Bis(2-pyridylimino)isoindole (BPI) ligands with novel linker units: Synthesis and characterization of their palladium and platinum complexes

Article abstract of DOI:10.1007/s00706-005-0368-x

With the aim of immobilizing bis(2-pyridylimino)isoindolate (BPI) ligands their backbone structure has been functionalized with several linker units. Their fixation was carried out at the stage of the phthalodinitrile precursor by nucleophilic ipso-substi

Full text of DOI:10.1007/s00706-005-0368-x

Monatshefte f€ur Chemie 136, 1693–1706 (2005)
DOI 10.1007/s00706-005-0368-x
Bis(2-pyridylimino)isoindole (BPI)
Ligands with Novel Linker Units: Synthesis
and Characterization of Their Palladium
and Platinum Complexes
ꢀ
€
Anorganisch-Chemisches Institut, Universitat Heidelberg, 69120 Heidelberg, Germany
Markus Meder, Christian H. Galka, and Lutz H. Gade
Received March 9, 2005; accepted March 22, 2005
Published online September 26, 2005 # Springer-Verlag 2005
Summary. With the aim of immobilizing bis(2-pyridylimino)isoindolate (BPI) ligands their backbone
structure has been functionalized with several linker units. Their fixation was carried out at the stage of
the phthalodinitrile precursor by nucleophilic ipso-substitution of 4-nitrophthalodinitrile. Subsequent
synthesis of the functionalized phthalodinitriles with two molar equivalents of the 2-aminopyridine
derivatives gave the corresponding BPI ligands. Reaction of the ethyleneglycol functionalized BPI
derivative with the zeroth generation carbosilane dendrimer [G-0]4-exo-Cl yielded the functionalized
dendrimer [G-0]4-exo-[O(CH2)2O]-10-MeBPI (7). The synthesis of the palladium complexes was car-
ried out by reaction of the protioligands with [(PhCN)2PdCl2] in benzene using triethylamine as
auxiliary base whereas the first examples of BPI-platinum complexes were prepared using
[(COD)PtCl2] as starting material.
Keywords. Palladium; Platinum; Ligand design; Dendrimers.
Introduction
The aim of the extensive studies towards the immobilization of molecular catalysts
has been the development of catalytic phases which combine the virtues of homo-
geneous catalysis (high activity and selectivity, directed catalyst design) with those
of heterogeneous catalysts (e.g. facile catalyst separation and recycling) [1]. The
results obtained in this field have revealed that leaching of the metal is a major
practical problem, regardless of the method of catalyst fixation and the nature of
the support material [2]. This may be suppressed to various degrees by using
polydentate ligands which form thermally and kinetically stable complexes with
the catalyst metal. A second problem frequently encountered when using immo-
bilized phosphorus-based ligands is their propensity to be oxidized if exposed to air
ꢀ
Corresponding author. E-mail: lutz.gade@uni-hd.de

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M. Meder et al.
Formula 1
over extended periods of time. This has set limits to their recycling potential and
has encouraged research into non-phosphorus-containing (in particular, hydrogena-
tion) catalysts which combine molecular stability with sufficient activity [3].
We have recently begun to study the catalytic activity of palladium complexes
containing derivatives of the well established bis(2-pyridylimino)isoindolate (BPI)
ligands (Formula 1) [4]. These BPI-palladium compounds have proved to be a
promising new non-phosphine based class of molecular hydrogenation catalysts
for alkenes. Prior to this work, the tridentate BPI ligands have been extensively
studied in oxidation catalysis induced by the middle and late transition metals
[5–13]. However, the use of such systems in heterogenized metal catalysts requires
the functionalization of their backbone structure, introducing an appropriate linker
unit. In this work we report the preparation of such modified BPI ligands and the
synthesis of their palladium and platinum complexes.
Results and Discussion
Synthesis of the Bis(2-pyridylimino)isoindole (BPI) Ligands
with Linker Units
The fixation of linker units at the ligand framework of bis(2-pyridylimino)isoindole
was carried out at the stage of the phthalodinitrile precursor. As Brewis et al. have
shown in their synthesis of phthalocyanines at the core of polyarylether dendrimers
[14], the introduction of such linkers is readily achieved by the nucleophilic sub-
stitution of 4-nitrophthalodinitrile with the in situ generated alcoholates. The synthe-
sis of the BPI ligands was subsequently achieved by stirring the functionalized
phthalodinitriles with two molar equivalents of the 2-aminopyridine derivatives in
the presence of CaCl2 in hexanol under reflux for 20–25 h to give the protioligands
displayed in Scheme 1 as yellow microcrystalline solids.
Reaction of the ethyleneglycol functionalized BPI derivative 5 with the zeroth
generation carbosilane dendrimer [G-0]4-exo-Cl [15] using LDA as a base in THF
cleanly yielded the functionalized dendrimer [G-0]4-exo-[O(CH2)2O]-10-MeBPI (7)
(Scheme 2). The base LDA was employed due to the instability of the BPI ligands
towards alkyllithium reagents and the non-reactivity of NaH towards 5. With the
preparation of compound 7 we have shown the possibility of attaching BPI systems
to carbosilane dendrimers similar to the immobilization of polydentate phosphines
which we reported previously [16].

Bis(2-pyridylimino)isoindole Ligands
1695
Scheme 1
Scheme 2
1
In the H NMR spectrum of the dendritic compound the resonance of the
Si(CH3)2 groups is detected at 0.14 ppm, the corresponding 13C NMR chemical
shift being ꢁ1.8 ppm while there are practically no coordination shifts of the

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M. Meder et al.
signals assigned to the BPI units. The 29Si NMR signals were observed at ꢀ ¼ 0.4
(core) and 18.8 ppm [Si(CH3)2]. The molecular ion peak in the FAB mass spectrum
of 7 was found at m=z ¼ 1974.9 confirming the completeness of the ligand fixation
to the [G-0] carbosilane dendrimer.
Synthesis and Structural Characterization of BPI-Palladium Complexes
with Linker Units
The synthesis of the palladium complexes was carried out as reported previously
by reaction of the protioligands with [(PhCN)2PdCl2] in benzene using triethyl-
amine as auxiliary base (Scheme 3). The metallation of the BPI protioligands is
conveniently followed by 1H and 13C NMR spectroscopy. The coordination shift of
the signals attributed to the protons in ꢁ-position of the pyridyl substituents from
around 8.4 to ca. 9.5 ppm along with the disappearance of the NH-resonance of the
isoindol unit are particularly diagnostic.
Scheme 3
ꢂ
˚
Fig. 1. a) Molecular structure of complex 8; principal bond lengths (A) and angles ( ): Pd–N3
1.965(5), N3–Pd–N5 89.7(2), Pd–N5 2.068(6), N3–Pd–N1 88.5(2), Pd–N1 2.057(6), N5–Pd–N1
175.1(2), Pd–Cl 2.332(2), N3–Pd–Cl 173.1(1), C9–O 1.369(8), N5–Pd–Cl 91.4(2), O–C20 1.459(9),
N1–Pd–Cl 90.9(2), C20–C21 1.48(1), C9–O–C20 118.0(6), C22–C23 1.18(2), C21–C22–C23
140(1); b) view of the packing of compound 8 in the crystal

Bis(2-pyridylimino)isoindole Ligands
1697
In order to establish the structural details of the palladium complexes a single
crystal X-ray diffraction study of one derivative, complex 8, was carried out. Its
molecular structure is displayed in Fig. 1a along with the principal bond lengths
˚
and angles. As we have found previously, the amido-type Pd–N3 bond [1.957(6) A]
˚
is ca. 0.1 A shorted than the metal–nitrogen bonds of the neutral pyridyl donor
˚
units, while the Pd–Cl bond length of 2.332(3) A is comparable to palladium–Cl
distances reported in the literature [17].
The coordination geometry around the metal centre deviates slightly from the
ideal square planar arrangement as reflected in the N3–Pd–Cl angle of 173.1(1)ꢂ.
A closer inspection of the molecular packing of the complexes in the unit cell in
Fig. 1b reveals the formation of a stacked arrangement of a type not observed for
other BPI complexes.
Synthesis and Structural Characterization of BPI-Platinum Complexes
The extension of the synthetic method employed for the palladium complexes to
their heavier Pt congeners by reaction of the protioligands with [(PhCN)2PtCl2]
proved to be hampered by the greater kinetic inertness of the precursor complex.
However, using [(COD)PtCl2] as an alternative starting material led to the prepara-
tion of the first BPI-platinum complexes (Scheme 4).
As previously observed for the BPI-palladium complexes the platinum ana-
logues with no or only small substituents at the BPI ligands proved to be only
sparingly soluble. It was therefore not possible to record a 13C NMR spectrum of
the unsubstituted derivative 11 even at 353 K in DMSO. Complex 11 was never-
theless adequately characterized by the usual analytical and spectroscopic methods.
A useful spectroscopic probe is again the significant coordination shift of the ꢁ-
pyridyl protons from 8.5 ppm in the protioligand to values around 10 ppm observed
3
for the complexes, as well as their J(195Pt–1H) coupling of ca. 19 Hz with the
metal nucleus. In order to establish the structural details of these first examples of
BPI-platinum complexes, a single crystal X-ray structure analysis of compound 13
was carried out. Its molecular structure is displayed in Fig. 2 along with the
principal bond lengths and angles.
Scheme 4

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M. Meder et al.
ꢂ
˚
Fig. 2. Molecular structure of complex 13; principal bond lengths (A) and angles ( ): Pt–N3
1.966(3), N3–Pt–N5 89.50(15), Pt–N5 2.049(4), N3–Pt–N1 88.65(15), Pt–N1 2.060(4), N5–Pt–
N1 178.57(13), Pt–Cl 2.335(2), N3–Pt–Cl 170.14(12), N5–Pt–Cl 89.12(11), N1–Pt–Cl 91.92(11)
Complex 13 possesses the expected square planar geometry with Pt–N
˚
distances of ca. 2 A and a Pt–Cl bond length of 2.335(2) A which is compara-
˚
ble to the literature data for platinium(II) complexes [18].
Conclusions
The attachment of linkers to the BPI ligand system by nucleophilic ipso-substitu-
tion at the 4-nitrophthalodinitrile precursor stage has proved to be straightforward
and may serve as a general approach to the immobilization of their complexes.
This is of considerable interest due to the observed activity of the palladium com-
plexes in the hydrogenation of olefins at ambient dihydrogen pressure [4a, c] and
thus the possibility of recycling such catalysts at the end of the conversion. Our
current and future activities in this area are aimed at the development of recyclable
BPI-Pd catalysts based on the methodology presented in this paper.
Experimental Section
All manipulations were performed under nitrogen. Solvents were dried according to standard methods
and saturated with nitrogen. The deuterated solvents used for the NMR spectroscopic measurements
˚
were degassed by three successive ‘‘freeze–pump–thaw’’ cycles and stored over 4 A molecular sieves.
Solids were separated from suspensions by filtration through dried Celite or by centrifugation. The 1H,
13C, and 29Si NMR spectra were recorded on Bruker AC 200, Bruker Avance 250, and Bruker AMX
400 FT-NMR spectrometers. Infrared spectra were recorded on a Nicolet Magna IRTM 750 spectro-
meter. Elemental analyses were carried out by the microanalytical service at the chemistry department
at Strasbourg; results agreed favourably with calculated values. [(PhCN)2PdCl2] [19], [(COD)PtCl2]
[20], THP–OCH2CH2OH [21] were prepared according to published procedures. All other chemicals
used as starting materials were obtained commercially and used without further purification.
4-(3-Butenoxy)phthalodinitrile (1, C12H10N2O)
4-Nitrophthalodinitrile (1.00 g, 5.77mmol) and K2CO3 (1.59 g, 11.5mmol) were dissolved in DMF
(25 cm3) and heated to 50ꢂC. 3-Butenol (0.83 g, 11.5mmol) was added over a period of 30min, the

Bis(2-pyridylimino)isoindole Ligands
1699
reaction mixture was stirred at 50ꢂC for another 20h and then cooled to room temperature. After the
addition of water (100cm3) the mixture was extracted with toluene, the extract dried over MgSO4, and
the reaction product obtained as a colourless solid after removal of the solvent in vacuo. Yield 1.02g
(5.14 mmol, 89%); mp 49ꢂC; 1H NMR (300.17 MHz, CDCl3, 298 K): ꢀ ¼ 2.56 (dt, 3JHH ¼ 6.5 Hz, 2H,
OCH2CH2), 4.01 (t, 3JHH ¼ 6.5 Hz, 2H, OCH2), 5.15 (m, 2H, ¼CH2), 5.83 (m, 1H, ¼CH–), 7.19 (dd,
3JHH ¼ 8.8 Hz, 4JHH ¼ 2.8 Hz, 1H, 5-H), 7.22 (d, 4JHH ¼ 2.8 Hz, 1H, 3-H), 7.69 (d, 3JHH ¼ 8.8 Hz, 1H,
6-H) ppm; {1H}13C NMR (75.5 MHz, CDCl3, 298 K): ꢀ ¼ 32.9 (OCH2CH2), 68.3 (OCH2), 106.8 (C-
1), 115.2 (C-7), 115.6 (C-7), 117.1 (C-2), 117.8 (¼CH2), 119.2 (C-3), 119.6 (C-5), 133.1 (¼C(H)–),
135.1 (C-6), 161.9 (C-4) ppm; IR (KBr): ꢂꢀ¼ 3080 (w), 2990 (w), 2933 (m), 2896 (w), 2229 (s), 1644
(m), 1602 (s), 1562 (s), 1486 (s), 1465 (m), 1430 (w), 1397 (m), 1309 (s), 1251 (s), 1172 (m), 1095 (s),
1009 (m), 988 (m), 923 (m), 884 (m), 840 (m), 801 (vw), 723 (vw), 641 (w), 560 (vw), 523 (s) cmꢁ1
.
4-(THP–OCH2CH2O)phthalodinitrile (2a, C15H16N2O3)
4-Nitrophthalodinitrile (5.00 g, 28.9mmol) and K2CO3 (7.98 g, 57.8mmol) were dissolved in DMF
(50 cm3) and heated to 50ꢂC. The protected alcohol THP–OCH2CH2OH (8.44 g, 57.8mmol) was
added over a period of 30 min, the reaction mixture stirred at 50ꢂC for another 20h and then cooled
to room temperature. After the addition of water (100cm3) the mixture was extracted with toluene and
the reaction product obtained as a colourless solid after removal of the solvent in vacuo. Yield 6.45g
(23.6mmol, 82%); mp 75ꢂC; 1H NMR (300.17 MHz, CDCl3, 298K): ꢀ ¼ 1.76–1.50 (m, 6H, e-H, f-H,
g-H), 3.48 (m, 1H, d-Haxial), 3.78 (m, 2H, b-H), 4.04 (m, 1H, d-Hequat), 4.23 (m, 2H, a-H), 4.63 (m, 1H,
3
4
4
c-H), 7.21 (dd, JHH ¼ 8.7 Hz, JHH ¼ 2.6 Hz, 1H, 5-H), 7.31 (d, JHH ¼ 2.6Hz, 1H, 3-H), 7.67 (d,
3JHH ¼ 8.7 Hz, 1H, 6-H) ppm; {1H}13C NMR (50.3 MHz, CDCl3, 295 K): ꢀ ¼ 19.3 (C-f), 25.2 (C-e),
30.4 (C-d), 62.4 (C-g), 65.4 (C-b), 68.6 (C-a), 99.2 (C-c), 107.3 (C-1), 115.2 (C-7), 115.6 (C-7), 117.3
(C-2), 119.6 (C-3), 119.8 (C-5), 135.1 (C-6), 162.1 (C-4) ppm; IR (KBr): ꢂꢀ¼ 3082 (w), 2936 (m),
2872 (w), 2230 (s), 1601 (s), 1562 (m), 1490 (m), 1452 (vw), 1431 (vw), 1353 (vw), 1312 (s), 1288
(w), 1256 (s), 1200(w), 1180 (w), 1144 (m), 1123 (m), 1089 (m), 1082 (m), 1046 (m), 1023 (m), 985
(s), 873 (w), 835 (m), 816 (w) cmꢁ1
.
4-(HOCH2CH2O)phthalodinitrile (2b, C10H8N2O2)
The THP-protected phthalodinitrile 2a was suspended in 50cm3 of methanol and subsequently treated
with 10 cm3 of HCl=Et2O. After stirring at ambient temperature for 12h the volatiles were removed in
vacuo and the residue dissolved in water. By slow addition of an aqueous solution of K2CO3 a pH of 7
was obtained and the aqueous phase extracted several times with CH2Cl2. The combined organic
extracts were dried over MgSO4 and upon removal of the solvents in vacuo compound 2b was obtained
as an analytically pure colourless crystalline (needles) solid. Yield 4.31g (22.9mmol, 97%); mp 97ꢂC;
3
1H NMR (300.17 MHz, CDCl3, 298 K): ꢀ ¼ 2.31 (s, br, 1H, –OH), 3.96 (t, JHH ¼ 4.6 Hz, 2H, b-H),
3
3
4
4
4.13 (t, JHH ¼ 4.6 Hz, 2H, a-H), 7.20 (dd, JHH ¼ 8.7 Hz, JHH ¼ 2.6Hz, 1H, 5-H), 7.26 (d, JHH
¼
2.6 Hz, 1H, 3-H), 7.68 (d, JHH ¼ 8.7 Hz, 1H, 6-H) ppm; {1H}13C NMR (50.3 MHz, CDCl3, 295 K):
ꢀ ¼ 60.5 (C-b), 70.3 (C-a), 107.2 (C-1), 115.2 (C-7), 115.6 (C-7), 117.1 (C-2), 119.4 (C-3), 119.6 (C-
5), 135.2 (C-6), 161.8 (C-4) ppm; IR (KBr): ꢂꢀ¼ 3307 (m, br), 3082 (w), 2962 (m), 2235 (s), 1599 (s),
1564 (s), 1496 (s), 1452 (w), 1427 (vw), 1313 (s), 1293 (m), 1260 (s), 1100 (m), 1070 (m), 1044 (m),
3
961 (w), 898 (m), 854 (m), 727 (w) cmꢁ1
.
4-Me-10-tBuBPI (3, C27H31N5)
4-Methylphthalodinitrile (1.50 g, 10.6mmol), 2-amino-4-tbutylpyridine (3.96 g, 26.1mmol), and CaCl2
(0.16 g, 1.36 mmol) were suspended in 1-hexanol (50 cm3) and heated at reflux for 18h. After cooling
to room temperature the reaction product was isolated as a yellow solid (yellow needles) washed with
water and dried over P4O10. Yield 2.53g (5.94 mmol, 56%); mp 204ꢂC; 1H NMR (400.16 MHz, C6D6,
298 K): ꢀ ¼ 1.1, 1.2 (2s, 2ꢃ9H, 10-tBu), 2.05 (s, 3H, 4-CH3), 6.84 (m, 2H, 11-H), 6.94 (d, br,
3
3JHH ¼ 7.9 Hz, 1H, 5-H), 7.72 (m, 2H, 9-H), 8.02 (s, br, 1H, 3-H), 8.12 (d, JHH ¼ 7.9 Hz, 1H, 6-H),
3
8.60 (d, JHH ¼ 5.3 Hz, 2H, 12-H), 11.91 (s, br, 1H, N–H) ppm; {1H}13C NMR (100.6MHz, C6D6):

1700
M. Meder et al.
ꢀ ¼ 21.6 (4-CH3), 30.4 (10-C(CH3)3), 34.5 (10-C(CH3)3), 117.7 (C-11), 121.1 (C-9), 122.9 (C-5),
123.6 (C-6), 132.8 (C-3), 137.2 (C-1, C-2), 141.9 (C-4), 148.1 (C-12), 154.1 (C-7), 161.8 (C-8, C-
10) ppm; IR (KBr): ꢂꢀ¼ 3237 (m, br), 2962 (m), 2867 (w), 1633 (m), 1590 (s), 1534 (w), 1477 (w),
1401 (w), 1365 (w), 1354 (w), 1310 (vw), 1285 (w), 1265 (w), 1219 (w), 1201 (vw), 1180 (vw), 1108
(vw), 1037 (vw), 928 (m), 890 (m), 826 (m), 716 (m) cmꢁ1
.
4-(3-Butenoxy)-10-MeBPI (4, C24H23N5O)
4-(3-Butenoxy)phthalodinitrile (1, 1.00 g, 5.05mmol), 2-amino-4-methylpyridine (1.37 g, 12.6mmol),
and CaCl2 (0.16 g, 1.36mmol) were suspended in 1-hexanol (80 cm3) and heated at reflux for 72h.
After cooling to room temperature the reaction product was isolated as a yellow solid (yellow needles)
washed with water and dried over P4O10. Yield 1.04 g (2.62 mmol, 52%); mp 127ꢂC; 1H NMR
(300.17 MHz, CDCl3, 298 K): ꢀ ¼ 2.36 (s, 6H, 10-CH3), 2.58 (m, 2H, OCH2CH2), 4.15 (t,
3JHH ¼ 6.9 Hz, 2H, –OCH2–), 5.14 (m, 2H, ¼CH2), 5.90 (m, 1H, ¼C(H)–), 6.89 (m, 2H, 11-H),
7.12 (dd, 3JHH ¼ 8.3 Hz, 4JHH ¼ 2.2 Hz, 1H, 5-H), 7.24 (s, br, 2H, 9-H), 7.52 (d, 4JHH ¼ 2.2 Hz, 1H, 3-
H), 7.98 (d, 3JHH ¼ 8.3 Hz, 1H, 6-H), 8.43 (m, 2H, 12-H), 10.90 (s, br, 1H, NH) ppm; {1H}13C NMR
(75.5MHz, CDCl3, 298 K): ꢀ ¼ 20.9 (10-CH3), 33.4 (OCH2CH2–), 67.7 (OCH2), 106.4 (C-3), 117.2
(¼CH2), 119.6 (C-5), 121.0=121.2 (C-9), 123.4=123.5 (C-11), 123.7 (C-6), 128.0 (C-1), 134.0
(¼C(H)–), 137.9 (C-2), 147.3=147.4 (C-12) 149.1 (C-10), 153.6 (C-7), 160.3=160.5 (C-8), 162.2
(C-4) ppm; IR (KBr): ꢂꢀ¼ 3219 (vw), 3042 (vw), 2923 (vw), 2863 (vw), 1630 (s), 1584 (s), 1541
(m), 1488 (m), 1463 (m), 1352 (w), 1328 (m), 1276 (w), 1235 (s), 1195 (vw), 1162 (w), 1100 (m),
1033 (s), 918 (vw), 836 (vw), 813 (w), 714 (vw), 456 (w) cmꢁ1
.
4-(2-Hydroxyethanoxy)-10-MeBPI (5, C22H21N5O2)
4-(2-Hydroxyethanoxy)phthalodinitrile (2a, 1.00g, 5.34 mmol), 2-amino-4-methylpyridine (1.44 g,
13.4mmol), and CaCl2 (0.16 g, 1.36 mmol) were suspended in 1-hexanol (50 cm3) and heated at reflux
for 72h. After cooling to room temperature the reaction product was isolated as a yellow solid (needle-
shaped crystals), washed with water, and dried over P4O10. Yield 1.26 g (3.36 mmol, 61%); mp 202ꢂC;
1H NMR (300.17 MHz, d6-DMSO, 298 K): ꢀ ¼ 2.35, 2.36 (2s, 2ꢃ3H, 10-CH3), 3.78 (m, 2H,
3
3
OCH2CH2), 4.18 (t, JHH ¼ 4.7Hz, 2H, –OCH2–), 4.96 (t, JHH ¼ 5.6Hz, 1H, –OH), 7.07 (m, 2H,
11-H), 7.24 (m, 3H, 5-H, 9-H), 7.43 (d, 4JHH ¼ 2.3Hz, 1H, 3-H), 7.86 (d, 3JHH ¼ 8.5 Hz, 1H, 6-H), 8.50
(m, 2H, 12-H), 8.99 (s, br, 1H, NH) ppm; {1H}13C NMR (100.6MHz, d6-DMSO, 298K): ꢀ ¼ 20.3 (10-
CH3), 59.4 (HOCH2–), 70.3 (–CH2O–), 106.4 (C-3), 119.5 (C-5), 121.4=121.6 (C-9), 123.1=123.3 (C-
11), 123.7 (C-6), 127.1 (C-1), 137.2 (C-2), 147.5=147.6 (C-12), 149.3 (C-10), 152.3 (C-7),
159.5=159.7 (C-8), 162.1 (C-4) ppm; IR (KBr): ꢂꢀ¼ 3208 (vw), 2920 (vw), 1634 (s), 1596 (s), 1543
(m), 1485 (m), 1467 (m), 1365 (m), 1327 (vw), 1295 (w), 1286 (w), 1245 (m), 1230 (m), 1195 (vw),
1169 (m), 1119 (w), 1057 (vw), 1032 (vw), 927 (m), 813 (m), 720 (w) cmꢁ1
.
4-(2-Hydroxyethanoxy)-10-tBuBPI (6, C28H33N5O2)
4-(2-Hydroxyethanoxy)phthalodinitrile (2b, 0.59 g, 3.14mmol), 2-amino-4-tbutylpyridine (1.18 g,
7.85mmol), and CaCl2 (0.07 g, 0.68 mmol) were suspended in 1-hexanol (50 cm3) and heated at reflux
for 18 h. After cooling to room temperature the reaction product was isolated as a yellow solid
1
(needles) washed with water and dried over P4O10. Yield 0.67 g (1.41 mmol, 45%); mp 210ꢂC; H
3
NMR (400.16 MHz, CD2Cl2, 298 K): ꢀ ¼ 1.36 (s, 18H, 10-C(CH3)3), 4.00 (t, JHH ¼ 4.2 Hz, 2H,
3
HOCH2–), 4.24 (t, JHH ¼ 4.2 Hz, 2H, –OCH2–), 7.15 (m, 3H, 5-H, 11-H), 7.42 (m, 2H, 9-H), 7.53
3
(s, br, 1H, 3-H), 7.90 (d, JHH ¼ 8.5 Hz, 1H, 6-H), 8.21 (s, br, 1H, NH), 8.51 (m, 2H, 12-H) ppm;
{1H}13C NMR (100.6 MHz, CD2Cl2, 298 K): ꢀ ¼ 30.4 (10-C(CH3)3), 34.8 (10-C(CH3)3), 61.2
(HOCH2–), 70.2 (–CH2O–), 106.4 (C-3), 117.6=117.8 (C-9), 119.4 (C-5), 119.9=120.0 (C-11),
123.7 (C-6), 128.5 (C-1), 138.2 (C-2), 147.6=147.7 (C-12), 153.2 (C-7), 160.6=160.7 (C-8), 162.1
(C-4), 162.5=162.6 (C-10) ppm; IR (KBr): ꢂꢀ¼ 3244 (w, br), 2962 (m), 2869 (w), 1633 (s), 1590 (s),
1536 (m), 1488 (m), 1477 (m), 1401 (w), 1366 (m), 1355 (w), 1327 (m), 1295 (w), 1286 (w), 1245 (m),
1225 (m), 1113 (w), 1085 (vw), 1051 (w), 915 (w), 834 (w), 720 (w) cmꢁ1
.

Bis(2-pyridylimino)isoindole Ligands
1701
[G-0]4-exo-4-[O(CH2)2O]-10-MeBPI (7, C108H128N20O8Si5)
To a solution of tetraallylsilane (38.5 mg, 0.20 mmol) in 1 cm3 of benzene were added 1 cm3 of di-
methylchlorosilane and a few drops of a solution of Karsted’s catalyst, and the reaction mixture was
subsequently stirred at 50ꢂC for 12 h. After removal of the volatiles the zeroth generation [G-0]4-exo-Cl
was obtained as a light brown oil which was used without further purification. In a separate re-
action vessel 0.31g (0.80 mmol) of Si{(CH2)3SiMe2Cl}4 were dissolved in 80cm3 of THF and then
cooled to ꢁ80ꢂC. After the dropwise addition of 0.4 cm3 of a 2 M solution of LDA in THF, the
reaction mixture was warmed to ꢁ40ꢂC and stirred for 30min. After recooling to ꢁ80ꢂC a solution
of [G-0]4-exo-Cl in benzene was added, the reaction mixture subsequently warmed to ambient tem-
perature and stirred for another 16 h. After removal of the volatiles in vacuo and redissolution in
benzene, the insoluble components were removed by centrifugation and the solvents removed in vacuo.
The clear yellow oil was washed several times with n-pentane and then dried in vacuo to give 7 as an
1
amorphous yellow solid. Yield 0.36 g (0.18 mmol, 91%); mp 61ꢂC; H NMR (300.17 MHz, CDCl3,
298 K): ꢀ ¼ 0.14 (s, 24H, c-H), 0.68 (m, 8H, f-H), 0.71 (m, 8H, d-H), 1.41 (m, 8H, e-H), 2.34 (s, 24H,
10-CH3), 3.95 (t, 3JHH ¼ 5.0 Hz, 8H, b-H), 4.15 (t, 3JHH ¼ 5.0 Hz, 8H, a-H), 6.89 (m, 8H, 11-H), 7.11
(m, 4H, 5-H), 7.22 (m, 8H, 9-H), 7.47 (d, 4JHH ¼ 2.2 Hz, 4H, 3-H), 7.88 (d, 3JHH ¼ 8.1 Hz, 4H, 6-H),
8.41 (m, 8H, 12-H), 13.81 (s, br, 4H, NH) ppm; {1H}13C NMR (75.5 MHz, CDCl3, 298 K): ꢀ ¼ ꢁ1.8
(C-c), 17.2=17.9 (C-d, C-f), 20.9 (10-CH3), 21.2 (C-e), 61.3 (C-b), 69.9 (C-a), 106.5 (C-3), 119.6
(C-5), 121.0=121.2 (C-9), 123.4=123.6 (C-11), 123.7 (C-6), 128.2 (C-1), 138.0 (C-2), 147.4=147.5
(C-12), 149.1 (C-10), 153.6 (C-7), 160.5=160.6 (C-8), 162.2 (C-4) ppm; {1H}29Si NMR (79.5MHz,
CDCl3, 298 K): ꢀ ¼ 0.4 (Si(CH2)–), 18.8 (Si–O) ppm; IR (KBr): ꢂꢀ¼ 3420 (m, br), 2948 (w), 2914 (w),
2862 (w), 1631 (s), 1591 (s), 1543 (m), 1486 (m), 1466 (m), 1400 (vw), 1359 (w), 1328 (w), 1280 (w),
1243 (m), 1191 (vw), 1163 (w), 1100 (m), 924 (vw), 822 (m), 717 (vw), 457 (m) cmꢁ1; MS (FAB):
m=z ¼ 1974.9 [M].
(4-(HOCH2CH2–)-10-MeBPI)PdCl (8, C22H20ClN5O2Pd)
4-(2-Hydroxyethanoxy)-10-MeBPI (5, 0.12 g, 0.30 mmol) and (PhCN)2PdCl2 (0.13 g, 0.33mmol) were
dissolved in benzene (10 cm3) and NEt3 (33.0 mg, 0.33mmol) was then added to this solution which
was subsequently stirred at room temperature for 15h. The crude palladium complex and NEt3HCl
were isolated by filtration, the ammonium salt was removed by extraction with water, and the reaction
product was recrystallized from CH2Cl2=n-hexane, giving 8 as a yellow microcrystalline solid. Yield
1
0.11g (0.21 mmol, 69%); mp 151ꢂC; H NMR (300.17 MHz, d6-DMSO, 298 K): ꢀ ¼ 2.32, 2.33 (s,
3
3ꢃ3H, 10-CH3), 3.78 (m, 2H, –OCH2CH2), 4.06 (t, JHH ¼ 4.7 Hz, 2H, –OCH2–), 4.97 (t,
3
3JHH ¼ 5.5 Hz, 1H, –OH), 6.94 (m, 3H, 5-H, 11-H), 7.12 (m, 3H, 3-H, 9-H), 7.53 (d, JHH ¼ 8.0 Hz,
1H, 6-H), 9.29 (m, 2H, 12-H) ppm; {1H}13C NMR (75.5 MHz, d6-DMSO, 298 K): ꢀ ¼ 19.9 (10-CH3),
59.4 (HOCH2–), 69.9 (–CH2O–), 106.0 (C-3), 118.3 (C-5), 120.8=121.0 (C-9), 123.0 (C-6),
126.1=126.2 (C-11), 128.9 (C-1), 138.2 (C-2), 150.2=150.4=151.1 (C-7=C-8=C-10), 152.0 (C-12),
161.5 (C-4) ppm; IR (KBr): ꢂꢀ¼ 3214 (w, br), 2922 (w), 2850 (w), 1634 (m), 1579 (s), 1515 (m),
1470 (m), 1366 (w), 1331 (w), 1292 (w), 1233 (w), 1078 (w, br), 1027 (vw), 819 (m), 748 (vw), 716
(vw), 669 (vw) cmꢁ1
.
(4-(HOCH2CH2–)-10-tBuBPI)PdCl (9, C28H32ClN5O2Pd)
4-(2-Hydroxyethanoxy)-10-tBuBPI (6, 0.20 g, 0.50 mmol) and (PhCN)2PdCl2 (0.21 g, 0.55 mmol) were
dissolved in benzene (10 cm3) and NEt3 (56.0 mg, 0.55mmol) was then added to this solution which
was subsequently stirred at room temperature for 15h. The crude palladium complex and NEt3HCl
were isolated by filtration, the ammonium salt was removed by extraction with water, and the reaction
product was recrystallized from CH2Cl2=n-hexane, giving 9 as a yellow microcrystalline solid. Yield
1
0.13g (0.21 mmol, 88%); mp 165ꢂC; H NMR (400.16 MHz, CD2Cl2, 298 K): ꢀ ¼ 1.39 (s, 18H,
3
3
10-tBu), 2.53 (s, br, 1H, –OH), 3.99 (t, JHH ¼ 4.4 Hz, 2H, HOCH2–), 4.22 (t, JHH ¼ 4.4Hz, 2H,
4
–OCH2–), 7.05 (m, 3H, 5-H, 11-H), 7.39 (d, JHH ¼ 2.1 Hz, 1H, 3-H), 7.45=7.48 (2d, 2ꢃ
3
3
4JHH ¼ 2.1 Hz, 2ꢃ1H, 9-H), 7.72 (d, JHH ¼ 8.2 Hz, 1H, 6-H), 9.62 (d, JHH ¼ 6.7Hz, 2H,

1702
M. Meder et al.
12-H) ppm; {1H}13C NMR (100.6MHz, CD2Cl2, 298 K): ꢀ ¼ 31.5 (10-C(CH3)3), 36.4 (10-C(CH3)3),
62.7 (HOCH2–), 71.7 (–CH2O–), 108.4 (C-3), 119.1=119.3 (C-9), 120.1 (C-5), 124.4=124.5 (C-11),
124.9 (C-6), 131.9 (C-1), 141.6 (C-2), 153.3=153.4 (C-7), 154.1=154.2 (C-12), 154.7=154.8 (C-8),
163.5 (C-4), 165.3=165.4 (C-10) ppm; IR (KBr): ꢂꢀ¼ 3244 (w, br), 2961 (m), 2904 (w), 2868 (w), 1602
(s), 1579 (s), 1520 (m), 1505 (m), 1480 (s), 1403 (m), 1367 (s), 1330 (m), 1269 (m), 1251 (w), 1230
(m), 1187 (m), 1145 (m), 1105 (s), 1078 (m), 925 (m) cmꢁ1
.
(4-(3-Butenoxy)-10-MeBPI)PdCl (10, C24H22ClN5OPd)
4-(3-Butenoxy)-10-MeBPI (12, 0.20 g, 0.50 mmol) and (PhCN)2PdCl2 (0.21 g, 0.55mmol) were dis-
solved in benzene (10 cm3) and NEt3 (56.0mg, 0.55mmol) was then added to this solution. After
stirring for 15 h the volatiles were removed in vacuo, the residue was extracted with benzene, and the
NEt3HCl formed in the reaction was removed by filtration through Celite. The solvent of the filtrate
was evaporated in vacuo, the yellow solid residue extracted with water and n-hexane, and then
recrystallized from CH2Cl2=n-hexane to give the pure palladium complex 10. Yield 0.22g (0.41 mmol,
1
81%); mp 166ꢂC; H NMR (300.17 MHz, CDCl3, 298K): ꢀ ¼ 2.37 (s, 6H, 10-CH3), 2.59 (m, 2H,
OCH2CH2), 4.12 (t, 3JHH ¼ 6.6 Hz, 2H, –OCH2–), 5.20 (m, 2H, ¼CH2), 5.92 (m, 1H, ¼C(H)–), 6.78
(m, 2H, 11-H), 6.97 (d, br, 3JHH ¼ 8.1 Hz, 1H, 5-H), 7.26 (s, br, 2H, 9-H), 7.35 (s, br, 1H, 3-H), 7.74 (d,
3JHH ¼ 8.1 Hz, 1H, 6-H), 9.57 (m, 2H, 12-H) ppm; {1H}13C-NMR (75.5 MHz, CDCl3, 298K):
ꢀ ¼ 20.6 (10-CH3), 33.5 (OCH2CH2–), 67.7 (OCH2), 106.7 (C-3), 117.3 (¼CH2), 118.8 (C-5),
120.9=121.0 (C-9), 123.6 (C-6), 126.3=126.4 (C-11), 129.8 (C-1), 134.1 (¼C(H)–), 139.7 (C-2),
150.9 (C-10), 151.3 (C-7=C-8), 152.5=152.6 (C-12), 153.3=153.5 (C-7=C-8), 162.1 (C-4) ppm; IR
(KBr): ꢂꢀ¼ 3124 (vw), 3078 (vw), 2924 (vw), 2873 (vw), 1582 (s), 1518 (m), 1468 (s), 1364 (m), 1332
(m), 1292 (m), 1231 (m), 1190 (m), 1175 (w), 1109 (m), 1082 (m), 1027 (w), 929 (vw), 877 (vw), 860
(vw), 820 (w), 751 (vw), 712 (vw), 670 (vw) cmꢁ1
.
(BPI)PtCl (11, C18H12ClN5Pt)
BPI (0.14 g, 0.48 mmol) and [(COD)PtCl2] (0.20 g, 0.52mmol) were suspended in MeOH (10 cm3). To
this suspension NEt3 (53.0 mg, 0.52mmol) was added and the reaction mixture was subsequently
stirred at 50ꢂC for 24h. The crude platinum complex and NEt3HCl were isolated by filtration and
the ammonium salt was removed by extraction with water. The orange reaction product was purified by
1
recrystallization from CH2Cl2=n-hexane (1:1). Yield 0.19g (0.36 mmol, 75%); mp 303ꢂC. H NMR
(300.17 MHz, CDCl3=d6-DMSO, 298 K): ꢀ ¼ 6.81 (m, 2H, 11-H), 7.39 (m, 4H, 4-H, 5-H, 9-H), 7.72
(m, 2H, 10-H), 7.82 (m, 2H, 3-H, 6-H), 10.01 (d, 3JHH ¼ 6.7 Hz, 2H, 12-H) ppm; IR (KBr): ꢂꢀ¼ 2939
(vw), 1586 (s), 1531 (s), 1465 (s), 1432 (m), 1386 (m), 1299 (w), 1189 (w), 1119 (m), 1109 (m), 914
(w), 765 (m), 698 (m) cmꢁ1; MS (FAB): m=z ¼ 528.7 [M]þ.
(4-MeBPI)PtCl (12, C19H14ClN5Pt ꢄ C5H12)
4-MeBPI (0.13 g, 0.40mmol) and [(COD)PtCl2] (0.16 g, 0.44 mmol) were suspended in MeOH
(10 cm3). To this suspension NEt3 (45.0mg, 0.44mmol) was added and the reaction mixture was

Bis(2-pyridylimino)isoindole Ligands
1703
subsequently stirred at 50ꢂC for 24 h. The crude platinum complex and NEt3HCl were isolated by
filtration and the ammonium salt was removed by extraction with water. The orange reaction product
was purified by recrystallization from CH2Cl2=n-hexane (1:1). Yield 0.18g (0.30 mmol, 75%); mp
226ꢂC; 1H NMR (400.16 MHz, CDCl3, 298 K): ꢀ ¼ 2.48 (s, 3H, 4-CH3), 6.94 (m, 2H, 11-H), 7.36 (d,
3JHH ¼ 7.3 Hz, 1H, 5-H), 7.51 (dd, 3JHH ¼ 7.5 Hz, 4JHH ¼ 1.8 Hz, 2H, 9-H), 7.78 (s, br, 1H, 3-H), 7.84
3
3
(m, 3H, 6-H, 10-H), 10.22 (d, JHH ¼ 6.6 Hz, JPtH ¼ 19.7Hz, 2H, 12-H) ppm; {1H}13C NMR
(100.6 MHz, CDCl3, 298 K): ꢀ ¼ 21.9 (4-CH3), 119.5 (C-11), 122.1 (C-5), 122.8 (C-6), 127.4
(C-9), 132.1 (C-3), 134.8 (C-1), 137.7 (C-2), 137.9 (C-10), 142.2 (C-4), 149.9=151.1 (C-7=C-8),
152.4 (C-12) ppm; IR (KBr): ꢂꢀ¼ 2920 (m), 2849 (w), 1653 (vw), 1585 (s), 1527 (m), 1465 (s),
1424 (vw), 1375 (m), 1287 (w), 1263 (vw), 1188 (w), 1133 (m), 1088 (w), 1020 (w), 829 (vw),
790 (vw), 780 (w) cmꢁ1
.
(4-Me-10-tBuBPI)PtCl (13, C27H30ClN5Pt)
4-Me-10-tBuBPI (11, 80.0 mg, 0.19 mmol) and [(COD)PtCl2] (78.0 g, 0.21 mmol) were suspended in
MeOH (10 cm3). To this suspension NEt3 (22.0 mg, 0.21mmol) was added and the reaction mixture was
subsequently stirred at 50ꢂC for 24h. After removal of the volatiles in vacuo, the orange-red residue
was extracted first with water and then with diethyl ether and n-hexane. The crude solid was recrys-
tallized from CH2Cl2=n-hexane (1:1) to give the pure compound 13. Yield 92.0mg (0.14mmol, 74%);
mp 76ꢂC; 1H NMR (400.16 MHz, CD2Cl2, 298K): ꢀ ¼ 1.28 (s, 18H, 10-tBu), 2.42 (s, 3H, 4-CH3), 6.90
(dd, 3JHH ¼ 6.3 Hz, 4JHH ¼ 2.2 Hz, 2H, 11-H), 7.32 (d, 3JHH ¼ 7.6Hz, 1H, 5-H), 7.39 (m, 2H, 9-H), 7.69
3
3
(s, br, 1H, 3-H), 7.74 (d, 3JHH ¼ 7.6 Hz, 1H, 6-H), 9.96 (d, JHH ¼ 6.3 Hz, JPtH ¼ 19.9Hz, 2H, 12-H)
ppm; {1H}13C NMR (100.6MHz, CD2Cl2, 298 K): ꢀ ¼ 20.3 (4-CH3), 28.4 (10-C(CH3)3), 33.4
(10-C(CH3)3), 116.3 (C-11), 120.4 (C-5), 121.1 (C-6), 122.4 (C-9), 130.6 (C-3), 133.5 (C-1), 136.5
(C-2), 140.8 (C-4), 148.3=149.5 (C-7=C-8), 150.0 (C-12), 161.3 (C-10) ppm; IR (KBr): ꢂꢀ¼ 2958 (m),
2868 (w), 1653 (w), 1612.5 (m), 1582 (s), 1502 (s), 1478 (s), 1404 (m), 1373 (m), 1321 (w), 1295 (m),
1184 (m), 1116 (m), 1087 (m), 1023 (w), 949 (w), 888 (w), 822 (w), 713 (w) cmꢁ1
.
(4-(3-Butenoxy)-10-MeBPI)PtCl (14, C24H22ClN5OPt)
4-(3-Butenoxy)-10-MeBPI (12, 0.15 g, 0.39mmol) and [(COD)PtCl2] (0.16 g, 0.42 mmol) were sus-
pended in MeOH (15 cm3). To this suspension NEt3 (43.0mg, 0.42mmol) was added and the reaction
mixture was subsequently stirred at 50ꢂC for 24h. After removal of the volatiles in vacuo, the orange-
red residue was extracted first with water and then with diethyl ether and n-hexane. The crude solid
was recrystallised from CH2Cl2=n-hexane (1:1) to give the pure compound 14. Yield 0.18g
1
(0.29 mmol, 74%); mp 154ꢂC (dec); H NMR (300.17MHz, CDCl3, 298K): ꢀ ¼ 2.35 (s, 6H, 10-
CH3), 2.62 (m, 2H, OCH2CH2), 4.18 (t, 3JHH ¼ 6.6 Hz, 2H, –OCH2–), 5.19 (m, 2H, ¼CH2), 5.94 (m,
1H, ¼C(H)–), 6.81 (m, 2H, 11-H), 7.11 (dd, 3JHH ¼ 8.4 Hz, 4JHH ¼ 2.2 Hz, 1H, 5-H), 7.37 (s, br, 2H, 9-
4
3
H), 7.51 (d, JHH ¼ 2.2 Hz, 1H, 3-H), 7.90 (d, JHH ¼ 8.4 Hz, 1H, 6-H), 10.08 (m, 2H, 12-H) ppm;
{1H}13C NMR (75.5 MHz, CDCl3, 298 K): ꢀ ¼ 20.7 (10-CH3), 33.5 (OCH2CH2–), 67.8 (OCH2), 106.7
(C-3), 117.3 (¼CH2), 118.5 (C-5), 120.9=121.1 (C-9), 123.4 (C-6), 127.3 (C-11), 129.6 (C-1), 134.1
(¼C(H)–), 139.6 (C-2), 149.5=149.6=149.7=149.8=150.7=150.9 (C-7=C-8=C-10), 151.4 (C-12), 162.2
(C-4) ppm; IR (KBr): ꢂꢀ¼ 2918 (w), 1582 (s), 1515 (m), 1470 (m), 1372 (m), 1333 (w), 1290 (w, br),
1229 (w), 1191 (m), 1109 (m), 1026 (w), 813 (w, br) cmꢁ1
.
X-Ray Crystallographic Study of 8 and 13
Suitable crystals of the complexes 8 and 13 were obtained by layering concentrated solutions of the
compounds in dichloromethane or chloroform with hexanes and allowing slow diffusion at room
temperature. The crystal data for 8 were collected on a Nonius Kappa CCD diffractometer at
ꢁ100ꢂC and transfered to a DEC Alpha workstation; for all subsequent calculations the Nonius
OpenMoleN package was used [22]. The data for 13 were collected on a CAD4 (Enraf-Nonius) four
circle diffractometer at ꢁ80ꢂC and the structure solution was carried out using the SHELX-97
structure solution packages.

1704
M. Meder et al.
All structures were solved using direct methods with absorption corrections being part of the
scaling procedure of the data reductions. After refinement of the heavy atoms, difference Fourier
maps revealed the maxima of residual electron density close to the positions expected for the hydrogen
atoms; they were introduced as fixed contributors in the structure factor calculations with fixed
2
˚
˚
coordinates (C–H: 0.95 A) and isotropic temperature factors (B(H) ¼ 1.3 Beqv(C) A ) but not refined.
The hydrogen atoms of the solvents were not refined. Full least-square refinements on F2. A final
difference map revealed no significant maxima of electron density. The scattering factor coefficients
and the anomalous dispersion coefficients were taken from Ref. [23]. Crystal data and experimental
details for the crystals of 8 and 13 are given in Table 1.
Crystallographic data (excluding structure factors) for the structures reported in this paper
have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication
Table 1. X-Ray experimental data of compounds 8 and 13
8
13
Formula
C24H22ClN5Opd
C27H30ClN5Pt
655.10
Molecular weight
Crystal system
Space group
˚
a=A
˚
b=A
538.33
monoclinic
triclinic
P-21=c
10.8058(2)
P-1
10.4591(16)
10.698(2)
11.585(2)
90.084(12)
103.972(10)
98.553(10)
1243.0(4)
2
25.8236(6)
˚
c=A
8.2113(4)
ꢁ=ꢂ
ꢃ=ꢂ
ꢄ=ꢂ
–
103.923(5)
–
3
˚
V=A
2224.0(1)
Z
4
Color
yellow
yellow
Crystal dim (mm)
Dcalc=gcmꢁ3
F000
0.16ꢃ0.06ꢃ0.04
0.30ꢃ0.30ꢃ0.30
1.75
1.61
1088
644
ꢅ=mmꢁ1
0.982
5.777
Trans. min and max
0.8131=1.0000
173
0.9981=0.6483
193
Temperature=K
˚
Wavelength=A
Radiation
0.71073
0.71073
MoKꢁ
ꢆ-scans
MoKꢁ
Scan mode
!=ꢇ-scan
ꢁ13=13, ꢁ13=13, ꢁ14=14
2.03=27.01
5424
hkl limits
ꢇ-limits=ꢂ
Number of data meas.
ꢁ8=8, ꢁ31=33, ꢁ13=13
2.5=27.46
7937
Number of data with I>3ꢈ(I)
Number of variables
2694 I>2ꢈ(I)
4844
289
0.058
0.072
–
388
R
Rw
R1
0.0301
0.0701
1.044
wR2
–
GOF
1.217
1.076
Largest peak iꢁn3final
1.282
˚
difference=eA

Bis(2-pyridylimino)isoindole Ligands
1705
nos. CCDC 265747 and 265748. Copies of the data can be obtained free of charge on application to
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: þ(44) 1223-336-033, e-mail: deposit@ccdc.
cam.ac.uk).
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