Synthesis, structure and spectroscopic properties of novel 9,10-bis{[6-(diphenylphosphanyl)-2-pyridylmethyl]propylaminomethyl} anthracene-bridged group 11 metal (M = CuI and AgI) dinuclear complexes

Article abstract of DOI:10.1002/ejic.200500050

Dinuclear complexes [M₂(μ-BPNNAn)]X₂ (M = Cu ^I, X = ClO₄^- 1, 1X = BF₄^- 2; M = Ag^I, X = BF₄^- 3, X = ClO ₄^- 4) have been prepared by treating 9,10-bis{[6- (diphenylphosphanyl)-2-pyridylmethyl]propylaminomethyl}anthracene (BPNNAn) with M(CH₃CN)₄X in CH₂Cl₂. The structures of complexes 1, 2 and 3 have been determined by single-crystal X-ray diffraction studies. In the complexes, BPNNAn acts as a chelating ligand and two metal ions riding on two bridgehead carbon atoms in the anthracene group leads to the deformation of the anthracenyl ring. The Cu-Arene charge transfer interaction is observed from the nonfluorescent emission of Cu complex 1, while the Ag complex 3 exhibits dual emission at high concentrations in a CH ₂Cl₂ solution. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.

Full text of DOI:10.1002/ejic.200500050

FULL PAPER
Synthesis, Structure and Spectroscopic Properties of Novel
9,10-Bis{[6-(diphenylphosphanyl)-2-pyridylmethyl]propylaminomethyl}anthracene-
Bridged Group 11 Metal (M = CuI and AgI) Dinuclear Complexes
Hu Xu,[a] Feng-Bo Xu,*[a] Qing-Shan Li,[a] Wei-Guo Duo,[a] Hai-Bin Song,[a] and
Zheng-Zhi Zhang*[a]
Keywords: Dinuclear complexes / Phosphanyl-pyridine ligands / Copper / Silver / Charge transfer interaction / Dual
emission
Dinuclear complexes [M2(μ-BPNNAn)]X2 (M = CuI, X =
bon atoms in the anthracene group leads to the deformation
of the anthracenyl ring. The Cu–Arene charge transfer inter-
action is observed from the nonfluorescent emission of Cu
complex 1, while the Ag complex 3 exhibits dual emission at
high concentrations in a CH2Cl2 solution.
–
–
–
–
ClO4 1, X = BF4 2; M = AgI, X = BF4 3, X = ClO4 4) have
been prepared by treating 9,10-bis{[6-(diphenylphosphanyl)-
2-pyridylmethyl]propylaminomethyl}anthracene (BPNNAn)
with M(CH3CN)4X in CH2Cl2. The structures of complexes
1, 2 and 3 have been determined by single-crystal X-ray dif-
fraction studies. In the complexes, BPNNAn acts as a chelat-
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
ing ligand and two metal ions riding on two bridgehead car- Germany, 2005)
Introduction
Results and Discussion
BPNNAn was prepared from 9,10-bis(propylamino-
methyl)anthracene, 6-(bromomethyl)-2-chloropyridine and
lithium diphenylphosphide by two-step reactions. In the li-
gand molecule, two dppy units are linked together through
an eight atom chain. Meanwhile, there are two lone-pair
electrons belonging to two tertiary N atoms associated with
the dppy units by a methylene spacer. Hence, it is poten-
tially a polydentate ligand. Its Group 11 dinuclear com-
In recent years increasing interest, focused on phos-
phanyl-pyridine ligands as building blocks, stems from its
ability to form hetero- or homonuclear metal complexes.[1]
The typical representative 2-(diphenylphosphanyl)pyridine
(dppy) has been widely used to synthesize dppy-bridged di-
nuclear species because of the short bite between the two
donor atoms and the poor flexibility.[2] On the other hand,
anthracenyl rings exist in a great deal of organic com-
pounds as a good fluorophore. These types of compounds
have been applied as a fluorescence chemosensor for small
molecules or metal ions.[3] Therefore, we wish to associate
two dppy units with an anthracenyl group through long
chain spacers to form a polydentate ligand and to explore
the change in fluorescence after the bonding to metal
atoms. Herein we report the novel dinuclear complexes
–
plexes [M2(μ-BPNNAn)]X2 (M = Cu, X = ClO4 1, X =
–
–
–
BF4 2; M = Ag, X = BF4 3, X = ClO4 4) were obtained
by the reaction of BPNNAn with M(CH3CN)4X (M = Cu
–
or Ag; X = ClO4– or BF4 ) in a 1:2 mol ratio and are stable
in air and moisture in the solid state, and soluble in dichlo-
romethane and acetone (Scheme 1).
Slow evaporation of a solution of complex 1 in acetone
and ethyl acetate yields bright yellow crystalline material,
which has been determined as 1·2CH3COCH3 (Figure 1a)
by a single-crystal X-ray diffraction study. Using similar
methods, bright yellow crystalline 2·1.5ClCH2CH2Cl and
pale green crystalline 3·2CH3OH (Figure 1b, only one of
the two independent molecules is shown) can be obtained.
The detailed crystallographic data and structural refine-
ments for 1, 2 and 3 are summarized in Table 1.
It can be envisaged that two dppy units contained in
BPNNAn occur at a relatively extended distance to relieve
their mutual repulsion. However, after coordination with
the group 11 metals (M = Cu, Ag) a great conformational
change of the ligand takes place. BPNNAn acts as a chelat-
ing ligand, in which the dppy-N and tertiary N atoms from
–
–
[M2(μ-BPNNAn)]X2 (M = Cu, X = ClO4 1, X = BF4 2;
–
–
M = Ag, X = BF4 3, X = ClO4 4) constructed from the
polydentate phosphanyl-pyridyl ligand 9,10-bis{[6-(di-
phenylphosphanyl)-2-pyridylmethyl]propylaminomethyl}-
anthracene (BPNNAn) and Group 11 metals. The Cu com-
plexes are formed through charge transfer interactions and
Ag complexes give dual fluorescence emission at high con-
centrations in CH2Cl2 solution.
[a] State Key Laboratory of Element-Organic Chemistry, Nankai
University,
Tianjin 300071, People’s Republic of China
E-mail: zzzhang@public.tpt.tj.cn
xfbo@eyou.com
Eur. J. Inorg. Chem. 2005, 2869–2874
DOI: 10.1002/ejic.200500050
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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H. Xu, F.-B. Xu, Q.-S. Li, W.-G. Duo, H.-B. Song, Z.-Z. Zhang
FULL PAPER
Scheme 1. Synthesis of [M2(μ-BPNNAn)]X2.
one arm and the P atom from the other simultaneously cap-
ture one of the M atoms. Each metal center exhibits a three
coordinated trigonal pyramidal geometry. The two metal
atoms ride on the two bridgehead carbon atoms in the an-
thracene group as shown in Figure 2 (only displaying com-
plex 1). Such a coordination mode leads to a remarkable
structural change in the anthracenyl ring. To relieve the ste-
ric repulsion, the 9,10-carbon atoms of the anthracenyl ring
are markedly bent towards the two metal cores, out of the
coplanar configuration, and form dihedral angles of 20.1°
(1) and 9.3° (10.8°) (3) between the side benzene rings in
the anthracenyl units. The values are larger than that of 7.7°
in our mono-Cu–η6–arene complex.[4] For the same reason
n-propyl groups on the tertiary N atoms and two phenyl
rings on the P atoms stretch away from the M cores in a
linear direction as much as possible. The dinuclear cations
of 1 (Figure 1a), and 3 (Figure 1b) possess the C2-symmet-
ric structures. No interaction is observed between cations
and anions. Selected bond lengths [Å] and angles [°] for
complexes 1, 2 and 3 are summarized in Table 2.
Figure 1. (1a) Perspective view (35% thermal ellipsoids) of the
[Cu2(μ-BPNNAn)]2+ cation in 1·2CH3COCH3. (1b) Perspective
view (35% thermal ellipsoids) of eight-membered ring M2P2N2C2
from the anthracene plane in 3·2CH3OH. Only the ipso carbons of
the phenyl groups of the P atoms are shown, and the hydrogen
atoms have been omitted for clarity.
Figure 2. Space filling view of the Cu···Cu cores riding on 9,10-
bridgehead carbon atoms of anthracene unit in complex 1.
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Dinuclear Complexes with Phosphanylpyridine Ligands
FULL PAPER
Table 1. Crystal data and structure refinement for 1, 2 and 3.
1·2CH3COCH3
2·1.5ClCH2CH2Cl
3·2CH3OH
Chemical formula
Formula mass
Crystal system
Space group
C60H68Cl2Cu2N4O10P2
1313.14
triclinic
P-1
C30.50H31BCl1.50CuF4N2P
660.07
triclinic
P-1
C60H64Ag2B2F8N4O2P2
1324.45
monoclinic
C2/c
a [Å]
b [Å]
c [Å]
α [°]
12.706(6)
13.390(6)
18.865(8)
83.765(8)
82.941(8)
77.030(8)
3093(2)
2
13.252(7)
13.596(7)
17.908(9)
79.657(9)
77.676(9)
76.604(9)
3037(3)
4
28.330(18)
25.547(17)
21.349(14)
90
131.005(8)
90
11660(13)
8
1.509
β [°]
γ [°]
V [Å3]
Z
Dcalcd. [mgm–3]
1.410
0.887
1.443
0.952
μ [mm–1]
0.798
F(000)
T [K]
1364
293(2)
1354
293(2)
5392
293(2)
No. of data collected
No. of unique data
No. of refined parameters
Goodness-of-fit on F2 [a]
16067
10821
790
1.065
15927
10666
833
1.030
33453
11903
810
1.015
[b]
R1
0.0708
0.0621
0.0406
wR2
R1
0.1533
0.1517
0.1546
0.1182
0.0851
0.0959
[b]
wR2
0.1974
0.2030
0.1083
[a] GOF = {Σ[w(Fo – Fc ) /(n – p)]1/2, where n is the number of reflections and p is the number of parameters refined. [b] R1 = Σ(||Fo| –
2
2 2
2
2
|Fc||)/Σ|Fo|; wR2 = 1/[σ2(Fo2) + (0.0691P) + 1.4100P] where P = (Fo + 2Fc )/3.
Table 2. Selected bond lengths [Å] and angles [°] for complexes 1, 2 and 3.[a]
1·2CH3COCH3
2·1.5ClCH2CH2Cl
3·2CH3OH
Cu(1)–Cu(2)
Cu(1)–P(1)
Cu(1)–N(2)
Cu(1)–N(4)
2.9734(16)
2.177(2)
2.150(5)
2.007(5)
Cu(1)–N(4)
Cu(1)–N(2)
Cu(1)–P(1)
2.034(5)
2.132(5)
2.1836(19)
Ag(2)–Ag(2)#2
Ag(2)–N(4)#2
Ag(2)–P(2)
3.0874(19)
2.287(3)
2.3699(18)
2.434(4)
Ag(2)–N(3)#2
N(2)–Cu(1)–P(1)
N(4)–Cu(1)–P(1)
P(1)–Cu(1)–Cu(2)
N(2)–Cu(1)–Cu(2)
N(4)–Cu(1)–N(2)
N(4)–Cu(1)–Cu(2)
126.76(15)
140.09(16)
79.91(6)
144.70(14)
83.5(2)
N(4)–Cu(1)–N(2)
N(4)–Cu(1)–P(1)
N(2)–Cu(1)–P(1)
84.01(19)
139.16(14)
130.08(14)
N(4)#2–Ag(2)–P(2)
N(4)#2–Ag(2)–N(3)#2
P(2)–Ag(2)–N(3)#2
N(4)#2–Ag(2)–Ag(2)#2
P(2)–Ag(2)–Ag(2)#2
N(3)#2–Ag(2)–Ag(2)#2
150.32(10)
74.55(13)
133.76(9)
84.67(10)
78.51(5)
87.28(16)
135.22(9)
[a] Symmetry transformations used to generate equivalent atoms: #2 –x + 1, y, –z + 3/2.
Apart from the two tertiary N atoms, two dppy units in (MeCN)]+,[10] [Cu2(μ-L1)2(MeCN)2]2+ [L1 = 2-(diphenyl-
a head-to-tail mode forming an eight-membered ring phosphanyl)-6-(pyrazol-1-yl)pyridine][7] and [Cu2(μ-L)2-
M2P2N2C2, which has an eclipsed conformation, bridge the (MeCN)2]2+ (L
=
6-(diphenylphosphanyl)-2,2Ј-bipyri-
metal atoms. The torsion angle P(1)–Cu(1)–Cu(2)–P(2) of dine),[6] respectively.
117.8° for 1 is much smaller than that of 125.2°(128.3°) for
The Ag···Ag separation of 3.0874(19) Å [3.0963(16) Å] in
3. While in [Ag2(μ-L1)2(MeCN)2]2+ [L1 = 2-(diphenylphos- 3 is slightly shorter than that of 3.145 Å in [Ag2-
phanyl)-6-(pyrazol-1-yl)pyridine],[5] [Cu2(μ-L)2(MeCN)2]2+ (dppy)2]2+[11] and 3.162(1)–3.223(1) Å in [Ag3{HC-
(L = 6-(diphenylphosphanyl)-2,2Ј-bipyridine)[6] and [Cu2(μ- (PPh2)3}2]3+ [12]
And the value compares with those found
.
L1)2(MeCN)2]2+ [L1 = 2-(diphenylphosphanyl)-6-(pyrazol- in [Ag2(η1-dppy)(μ-dppy)2]2+ [3.072(1) Å],[13] [Ag2Cl2-
1-yl)pyridine],[7] the similar eight-membered rings are stag- (dppy)3] [3.074(2) Å][14] and [Ag2(dpm)2(NO3)2] (3.085 Å)
gered conformations.
[dpm =
bis(diphenylphosphanyl)methane].[15] But the
The Cu···Cu distance 2.9734(16) Å for 1 is close to the Ag···Ag distance of 3 is slightly longer than that of
sum of the van der Waals radii of CuI centers and lies 2.964(1) Å reported in [Ag2(μ-L1)2(MeCN)2]2+ [L1 = 2-(di-
towards the longer distances of the known Cu–Cu bonds phenylphosphanyl)-6-(pyrazol-1-yl)pyridine],[5] which indi-
[2.639(2)–2.938(2) Å] for dinuclear CuI complexes.[8] The cates the possibility of a weak Ag···Ag bond. Since the
value is slightly longer than that of 2.721(3) Å in [Cu2(μ- value of 3.30 Å represents the upper limit for the Ag···Ag
dppy)3(MeCN)]+[9] and much shorter than those of interactions in coordination compounds,[16] it can be con-
3.584(1) Å, 3.625(1) Å and 3.941(2) Å in [Cu2(μ-dppy)2- cluded that Ag···Ag interactions are present in complex 3.
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In addition, there is an intramolecular π-π stacking inter- emission peak results mainly from the anthracenyl ring.
action between two phenyl rings on two P atoms that are With the increase of the concentration, the excimer emis-
nearly orthogonal to the anthracene mean plane. They sion gradually appears and becomes dominant (Figure 4).
stack partially with separations of 3.33 Å and 3.47 Å Therefore, we propose that there is a series of conversion
(3.39 Å) for 1 and 3, respectively. The π-π stacking interac- processes for 3 in the CH2Cl2 solution. Firstly, the Ag···Ag
tions may be one of the reasons for drawing two metal bond separates away from the anthracenyl unit and the de-
atoms together that are located close to one another. The formation of the anthracenyl ring forms 3Ј. Then the com-
distance of the center of the M···M to the anthracene cen- bining of two 3Ј forms the dimer. But in the low concentra-
tral ring in 1 is 2.9 Å, while the corresponding value in 3 is tion range, 3Ј cannot efficiently form the dimer, which gen-
3.2 Å. When [M2(μ-BPNNAn)]X2 react with Na2S, the free erates a new emission. At high concentration, the dimer oc-
ligand BPNNAn can be recovered quantitatively by remov- curs in larger quantities than both 3 and 3Ј. So the new
ing the coordinated Cu or Ag atoms from the polydentate emission dominates in the emission spectrum in Ag com-
complexes (Scheme 1).
plexes at high concentration (Scheme 2). As for 1 the feeble
Compared with the free ligand, the fluorescence emission emission shows the formation of a charge transfer complex
intensity of [M2(μ-BPNNAn)]X2 changes dramatically. The in the Cu complex,[17] in which the charge transfer interac-
spectrum of BPNNAn in CH2Cl2 solution (1.0×10–5 m) at tion is fairly strong and prevents 1 from forming the ana-
room temperature displays the expected strong emission logs of 3Ј. On the other hand, complex 1 does not generate
peak for the anthracenyl fluorophore centered at 431 nm. the dual emission as 3 does, which also further proves the
Complex 1 in CH2Cl2 gives a feeble emission, while 3 gives presence of the aforementioned Cu–Arene charge transfer
a moderately strong peak (Figure 3). What is more interest- interaction in Cu complexes. Besides, we also observe the
ing is that a broad new emission peak, centered at 460 nm, fluorescence emission intensity change process for the solu-
emerges, except for the anthracenic emission of 3. The new tion of BPNNAn in CH2Cl2 containing Cu(CH3CN)4ClO4
emission for 3 is dependent on concentration and is ascrib- of different concentrations (Figure 5). With the increasing
able to the formation of excimer type intermolecular com- concentration of CuI, the fluorescence emission intensity of
plexes resulting from the interaction between the two an- the solution descends gradually until the emission becomes
thracenyl rings. When the concentration is very low, the weak. Recording the fluorescence intensity against the ratio
Figure 4. Fluorescene emission intensity of 3 in different concentra-
Figure 3. Fluoresence emission spectra of a (BPNNAn), b (3) and
c (1) (λex = 360 nm) at 298 K in CH2Cl2 (1.0×10–5 m).
tions of a CH2Cl2 solution: (a) 1.0×10–6 m, (b) 5.0×10–6 m, (c)
1.0×10–5 m.
Scheme 2. Conversion process of 3 in CH2Cl2 solution.
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Dinuclear Complexes with Phosphanylpyridine Ligands
FULL PAPER
[CuI] to [1], we get a corresponding curve, which indicates bent. Complexes [M2(μ-BPNNAn)]X2 react with Na2S to
that a compound like 1 will only be formed in the end if release quantitatively the free ligand BPNNAn. Cu···Arene
sufficient CuI exists in solution (Figure 6).
charge transfer interactions in the Cu complexes exist,
which leads to nonfluorescence emission of the complexes,
while Ag complexes, which possess Ag···Ag bonds, generate
dual fluorescence emission under the same conditions.
Experimental Section
General Procedures: All reactions were carried out under prepuri-
fied argon using standard Schlenk or vacuum line techniques unless
stated otherwise. The solvents were purified by standard methods.
1H and 31P NMR spectra were recorded on a Bruker AC-300 NMR
spectrometer. Elemental analyses were measured by using a Perkin–
Elmer 2400C Elemental Analyzer. The fluorescence spectroscopy
was measured with a Cary Eclipse fluorescence spectrophotometer.
CAUTION: Metal perchlorates are potentially explosive in reac-
tions with organic compounds and proper care should always be
taken.
Preparation of 9,10-Bis[(6-chloro-2-pyridylmethyl)propylaminometh-
yl]anthracene (L): 6-(bromomethyl)-2-chloropyridine (4.54 g,
22 mmol) and K2CO3 (5.52 g, 40 mmol) were added to a solution
Figure 5. Fluorescence emission spectra (λex = 360 nm) of solutions
containing Cu(CH3CN)4ClO4 of different concentrations in a
CH2Cl2 solution of BPNNAn (1.0×10–5 m) (a = 0×10–5 m, b =
0.2×10–5 m, c = 0.4×10–5 m, d = 0.6×10–5 m, e = 0.8×10–5 m, f =
1.0×10–5 m, g = 1.2×10–5 m, h = 1.4×10–5 m, i = 1.6×10–5 m, j =
1.8×10–5 m, k = 2.0×10–5 m, l = 2.2×10–5 m).
containing
9,10-bis(propylaminomethyl)anthracene
(3.0 g,
10 mmol) in MeCN (80 mL). The resulting mixture was stirred at
refluxing temperature for 3 days while being exposed to air. This
solution was cooled and then filtered through Celite. The solvent
was removed in vacuo and water (50 mL) was added. The aqueous
phase was extracted with CH2Cl2 (3×40 mL) and the organic
phase dried with anhydrous Na2SO4 overnight. Most of the CH2Cl2
was removed under vacuum and ether was added. Cooling to
–10 °C yielded a pale yellow solid, which was recrystallized with
dichloromethane-haxane to afford L. Yield: 2.64 g (46.2%). 1H
NMR (300 MHz, CDCl3): δ = 8.48–8.51(q, 4 H, AnH) (An = An-
thracene), 7.42–7.46(q, 4 H, AnH), 7.19–7.24(t, 2 H, PyH) (Py =
Pyridine), 6.99–7.02(d, 2 H, PyH), 6.86–6.89(d, 2 H, PyH), 4.55(s,
4
H, AnCH2), 3.61(s, 4 H, NCH2Py), 2.54–2.59(t, 4 H,
CH2CH2CH3), 1.57–1.69(m, 4 H, CH2CH2CH3), 0.76–0.81(t, 6 H,
CH2CH2CH3) ppm. Elemental analysis for C34H36Cl2N4 (571.6 g):
calcd. C 71.45, H 6.30, N 9.81; found: C 71.44, H 6.42, N 9.72.
Preparation of BPNNAn: A solution of nBuLi in hexane (4 mL,
1.88 m) was added dropwise to a solution of Ph2PH (1.29 g,
6.94 mmol) in THF (15 mL) at 0 °C with stirring and the resulting
solution was stirred for half an hour at this temperature. Then the
mixture was added dropwise to a solution of L (1.80 g, 3.15 mmol)
in THF (20 mL) at –78 °C and the mixture was allowed to warm
slowly to room temperature and continuously stirred for 5 h, after
which the solution was refluxed for 2 h. After cooling, the solvent
was removed in vacuo and water (50 mL) was added. The aqueous
phase was extracted with CH2Cl2 (3×30 mL) and the organic
phase dried with anhydrous Na2SO4 overnight. Most of the CH2Cl2
was removed under vacuum and the residue was cooled to 0 °C for
8 h to afford a light yellow solid BPNNAn. Yield: 1.6 g (57.4%).
1H NMR(300 MHz, CDCl3): δ = 8.52–8.55 (q, 4 H, AnH), 7.43–
7.46 (q, 4 H, AnH), 7.23–7.35 (m, 22 H, PhH and PyH), 7.04–
7.07(d, 2 H, PyH), 6.75–6.78(d, 2 H, PyH), 4.60(s, 4 H, AnCH2),
3.76(s, 4 H, NCH2Py), 2.54–2.59(t, 4 H, CH2CH2CH3), 1.57–
1.68(m, 4 H, CH2CH2CH3), 0.73–0.78 (t, 6 H, CH2CH2CH3) ppm.
31P NMR (300 MHz, CDCl3): δ = –4.42 (s) ppm. Elemental analy-
sis for C58H56N4P2 (871.1 g): calcd. C 79.90, H 6.43, N 6.43; found:
Figure 6. Plot of the recorded relation of fluorescence intensity at
431 nm against the ratio of [CuI] to [1] (1.0×10–5 m) in CH2Cl2.
There is a hemilabile coordination mode in these struc-
tures, which makes the study of the catalytic activity of
these BPNNAn systems with the late transition metals
highly feasible. The work in this field is presently under way.
Conclusions
We have prepared a new polydentate phosphane ligand
BPNNAn and obtained its Group 11 dinuclear complexes
1, 2, 3 and 4, in which anthracene planes are remarkably C 79.81, H 6.22, N 6.55.
Eur. J. Inorg. Chem. 2005, 2869–2874
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H. Xu, F.-B. Xu, Q.-S. Li, W.-G. Duo, H.-B. Song, Z.-Z. Zhang
FULL PAPER
Preparation of Complex [Cu2(μ-BPNNAn)](ClO4)2 (1): Solid [Cu-
(MeCN)4][ClO4] (0.107 g, 0.328 mmol) was added to a solution of
BPNNAn (0.143 g, 0.164 mmol) in CH2Cl2 (20 mL) with stirring
at –30 °C. The resulting solution was allowed to warm slowly to
room temperature and stirred continuously for 2 h at this tempera-
ture. Subsequent diffusion of diethyl ether into the concentrated
solution gave complex 1 as a yellow powder. Yield: 0.09 g (45.69%).
31P NMR (300 MHz, [D6]DMSO): δ = 12.80(s) ppm. Elemental
analysis for C58H56Cl2Cu2N4O8P2·2CH3C(O)CH3 (1313.1 g):
calcd. C 58.49, H 5.18, N 4.26; found: C 58.18, H 5.45, N 4.25.
Ackowledgments
We thank the National Natural Science Foundation for financial
support of this work through grant 20472036.
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S. Ramdeehul, J. A. Osborn, C. Carlotti, F. Taulelle, A. D.
Cian, J. Fisher, Eur. J. Inorg. Chem. 2000, 2523–2532; g) V. J.
Catalano, B. L. Bennett, S. Muratidis, B. C. Noll, J. Am. Chem.
Soc. 2001, 123, 173–174.
Preparation of Complex [Cu2(μ-BPNNAn)](BF4)2 (2): Complex 2,
as a bright yellow powder, was synthesized by BPNNAn (0.110 g,
0.126 mmol) and [Cu(MeCN)4][BF4] (0.079 g, 0.251 mmol) by the
same procedure as used for 1. Yield: 0.112 g (74.67%). 31P NMR
(300 MHz, [D6]DMSO): δ = 12.82(s) ppm. Elemental analysis for
C58H56Cu2B2N4F8P2·1.5ClCH2CH2Cl (1320.1 g): calcd. C 55.45,
H 4.70, N 4.24; found: C 55.05, H 4.91, N 4.47.
[2] a) Z.-Z. Zhang, H. Cheng, Coord. Chem. Rev. 1996, 147, 1–39;
b) S.-M. Kuang, H. Cheng, L.-J. Sun, Z.-Z. Zhang, Z.-Y. Zhou,
B.-M. Wu, T. C. W. Mak, Polyhedron 1996, 15, 3417–3426; c)
Z.-Z. Zhang, H. Cheng, S.-M. Kuang, Y.-Q. Zhou, Z.-X. Liu,
J.-K. Zhang, H.-G. Wang, J. Organomet. Chem. 1996, 516, 1–
10; d) S.-M. Kuang, F. Xue, C.-Y. Duan, T. C. W. Mak, Z.-Z.
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1997, 540, 55–60; f) S.-M. Kuang, F. Xue, T. C. W. Mak, Z.-Z.
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4419–4476; b) F.-B. Xu, Q.-S. Li, X.-S. Zeng, X.-B. Leng, Z.-
Z. Zhang, Organometallics 2002, 21, 4894–4896; c) F.-B. Xu,
Q.-S. Li, X.-B. Leng, Z.-Z. Zhang, Organometallics 2004, 23,
632–634.
Preparation of Complex [Ag2(μ-BPNNAn)](BF4)2 (3): Complex 3,
as a pale yellow powder, was synthesized by BPNNAn (0.143 g,
0.164 mmol) and [Ag(MeCN)4][BF4] (0.118 g, 0.328 mmol) by the
same procedure as used for 1, but in darkness. Yield: 0.120 g
(57.97%). 31P NMR (300 MHz, [D6]DMSO): δ = 21.97 ppm. Ele-
mental analysis for C58H56Ag2B2N4F8P2·2CH3OH (1324.5 g):
calcd. C 54.36, H 4.83, N 4.23; found: C 54.30, H 4.74, N 4.07.
Preparation of Complex [Ag2(μ-BPNNAn)](ClO4)2 (4): Complex 4,
as a pale yellow powder, was synthesized by BPNNAn (0.143 g,
0.164 mmol) and [Ag(MeCN)4][ClO4] (0.122 g, 0.328 mmol) by the
same procedure as used for 1, but in darkness. Yield: 0.150 g
(71.09%). 31P NMR (300 MHz, [D6]DMSO): δ = 22.04 ppm. Ele-
mental analysis for C58H56Ag2Cl2N4O8P2 (1285.8 g): calcd. C
54.12, H 4.35, N 4.35; found: C 53.76, H 4.43, N 4.03.
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Zeng, Y.-L. Chow, Z.-Z. Zhang, Organometallics 2003, 22, 633–
640.
Reaction of Complexes with Na2S: A solution of excess Na2S·9H2O
in distilled water (5 mL) was added to a solution of 1 (58 mg,
0.048 mmol) in acetone (15 mL) with stirring and a black precipi-
tate was immediately produced. Stirring was continued for 30 min
and a white solid was generated. CH2Cl2 (15 mL) was added to the
solution and stirring continued until the white solid disappeared.
The black precipitate was filtered and the solvent was removed un-
der vacuum. The residue was recrystallized from CH2Cl2-diethyl
ether to give BPNNAn. Yield: 30 mg (71.4%).
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Similar reactions for complex 2, 3 and 4 can be undertaken to give
BPNNAn quantitatively.
X-ray Crystallography: The structures of 1, 2 and 3 were solved
by direct methods and all non-hydrogen atoms were subjected to
anisotropic refinement by full-matrix least-squares on F2 using the
SHELXTL package. Data collection was performed at room tem-
perature with a Bruker SMART 1000 CCD diffractometer op-
erating at 50 kV and 20 mA using Mo-Kα radiation (0.71073 Å).
An empirical absorption correction was applied using the SADABS
program. All hydrogen atoms were generated geometrically (C–H
bond lengths fixed at 0.96 Å), assigned appropriate isotropic ther-
mal parameters and included in structure factor calculations.
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CCDC-244084, -258486 and -258487 contain the supplementary
crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
Received: January 17, 2005
Published Online: June 14, 2005
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Eur. J. Inorg. Chem. 2005, 2869–2874