The use of phosphirenes as conjugating spacers in polythiophene chains

Article abstract of DOI:10.1021/om060675w

A series of thienyl-substituted phosphirene P-W(CO)₅ complexes were synthesized by reaction of the transient terminal phosphinidene complex [Ph-P-W(CO)₅] with the appropriate thienyl-substituted alkynes. The X-ray structural study of these complexes shows coplanar thiophene and phosphirene rings, suggesting a good inter-ring conjugation. A combined ¹³C NMR-NBO analysis indicates that the C=C double bond of the phosphirene ring is highly polarizable. UV spectra show a red-shift of the absorption when converting the alkynes into the phosphirenes. CV data are also given.

Full text of DOI:10.1021/om060675w

5176
Organometallics 2006, 25, 5176-5179
The Use of Phosphirenes as Conjugating Spacers in Polythiophene
Chains
Ngoc Hoa Tran Huy,*,† Emilie Perrier,† Louis Ricard,† and Franc¸ois Mathey*,‡
Laboratoire “He´te´roe´le´ments et Coordination” UMR CNRS 7653, DCPH, Ecole Polytechnique, 91128
Palaiseau Cedex, France, and UCR-CNRS Joint Research Chemistry Laboratory, Department of
Chemistry, UniVersity of California, RiVerside, California 92521-0403
ReceiVed July 27, 2006
Summary: A series of thienyl-substituted phosphirene P-W(CO)5
complexes were synthesized by reaction of the transient terminal
phosphinidene complex [Ph-P-W(CO)5] with the appropriate
thienyl-substituted alkynes. The X-ray structural study of these
complexes shows coplanar thiophene and phosphirene rings,
suggesting a good inter-ring conjugation. A combined 13C
NMR-NBO analysis indicates that the CdC double bond of
the phosphirene ring is highly polarizable. UV spectra show a
red-shift of the absorption when conVerting the alkynes into the
phosphirenes. CV data are also giVen.
the chain.4 Thus, a conjugating spacer within a polythiophene
chain must induce a weakening of the thiophene aromaticity,
while favoring the highest possible conjugation between the
thiophene units. In this work, we demonstrate that the phos-
phirene ring meets all the criteria (accessibility, stability, and
conjugating properties) for its use as a conjugating spacer within
a polythiophene chain.
Results and Discussion
We first decided to synthesize a 2,3-bis(2-thienyl)phosphirene
complex using the classical phosphinidene approach (eq 1).5
Introduction
The incorporation of phosphorus centers within the backbone
of π-conjugated materials for molecular electronics and opto-
electronics has recently attracted a lot of attention.1 Indeed,
phosphorus allows an easy tuning of the electronic properties
of the materials by modification of the chemical environment
of the heteroatom (oxidation, quaternization, complexation).
When conceiving these new P-containing materials, the ease
of synthesis and the stability of the products are two crucial
criteria that must never be overlooked. For example, R-con-
nected polyphospholes are difficult to synthesize and seem to
display some instability above four phosphole units.2 This is
the reason mixed phosphole-thiophene chains are, by far, the
most studied oligomers in this category.3 From the electronic
standpoint, several theoretical studies on polyheterole chains
have clearly shown that there is a competition between the
aromaticity of the heterole and the desirable delocalization along
The reaction runs smoothly and produces complex 1, whose
X-ray crystal structure is shown in Figure 1. The thiophene and
phosphirene rings of 1 are coplanar with sulfur atoms facing
each other on the concave side of the chain. The thiophene-
phosphirene interplane angles are 4.82(0.23)° and 6.60(0.24)°.
Together with the coplanarity of the rings, the lengthening of
the endo C3-S1 by comparison with the exo C6-S1 bond
suggests that a significant interaction exists between the
phosphirene and thiophene π-systems.
To get more data and further establish the necessary synthetic
bases for our study of the phosphirene-thiophene chains, it was
also necessary to prepare phosphirene-thiophene-phosphirene
units. A positive result was not granted because it had been
previously shown that the reaction of terminal phosphinidene
complexes with 1,3-diynes can lead either to 2,2′-biphosphirenes
as expected6 or to alkynyl-substituted 1,2-diphosphetenes by
insertion of the second phosphinidene unit into the ring of the
initially formed 2-alkynylphosphirene.7 Thus we allowed our
* Corresponding authors. E-mail: francois.mathey@ucr.edu.
† Laboratoire “He´te´roe´le´ments et Coordination” UMR CNRS 7653.
‡ University of California.
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Jutand, A.; Amatore, C. New J. Chem. 1991, 15, 545. Hay, C.; Fischmeister,
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10.1021/om060675w CCC: $33.50 © 2006 American Chemical Society
Publication on Web 09/06/2006

Notes
Organometallics, Vol. 25, No. 21, 2006 5177
Figure 2. Molecular structure of 4. Main bond lengths (Å) and
angles (deg): W(1)-P(1) 2.4889(5), P(1)-C(1) 1.817(2), P(1)-
C(2) 1.786(2), C(2)-C(3) 1.429(2), C(1)-C(2) 1.327(2), P(1)-
C(9) 1.821(2), C(3)-C(4) 1.370(2) C(4)-C(5) 1.411(3), C(3)-
S(1) 1.726(2), Si(1)-C(1) 1.865(2), S(1)-C(6) 1.730(2), C(6)-
C(7) 1.421(2), C(7)-C(8) 1.205(3); C(1)-P(1)-C(2) 43.22(7),
C(1)-C(2)-P(1) 69.6(1), C(2)-C(1)-P(1) 67.1(1), P(1)-C(2)-
C(3) 143.6(1), P(1)-C(1)-Si(1) 140.9(1), C(2)-P(1)-C(9) 106.36-
(8), C(1)-P(1)-W(1) 124.15(6), C(3)-S(1)-C(6) 91.8(1), S(1)-
C(3)-C(4) 111.1(1).
Figure 1. Molecular structure of the 2,3-dithienylphosphirene
pentacarbonyltungsten complex (1). Main bond lengths (Å) and
angles (deg): P-W 2.4853(6), P-C(11) 1.828(2), P-C(1) 1.788-
(2), P-C(2) 1.787(2), C(1)-C(2) 1.324(3), C(2)-C(3) 1.431(3),
C(3)-S(1) 1.729(2), C(6)-S(1) 1.707(2); C-P-C 43.5(1).
phosphinidene precursor to react with 2,5-bis(alkynyl)thiophenes
as shown in eq 2. The necessary bis-alkynes were prepared on
a large scale through a Sonogashira coupling reaction of
2-bromo- and 2,5-dibromothiophene with (trimethylsilyl)acety-
lene or phenylacetylene.8
Figure 3. Molecular structure of meso-(5). Phenyl substituents at
P are omitted for clarity. Main bond lengths (Å) and angles (deg):
W(1)-P(1) 2.4832(8), P(1)-C(1) 1.818(3), P(1)-C(2) 1.784(3),
P(1)-C(8) 1.822(3), C(1)-C(2) 1.328(4), C(1)-Si(1) 1.867(3),
C(3)-S(1) 1.731(3), C(2)-C(3) 1.425(4), C(3)-C(4) 1.369(4),
C(4)-C(4)#4 1.412(5); C(2)-P(1)-C(1) 43.3(1), C(2)-C(1)-P(1)
67.0(2), C(1)-C(2)-P(1) 69.7(2), P(1)-C(2)-C(3) 144.9(3),
P(1)-C(1)-Si(1) 139.7(2), C(1)-P(1)-C(8) 106.8(1), C(1)-P(1)-
W(1) 122.9(1), C(3)#4-S(1)-C(3) 91.5(2), S(1)-C(3)-C(2) 121.2-
(2), S(1)-C(3)-C(4) 111.3(2).
With a P/diyne ratio of 1:1, the main product results from a
monocondensation. Compound 4 was fully characterized by
X-ray crystal structure analysis (Figure 2). With a 2:1 ratio,
only the bis-condensation products were obtained in very high
yields as 50/50 separable mixtures of meso + rac diastereomers.
The structures of meso-5 and rac-6 are shown in Figures 3 and
4. The most significant data come from the comparison between
the Th-C(phosphirene) and Ph-C(phosphirene) bridging bond
lengths (1.429(5) vs 1.453(5) Å) in 6. This suggests a better
conjugation between the thiophene and phosphirene than
between the benzene and phosphirene rings.
While collecting the 13C NMR data on these phosphirene-
thiophene chains, we found that the resonances of the carbons
of the phosphirene rings were highly dependent on the ring
substituents. To confirm our assignments, we decided to
compute the NMR parameters of 7 and 8 (GIAO, B3LYP/6-
311+G(d,p)).9 The structures were optimized at the B3LYP/
6-31G(d) level for all atoms except Cr (lanl2dz). A good
agreement was found between the computed structure of 7 and
the experimental structure of 1. In particular, the coplanarity of
the thiophene and phosphirene rings was perfectly reproduced
by the computation. The NMR results are pictorially shown in
Scheme 1. The calculations correctly reproduce the experimental
trends. These results suggest that the phosphirene CdC double
bond is easily polarized. This point was confirmed by a NBO
analysis of 8 (at the B3LYP 6/31G(d)-lanl2dz level): charge
at CSiMe3 -0.67, at CTh -0.24. The high polarizability of the
(8) Takahashi, S.; Kuroyama, Y.; Sonogashira, K.; Hagihara, N. Synthesis
1980, 627. Carpita, A.; Lessi, A.; Rossi, R. Synthesis 1984, 571. Neenan,
T. X.; Whitesides, G. M. J. Org. Chem. 1988, 53, 2489.
(9) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb,
M. A.; Cheeseman, J. R.; Montgomery, Jr., J. A.; Vreven, T.; Kudin, K.
N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.;
Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.;
Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.;
Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li,
X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.;
Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.;
Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.;
Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels,
A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.;
Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.;
Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz,
P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.;
Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson,
B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03,
Revision B.05; Gaussian, Inc.: Pittsburgh, PA, 2003.

5178 Organometallics, Vol. 25, No. 21, 2006
Notes
Figure 4. Molecular structure of the (S,S)-enantiomer of rac-6.
Phenyl substituents at P are omitted for clarity. Main bond lengths
(Å) and angles (deg): W(1)-P(1) 2.489(1), P(1)-C(1) 1.787(4),
P(1)-C(2) 1.804(4), P(1)-C(9) 1.810(4), C(1)-C(2) 1.332(5),
C(1)-C(15) 1.453(5), C(3)-S(1) 1.725(4), C(2)-C(3) 1.429(5),
C(3)-C(4) 1.372(5), C(4)-C(5) 1.409(5); C(2)-P(1)-C(1) 43.5-
(2), C(2)-C(1)-P(1) 68.9(2), C(1)-C(2)-P(1) 67.5(2), P(1)-
C(2)-C(3) 145.6(3), P(1)-C(1)-C(15) 145.0(3), C(1)-P(1)-C(9)
108.5(2), C(1)-P(1)-W(1) 124.1(1), C(3)-S(1)-C(6) 91.7(2),
S(1)-C(3)-C(2) 120.7(3), S(1)-C(3)-C(4) 111.3(3).
Figure 5. UV-visible absorption spectra of diynes 2 and 3 and
phosphirenyl-thiophenes 4, 5, and 6 (0.01 mM in CH2Cl2).
and 13C) and external 85% aqueous H3PO4(31P). Elemental analyses
were performed by the Service de Microanalyse du CNRS, Gif-
sur-Yvette, France. Cyclic voltammograms were recorded in CH3-
CN (product concentration (1-1.28) × 10-3 mol/L) in the presence
of Et4NBF4 (0.1 M) on a platinum disk (φ 1 mm) in a thermostati-
cally controlled electrochemical cell. Ag/Ag+ 10-2 M in acetonitrile
was used as the reference electrode. Platinum wire was used as an
auxiliary electrode. Curve recording was performed at constant
potential scan rate (100 mV s-1).
Scheme 1
1-Phenyl-2,3-bis(2-thienyl)phosphirene Pentacarbonyltung-
sten Complex 1. Bis(2-thienyl)acetylene (0.3 g, 1.58 × 10-3 mol)
and the phosphanorbornadiene precursor10 (1 g, 1.52 × 10-3 mol)
in toluene (10 mL) were heated together at 115 °C for 9 h. The
crude product was purified by chromatography on silica gel with
hexane/dichloromethane (4:1) as the eluent. Yield: 0.6 g (63%) of
pale yellow microcrystals. 31P NMR (CDCl3): δ -141.6. 13C NMR
(CDCl3): δ 117.82 (d, JC-P ) 7.9 Hz, C phosphirene), 128.80 (s,
CHâ′ Th), 128.80 (d, JC-P ) 10.5 Hz, meta CH Ph), 129.91 (d,
JC-P ) 8.3 Hz, CR Th), 131.00 (d, JC-P ) 2.1 Hz, para CH Ph),
131.36 (d, JC-P ) 15.8 Hz, ortho CH Ph), 131.43 (d, JC-P ) 2.9
Hz, CHâ Th), 131.66 (s, CHR′ Th), 137.61 (d, JC-P ) 6.2 Hz, ipso
C Ph), 195.82 (d, JC-P ) 8.5 Hz, CO), 197.75 (d, JC-P ) 31.8 Hz,
CO). The phosphirene ring appears to act as an electron-withdraw-
ing substituent for the thiophene rings, leading to a deshielding of
CHR′ and CHâ and a shielding of CR and CHâ′. Anal. Calcd for
C21H11O5PS2W: C, 40.53; H, 1.78. Found: C, 40.52; H, 1.85.
Complex 4: purified by chromatography on silica gel with
hexane/dichloromethane, 38% yield. 31P NMR (CDCl3): δ -167.1.
13C NMR (CDCl3): δ -0.90 and -0.14 (2s, SiMe3), 96.65 and
103.56 (2s, CtC), 128.77 (d, JC-P ) 10.6 Hz, meta CH Ph), 129.88
(s, CR′ Th), 130.47 (d, JC-P ) 2.3 Hz, para CH Ph), 130.47 (d,
JC-P ) 33.7 Hz, C-SiMe3 phosphirene), 131.14 (d, JC-P ) 16.2
Hz, ortho CH Ph), 131.77 (d, JC-P ) 11.3 Hz, CR Th), 132.07 (d,
CdC double bond of the phosphirene ring is a favorable factor
for the electronic delocalization along the chains containing the
phosphirene ring.
The UV-visible absorption spectra of diynes 2 and 3 and
phosphirenyl-thiophenes 4, 5, and 6 are shown in Figure 5.
The encouraging observation is that the grafting of the phos-
phinidene units onto the CtC triple bonds induces a red-shift
of the absorption maxima. We have also recorded some CV
data in acetonitrile solution (ref Ag/Ag+). Under comparable
conditions, [W(CO)5L] shows an irreversible oxidation wave
at +1.34 V (L ) CO), +0.81 V (L ) MeCN), and +1.04 V (L
) 1-phenyl-3,4-dimethylphosphole). Bis(2-thienyl)acetylene
displays two irreversible waves at +1.18 and +1.47 V. Complex
1 shows two irreversible waves at +0.98 and +1.40 V. By
comparison, we assign the first peak to the oxidation of W(CO)5
and the second peak to the oxidation of the chain. Even though
we are still far from the characteristics of a useful optoelectronic
polymer, we have all of the necessary synthetic tools to create
such a delocalized chain.
JC-P ) 2 Hz, CHâ Th), 133.71 (s, CHâ′ Th), 138.11 (d, JC-P
)
16.1 Hz, C-Th phosphirene), 138.75 (d, JC-P ) 6.3 Hz, ipso C
Ph), 196.19 (d, JC-P ) 8.7 Hz, CO), 197.93 (d, JC-P ) 32.1 Hz,
CO). The 13C NMR assignments have been made by comparison
with the 13C spectrum of a 1-alkyl-2-thienyl-3-trimethylsilylphos-
phirene complex (8). The huge polarity of the phosphirene double
1
bond and the strong JC-P couplings are noteworthy. Anal. Calcd
Experimental Section
for C25H25O5PSSi2W: C, 42.38; H, 3.56. Found: C, 42.31; H, 3.63.
Complex 5: obtained as a 50:50 mixture of two diastereomers
in 95% overall yield. 31P NMR (CH2Cl2): δ -164.2 and -164.8.
NMR spectra were recorded on a multinuclear Bruker AVANCE
300 MHz spectrometer operating at 300.13 for H, 75.47 for 13C,
1
and 121.50 MHz for 31P. Chemical shifts are expressed in parts
per million (ppm) downfield from internal tetramethylsilane (1H
(10) Marinetti, A.; Mathey, F.; Fischer, J.; Mitschler, A. J. Chem. Soc.,
Chem. Commun. 1982, 667.

Notes
Organometallics, Vol. 25, No. 21, 2006 5179
13C NMR (CDCl3): δ 0.00 (s, SiMe3), 129.64 (d, JC-P ) 10.1 Hz,
meta CH Ph), 131.57 (2d, para CH Ph), 132.10 (d, JC-P) 16.2 Hz,
ortho CH Ph), 133.87 and 134.02 (2 br s, CHâTh), 137.68 (d, JC-P
) 10.9 Hz, CR Th), 137.73 (d, JC-P ) 11.5 Hz, CR Th), 139.11 (d,
JC-P ) 16.1 C-Th phosphirene), 139.47 (d, JC-P ) 6.8 Hz, ipso
C Ph), 139.59 (d, JC-P ) 6.6 Hz, ipso C Ph), 197.09 and 197.11
(2d, JC-P ) 8.3 Hz, CO), 198.70 (d, JC-P ) 32.3 Hz, CO). The
13C resonances of the phosphirene C-SiMe3 carbons are partly
masked by the peaks corresponding to the â-carbons of the
thiophene ring.
Data collection for 4: pale yellow cube, 0.20 × 0.20 × 0.20
mm; triclinic, P1h, a ) 10.556(1) Å, b ) 10.720(1) Å, c ) 13.252-
(1) Å, R ) 104.060(1)°, â ) 92.010(1)°, γ ) 94.100(1)°, V )
1448.8(2) Å3, Z ) 2, Fcalc ) 1.624 g cm-3, µ ) 4.228 cm-1, F(000)
) 696, θmax ) 30.03°, hkl ranges -14 11; -12 15; -18 18, 12 420
data collected, 8425 unique data (Rint ) 0.0149), 8044 data with I
> 2σ(I), 323 parameters refined, GOF(F2) ) 1.017, final R indices
(R1 ) ∑||Fo| - |Fc||/∑|Fo|, wR2 ) [∑w(Fo2 - Fc2)2/∑w(Fo2)2]1/2),
R1 ) 0.0181, wR2 ) 0.0483, max./min. residual electron density
0.805(0.075)/-0.989(0.075) e A-3
.
Complex 6: obtained as a mixture of two diastereomers in 80%
overall yield. 31P NMR (CH2Cl2): δ -148.5 (major). 13C NMR
(CDCl3): δ 120.43 (m, C), 127.15 (d, JC-P ) 6.3 Hz, C), 128.23
(pseudo t, C), 129.14 (d, JC-P ) 10.5 Hz, meta Ph-P), 129.93 (s,
meta Ph-C), 130.84 (d, JC-P ) 5.1 Hz, ortho Ph-C), 131.35 (s,
para Ph-C), 131.53 (d, JC-P ) 2.2 Hz, para Ph-P), 131.64 (d,
JC-P ) 16.1 Hz, ortho Ph-P), 133.31 (br s, Câ Th), 135.44 (d,
Data collection for 5: yellow block, 0.20 × 0.20 × 0.20 mm;
monoclinic, P21/m, a ) 8.783(1) Å, b ) 31.771(1) Å, c ) 9.192-
(1) Å, â ) 101.970(1)°, V ) 2509.2(4) Å3, Z ) 2, Fcalc ) 1.734 g
cm-3, µ ) 4.995 cm-1, F(000) ) 1264, θmax ) 30.02°, hkl ranges
-12 12; -44 35; -12 12, 9389 data collected, 6849 unique data
(Rint ) 0.0182), 5601 data with I > 2σ(I), 245 parameters refined,
GOF(F2) ) 1.024, final R indices (R1 ) ∑||Fo| - |Fc||/∑|Fo|, wR2
) [∑w(Fo - Fc2)2/∑w(Fo2)2]1/2), R1 ) 0.0287, wR2 ) 0.0859,
2
JC-P ) 8.9 Hz, CR Th), 137.34 (m, ipso Ph-P), 196.11 (d, JC-P
)
8.3 Hz, cis CO), 197.80 (d, JC-P ) 31.5 Hz, trans CO). Anal. Calcd
for C42H22O10P2SW2: C, 43.93; H, 1.93. Found: C, 43.84; H, 1.81.
X-ray structure data: Nonius KappaCCD diffractometer, φ and
ω scans, Mo KR radiation (λ ) 0.71073 Å), graphite monochro-
mator, T ) 150 K, structure solution with SIR97,11 refinement
against F2 in SHELXL9712 with anisotropic thermal parameters for
all non-hydrogen atoms, calculated hydrogen positions with riding
isotropic thermal parameters.
max./min. residual electron density 1.506(0.129)/-1.633(0.129) e
A-3
.
Data collection for 6: yellow block, 0.20 × 0.18 × 0.18 mm;
triclinic, P1h, a ) 11.858(1) Å, b ) 12.283(1) Å, c ) 14.352(1) Å,
R ) 105.560(1)°, â ) 91.110(1)°, γ ) 91.840(1)°, V ) 2011.9(3)
Å3, Z ) 2, Fcalc ) 1.896 g cm-3, µ ) 5.902 cm-1, F(000) ) 1096,
θmax ) 30.03°, hkl ranges -16 16; -17 17; -19 20, 18 122 data
collected, 11 696 unique data (Rint ) 0.0199), 10 413 data with I
> 2σ(I), 515 parameters refined, GOF(F2) ) 1.150, final R indices
(R1 ) ∑||Fo| - |Fc||/∑|Fo|, wR2 ) [∑w(Fo2 - Fc2)2/∑w(Fo2)2]1/2),
R1 ) 0.0308, wR2 ) 0.0798, max./min. residual electron density
Data collection for 1: pale yellow block, 0.18 × 0.16 × 0.16
mm; triclinic, P1h, a ) 8.186(1) Å, b ) 10.799(1) Å, c ) 12.872-
(1) Å, R ) 93.410(1)°, â ) 91.550(1)°, γ ) 102.870(1)°, V )
2.443(0.143)/-1.343(0.143) e A-3
.
1106.39(19) Å3, Z ) 2, Fcalc ) 1.868 g cm-3, µ ) 5.511 cm-1
,
F(000) ) 596, θmax ) 30.03°, hkl ranges -11 11; -15 15; -18
18, 9668 data collected, 6423 unique data (Rint ) 0.0149), 5982
Acknowledgment. The authors thank Ecole Polytechnique,
the CNRS, and the University of California Riverside for the
financial support of this work. Many thanks also to Miss Me´lanie
Moreau (PMC Laboratory, Ecole Polytechnique), who recorded
the UV-vis spectra, and Mr. Jean-Pierre Pulicani (DCSO
Laboratory, Ecole Polytechnique), who recorded the CV data.
data with I > 2σ(I), 272 parameters refined, GOF(F2) ) 1.011,
2
final R indices (R1 ) ∑||Fo| - |Fc||/∑|Fo|, wR2 ) [∑w(Fo
-
Fc2)2/∑w(Fo2)2]1/2), R1 ) 0.0210, wR2 ) 0.0542, max./min. residual
electron density 0.853(0.096)/-1.051(0.096) e A-3
.
(11) Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, G.; Giacovazzo,
C.; Guagliardi, A.; Moliterni, A. G. G.; Polidori, G.; Spagna, R. SIR97, an
integrated package of computer programs for the solution and refinement
of crystal structures using single-crystal data.
(12) Sheldrick, G. M. SHELXL-97; Universita¨t Go¨ttingen: Go¨ttingen,
Germany, 1997.
Supporting Information Available: X-ray crystal structure
analyses of complexes 1, 4, 5, and 6. This material is available
free of charge via the Internet at http://pubs.acs.org.
OM060675W