3 (33), PF6 (34), OTf (35)
Fig. 6b. Space-filling diagram of the cation P-[Ag2(5)2]2+ in 26.
AgX
CH2Cl2/MeOH
of 24–41 indicate that the complexes are symmetrical on the NMR
timescale, and the 1H NMR chemical shifts data and coupling con-
stants for compounds 24, 25 and 26, or 27, 28 and 29, or 30, 31 and
32, or 33, 34 and 35, or 36, 37 and 38, or 39, 40 and 41 in (CD3)2SO,
CD3OD or CDCl3 solution are identical, respectively, consistent with
the formation of the same cation in compounds 24, 25 and 26, or
27, 28 and 29, or 30, 31 and 32, or 33, 34 and 35, or 36, 37 and
38, or 39, 40 and 41, respectively. The infrared spectra of these
complexes exhibit peaks corresponding to aromatic stretches in
addition to weak imine stretches at about 1620 cmꢀ1 for 24–26
and 30–35, and N–H stretches at about 3370 cmꢀ1 for 27–29 and
36–41. The solid-state structures of complexes 26, 29, 31, 35, 37
and 40 have been further confirmed by single-crystal X-ray diffrac-
tion analyses.
O
N
H
2
N
N
NH2
NH2
N
N
C7H8/m.s.
8
NaBH4
C7H8/MeOH
H
N
N
N
AgX
CH2Cl2/MeOH
N
N
N
The single-crystal structures of complexes 26, 31 and 35 show
that there are well-separated, alternating layꢀers of the complex
cation [Ag2(5)2]2+ and two free anion CF3SO3 and two solvated
H
H
X
Ag
N
N
H
methanol molecules for 26, [Ag2(7)2]2+ and two free anion PF6
ꢀ
for 31, [Ag2(8)2]2+ and two free anion CF3SO3 and two solvated
ꢀ
X = NO3 (36), PF6 (37), OTf (38)
9
methanol molecules for 35, in the lattice. In the each complex
ion [Ag2(5)2]2+, [Ag2(7)2]2+ or [Ag2(8)2]2+, coordination of two
Scheme 6. Synthesis of complexes 33–38.

H. Zhang et al. / Inorganica Chimica Acta 366 (2011) 320–336
331
N
Br
N
N
2
H
H
NH2
NH2
Pd(dba)3, DPPP
tBuONa
N
N
10
AgX
CH2Cl2/MeOH
Ag
Ag
N
N
N
HN
HN
NH
NH
X2
N
Fig. 7b. Space-filling diagram of the cation P-[Ag2(7)2]2+ in 31.
X = NO3 (39), PF6 (40), OTf (41)
Scheme 7. Synthesis of complexes 39–41.
Fig. 8a. Molecular structure of the cation [Ag2(8)2]2+ in 35 (thermal ellipsoids
drawn at the 35% probability level).
Fig. 7a. Molecular structure of the cation [Ag2(7)2]2+ in 31 (thermal ellipsoids
drawn at the 35% probability level).
ligands 5, 7 or 8 around two silver(I) cations results in the forma-
tion of [Ag2(5)2]2+, [Ag2(7)2]2+ or [Ag2(8)2]2+ as a P double helix
(Figs. 6a–8b). Each Ag(I) center is four-coordinate pseudo-tetrahe-
dral, bound to two pyridylimine units, each of which is approxi-
mately planar with pyridyl–imine torsion angles in the range of
0.2–9.3°. The aryl units are twisted with respect to the imine group
with torsion angles in the range of 32.5–42.6°, and the twisting be-
tween the aryl rings ranges from 73.0 to 81.3°. This gives rise to the
formation of a double helical structure, the chirality of the helical
arrays is imposed by the chiral twist inherent in the biaryl unit.
The two Ag(I) centers within the helical dications are separated
by 3.671(6) Å for 26, 3.448(8) Å for 31 and 3.597(6) Å for 35,
respectively. The average distance of Ag–N is 2.358(4) Å for 26,
2.381(5) Å for 31 and 2.355(5) Å for 35, respectively, which is close
Fig. 8b. Space-filling diagram of the cation P-[Ag2(8)2]2+ in 35.

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H. Zhang et al. / Inorganica Chimica Acta 366 (2011) 320–336
2.421(3) Å for 29, which is close to that found in 37 (2.460(2) Å).
The twisting torsion angles between two aryl rings is 80.4(3)° for
29 and 85.6(2)° for 37, indicating they are almost perpendicular
to each other.
3.4. Synthesis and characterization of Cu(II) complexes 42–45
Treatment of C1-symmetric ligand 1 with 1 equiv of CuCl2ꢁ2H2O
in mixed solvents of MeOH and CH2Cl2 (1:4) gives the complex
(1)CuCl2ꢁH2O (42ꢁH2O) in 89% yield (Scheme 8). Reaction of
CuCl2ꢁ2H2O or Cu(ClO4)2ꢁ2H2O with 1 equiv of C2-symmetric ligand
9 affords the complexes [(9)CuCl]Cl (43) and [(9)Cu(OHMe)](ClO4)2
(44), respectively, in good yields (Scheme 9). Under similar reac-
tion condition, treatment of C2-symmetric ligand 10 with 1 equiv
of CuCl2ꢁ2H2O in a mixed solvent of MeOH and CH2Cl2 (1:4) does
not give the expected complex [(10)CuCl]Cl or (10)CuCl2, instead,
Fig. 9a. Molecular structure of the cation [Ag2(10)2]2+ in 40 (thermal ellipsoids
drawn at the 35% probability level).
a
C1-symmetric complex [2-(2-NHC5H5N)-20-(2-NHC5H4N)-6,60-
Me2-(C6H3)2]CuCl3 (45) has been isolated in 75% yield (Scheme 10),
where [2-(2-NHC5H5N)-20-(2-NHC5H4N)-6,60-Me2-(C6H3)2] is
to those found in 11 (2.361(4) Å), 12 (2.354(2) Å), 13 (2.376(3) Å),
16 (2.362(2) Å) and 19 (2.380(2) Å).
a
monodentate ligand resulting from the protonation of one of the
pyridyl groups in 10 by hydrochloric acid. Complexes 42–45 are
air-stable and soluble in methanol, partially soluble in CH2Cl2,
CHCl3, but insoluble in n-hexane, toluene, and benzene. They have
been characterized by infrared spectroscopy, elemental analyses,
and X-ray diffraction analyses.
The single-crystal structure of complex 40 shows that there are
well-separated, alternating layers of the complex cation
[Ag2(10)2]2+ and two free anion PF6 and two solvated methanol
ꢀ
molecules and two solvated H2O molecules in the lattice. In the
complex ion [Ag2(10)2]2+, coordination of two ligands 10 around
two Ag(I) cations results in the formation of [Ag2(10)2]2+ as an M
double helix (Figs. 9a and 9b). Each Ag(I) center is bound to two
pyridyl units in a linear fashion (178.1(2)° and 175.4(2)°). The
twisting between the phenyl rings are 74.6(8) and 76.9(7)°, which
are smaller than those found in 35 (78.8(2)° and 81.3(2)°). The two
Ag(I) centers within the helical dications are separated by
3.238(1) Å, which is shorter than that found in 35 (3.597(6) Å).
The average distance of Ag–N is 2.139(6) Å, which is close to that
found in 21 (2.181(2) Å).
The single-crystal structure of complex 42 shows there is a
solvated H2O molecule in the lattice. The Cu2+ is
r-bound to two
chlorine atoms and two nitrogen atoms of the ligand 1 in a dis-
torted-tetrahedron geometry (Fig. 12). The average distance
(2.233(1) Å) of Cu–Cl is slightly shorter than that found in (PhCH2
NH2)2CuCl2 (2.429(2) Å) [38], and the average distance (2.041(2) Å)
of Cu–N is close to that found in (PhCH2NH2)2CuCl2 (1.983(3) Å)
[38]. The bond angle (93.2(1)°) of Cl(1)–Cu(1)–Cl(2) is smaller than
that found in (PhCH2NH2)2CuCl2 (108.9(1)°) [38]. The torsion angle
between the naphthalene rings is 68.3(3)°, which is smaller than
that found in 1 (75.6(3)°).
The single-crystal structures of complexes 29 and 37 show that
they consist of well-separated, alternꢀating layers of the complex
cation [Ag(6)]+ and free anion CF3SO3 for 29, cation [Ag(9)]+ and
free anion PF6ꢀ for 37, respectively, in the lattice. In the each com-
The single-crystal structure of complex 43 shows that it consists
of a well-separated, alternating layers of the complex cation
[(9)CuCl] and free anion Clꢀ in the lattice. In the complex cation
plex cation [Ag(6)]+ or [Ag(9)]+, the Ag+ ion is
r-coordinated to four
nitrogen atoms of the ligand 6 or 9 in a distorted-tetrahedral
geometry (Figs. 10 and 11). The average distance of Ag–N is
Fig. 10. Molecular structure of the cation [Ag(6)]+ in 29 (thermal ellipsoids drawn
at the 35% probability level).
Fig. 9b. Space-filling diagram of the cation M-[Ag2(10)2]2+ in 40.

H. Zhang et al. / Inorganica Chimica Acta 366 (2011) 320–336
333
Cl
Cl
N
Cl
Cu
N
N
N
H
N
H
CuCl2
CH2Cl2
MeOH
H
H
N
N
HN
10
45
Scheme 10. Synthesis of complex 45.
Fig. 11. Molecular structure of the cation [Ag(9)]+ in 37 (thermal ellipsoids drawn
at the 35% probability level).
Cl
Cl
N
N
Cu
CuCl2
N
N
NMe2
NMe2
CH2Cl2/MeOH
1
42
Fig. 12. Molecular structure of 42 (thermal ellipsoids drawn at the 35% probability
level).
Scheme 8. Synthesis of complex 42.
[(9)CuCl], the Cu2+ ion is
r-bound to one chlorine atom and four
The single-crystal structure of complex 45 shows that the Cu2+
r-bound to three chlorine atoms and one nitrogen atom of the
nitrogen atoms of the ligand 9 in a distorted-tetragonal–pyramidal
geometry (Fig. 13). The average distance of Cu–N is 2.070(2) Å,
which is close to that found in 42 (2.041(2) Å). The distance
(2.259(1) Å) of Cu–Cl is close to those found in 42 (2.227(1) and
2.239(1) Å). The torsion angle between two phenyl rings is
71.9(2)°, which is smaller than that found in 37 (85.6(2)°).
is
ligand 10 in a distorted-tetrahedron geometry (Fig. 15). The aver-
age distance (2.232(1) Å) of Cu–Cl is close to that found in 42
(2.233(1) Å). The distance of Cu–N is 2.017(3), which is close to
those found in 42 (2.037(3) and 2.044(3) Å). The bond angles of
Cl–Cu(1)–Cl are 137.1(1)°, 100.1(1)° and 96.4(1)°, which are larger
than that found in 42 (93.2(1)°). The torsion angle between two
phenyl rings is 75.7(5)°, which is comparable to those found in
40 (74.6(8) and 76.9(7)°).
The single-crystal structure of complex 44 shows that well-
separated, alternating layers of complex cation [Cu(8)(OHMe)]2+
-
and two free anions ClO4 in the lattice. In the complex cation
[Cu(8)(OHMe)]2+, the Cu2+ ion is
r-bound to four nitrogen atoms
of the ligand 8 and one oxygen atom of methanol in a distorted-
tetragonal–pyramidal geometry (Fig. 14). The average distance
(2.017(3) Å) of Cu–N is close to that found in 43 (2.070(2) Å). The dis-
tance (2.288(3) Å) of Cu–O(OHMe) is slightly shorter than that found
in {[S,S-C6H10-1,2-(NHCH2-2-C5H4N)2]Cu(OH2)}Cl2 (2.354(3) Å)
[39]. The torsion angle between two phenyl rings is 73.9(2)°, which
is larger than that found in 43 (71.9(2)°).
3.5. Catalytic activity of the complexes
To examine the catalytic ability of these complexes toward the
asymmetric reactions, allylation of benzaldehyde with allyltribu-
tyltin catalyzed by silver(I) complexes and Henry reaction (nitroal-
dol reaction) of benzaldehyde with nitromethane catalyzed by
H
NH
NH
43
NH
NH
N
N
N
N
Cu(ClO4)2
CuCl2
N
N
H
Cu Cl
[ClO ]
4 2
Cl
Cu OHMe
CH2Cl2
MeOH
CH2Cl2
MeOH
N
N
9
44
Scheme 9. Synthesis of complexes 43 and 44.

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H. Zhang et al. / Inorganica Chimica Acta 366 (2011) 320–336
Fig. 15. Molecular structure of 45 (thermal ellipsoids drawn at the 35% probability
level).
Fig. 13. Molecular structure of the cation [Cu(8)(Cl)]+ in 43 (thermal ellipsoids
drawn at the 35% probability level).
In Table 7, the results have shown that all Cu(II) complexes
42–45 are good catalysts for Henry reaction while the enantiose-
lectivity is low in each case. Enantioselectivity can be improved
by lowering the temperature at the accompanying expense of in-
creased the reaction time (Table 7, entries 3–5). In one instance,
the reaction in entry 5 (Table 7) is performed by mixing the reac-
tants and stirring the resulting solution at ꢀ20 °C for 72 h. Subse-
quent isolation affords the corresponding aldol adduct in 80%
yield with 32% ee. However, if the same reaction is carried out
at 20 °C, significant rate acceleration is noticed with an accompa-
nying decrease of the enantioselective excess to 16% ee (Table 7,
entry 3). Copper complex 45 can promote the reaction, but no
enantioselectivity is observed (Table 7, entry 6), presumably
due to its coordination mode (Fig. 15), in which the steric hin-
drance is far away from the metal center. Under similar reaction
conditions, treatment of Ag(I) complexes 11–41 with benzalde-
hyde and nitromethane in the presence of Et3N, each of them is
reduced to silver metal, and no product 1-phenyl-2-nitroethanol
has been isolated.
4. Conclusions
Fig. 14. Molecular structure of the cation [Cu(8)(CH3OH)]2+ in 44 (thermal
ellipsoids drawn at the 35% probability level).
A series of chiral Ag(I) and Cu(II) complexes have been prepared
from the reaction between AgX (X = NO3, PF6, OTf) or CuX2 (X = Cl,
ClO4) and chiral biaryldiamine-based N-ligands 1–10. The Cu(II)
complexes show no catalytic activity for allylation reaction, in con-
trast to Ag(I) complexes, but they do show catalytic activity for
Henry reaction (nitroaldol reaction) whereas the Ag(I) complexes
do not. The rigidity of the ligand plays an important role in the
Ag(I) complexes formation and their catalytic activity. For example,
treatment of ligand 5 with 1 equiv of AgOTf gives the chiral, binu-
clear double helicate Ag(I) complex [Ag2(5)2][OTf]2 (26), while li-
gand 6 induces a mono-nuclear single helicate Ag(I) complex
[Ag(6)](OTf) (29). Complex 29 shows an increased enantioselectiv-
ity in the allylation reaction, and a moderate ee value (up to 31%)
has been obtained, while complex 26 does not. Both asymmetric
allylation and Henry reaction results have demonstrated that the
yields are good but enantiomeric excesses are low. The reasons
for the low enantiomeric excess are not clear at this time, however,
the steric hindrance at the chiral ligand might not be sufficient to
afford one enantiomer. We are currently focusing on these
copper(II) complexes have been tested under the conditions given
in Tables 6 and 7, respectively.
The results (Table 6) have shown that the Ag(I) complexes 11–
13 and 15–41 are efficient catalysts for tributyltinylallylation of
benzaldehyde, however, the enantiomeric excess is low in all cases.
The bis-ligated complex 13 shows the highest enantioselectivity
for this transformation, but only a moderate ee value (48%) has
been obtained. The anion has a noticeable effect on the enantiose-
lectivity (Table 6, entries 1–3), but the temperature dependence of
the enantioselectivity in this reaction is not noticed (Table 6,
entries 3 and 4). When C2-symmetric ligands 5 and 6 are used,
the different enantioselectivity between the binuclear double
helicate complexes and mono-nuclear single helicate complexes
is observed (Table 6, entries 14–19), and a moderate enantioselec-
tivity (36% ee) mediated by complex 28 has been obtained. Under
similar reaction conditions, Cu(II) complexes 42–45 show no
catalytic activity for this allylation reaction.

H. Zhang et al. / Inorganica Chimica Acta 366 (2011) 320–336
335
Table 6
Enantioselective allylation reaction of benzaldehyde catalyzed by Ag(I) complexesa.
OH
*
O
1) Ag(I)-Cat* (20 mol%)
2) KF/H2O
H
+
Bu3Sn
Entry
Complex
Temperature (°C)
Time (h)
Yieldb (%)
Eec (%) (Config.)
1
2
3
4
5
6
7
8
(R,R)-11
(R,R)-12
(R,R)-13
(R,R)-13
(R,R)-15
(R,R)-16
(R,R)-17
(R,R)-18
(R,R)-19
(R,R)-20
(R,R)-21
(R,R)-22
(R,R)-23
(R,R)-24
(R,R)-25
(R,R)-26
(R)-27
20
20
20
0
60
60
60
72
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
92
88
82
18
90
87
85
82
75
78
91
88
83
78
80
72
86
80
82
78
72
76
86
82
84
88
80
86
90
85
82
24 (R)
27 (R)
48 (R)
50 (R)
26 (R)
23 (R)
22 (R)
10 (R)
8.5 (R)
13 (R)
19 (R)
19 (R)
17 (R)
17 (S)
28 (S)
17 (S)
30 (S)
36 (S)
31 (S)
18 (S)
14 (S)
11 (S)
13 (S)
9.3 (S)
13 (S)
14 (S)
15 (S)
12 (S)
8.1 (R)
12 (R)
11 (R)
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
(R)-28
(R)-29
(R,R)-30
(R,R)-31
(R,R)-32
(R,R)-33
(R,R)-34
(R,R)-35
(R)-36
(R)-37
(R)-38
(S,S)-39
(S,S)-40
(S,S)-41
a
b
c
All reactions were carried on a 0.5 mmol scale with 20 mol% of complex and 1.2 equiv of allyltributylstannane in a mixed solvent of THF (1.0 mL) and CH2Cl2 (1.0 mL).
Isolated yields.
Enantiomeric excess was determined by HPLC with a Chiralcel OD-H column, the configuration was determined by the comparison of the specific rotation values for the
product [32].
Table 7
Enantioselective Henry reaction catalyzed by Cu(II) complexesa.
OH
*
O
NO2
Cu(II)-Cat* (20 mol%)
H
+
CH3NO2
Entry
Complex
Temp. °C
Promotor
Time (h)
Yieldb (%)
Eec (%) (Config.)
1
2
3
4
5
6
(R)-42
(R)-43
(R)-44
(R)-44
(R)-44
(S)-45
20
20
20
0
-20
20
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
24
24
24
36
72
24
96
87
84
78
80
94
3.1 (S)
10 (S)
16 (S)
28 (S)
32 (S)
0
a
b
c
All reactions were carried on a 0.5 mmol scale with 20 mol% of complex and 20 equiv of nitromethane in 2.0 mL of ethanol.
Isolated yields.
Enantiomeric excess was determined by HPLC with a Chiralcel OD-H column, the configuration was determined by the comparison of the specific rotation values for the
product [33].
transformations, further optimization of the ligand architecture to
improve the enantiomeric excesses for these transformations and
the exploration of these catalysts toward other types of transfor-
mations are still underway.
Acknowledgments
This work was supported by the National Natural Science Foun-
dation of China (20972018 and 21074013), the Fundamental

336
H. Zhang et al. / Inorganica Chimica Acta 366 (2011) 320–336
[14] G. Zi, L. Xiang, Y. Zhang, Q. Wang, X. Li, Y. Yang, Z. Zhang, J. Organomet. Chem.
692 (2007) 3949.
Research Funds for the Central Universities, and Beijing Municipal
Commission of Education.
[15] L. Xiang, Q. Wang, H. Song, G. Zi, Organometallics 26 (2007) 5323.
[16] Q. Wang, L. Xiang, H. Song, G. Zi, Inorg. Chem. 47 (2008) 4319.
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666.
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4048.
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Appendix A. Supplementary material
CCDC 794803, 794804, 794805, 794806, 794807, 794808,
794809, 794810, 794811, 794812, 794813, 794814, 794815,
794816, 794817, 794818, 794819 and 794820 contain the supple-
mentary crystallographic data compounds 1, 11, 12, 13, 14, 16, 19,
22, 26, 29, 31, 35, 37, 40, 42, 43, 44 and 45. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif. Supplementary
data associated with this article can be found, in the online version,
at doi:10.1016/j.ica.2010.11.023.
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