Gold, silver and palladium complexes with the 2,2′-dipyridylamine ligand

Article abstract of DOI:10.1002/ejic.200200666

Reaction of the 2,2′-dipyridylamine (Py₂NH) ligand with various gold and silver starting products leads to three- or four-coordinate complexes. The structure of compound [Ag(NHPy₂)(PPh₃)]OTf shows weak interactions which produce bands of molecules parallel to the z axis. Other hydrogen bonds of the type C-H...O serve to link the ribbons. The derivative PPN[Au(Py₂N)₂] has also been obtained using PPN[Au(acac)₂] [PPN = bis(triphenylphosphanyl)iminio, acac = acetylacetonate] as starting product to deprotonate the ligand. The palladium complex [PdCl₂(Py₂NH)₂] is also reported. Wiley-VCH Verlag GmbH & Co, KGaA, 69451 Weinheim, Gemany, 2003.

Full text of DOI:10.1002/ejic.200200666

FULL PAPER
Gold, Silver and Palladium Complexes with the 2,2Ј-Dipyridylamine Ligand
[a]
[a]
[a]
[b]
´
Mercedes Burgos, Olga Crespo, M. Concepcion Gimeno, Peter G. Jones, and
Antonio Laguna*[a]
Keywords: Gold / N Ligands / Palladium / Silver
Reaction of the 2,2Ј-dipyridylamine (Py2NH) ligand with
various gold and silver starting products leads to three- or
four-coordinate complexes. The structure of compound
[Ag(NHPy2)(PPh3)]OTf shows weak interactions which pro-
duce bands of molecules parallel to the z axis. Other hydro-
gen bonds of the type C−H···O serve to link the ribbons. The
derivative PPN[Au(Py2N)2] has also been obtained using
PPN[Au(acac)2] [PPN
=
bis(triphenylphosphanyl)iminio,
acac = acetylacetonate] as starting product to deprotonate
the ligand. The palladium complex [PdCl2(Py2NH)2] is also
reported.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2003)
Introduction
uninvestigated, as far as we know. The silver derivatives
may be especially interesting due to the possibility of the
A search of the CSD affords more than two hundred formation of supramolecular structures. These structures
structures of coordination complexes containing the 2,2Ј- may be derived from building blocks linked by coordinate
dipyridylamine ligand (dpa). In most of them, the ligand covalent[17] or hydrogen bonds.[18] Such structures are an
shows a bidentate coordination mode,[1] but coordination active field of research, and many of them are afforded by
as a bridging ligand[2] is not unusual, and monodentate co- using N,NЈ-bidentate spacers.[19] Herein we report the syn-
ordination has been found in [M(dpa)2(CO)3][3] (M ϭ Mo, thesis of some gold and silver complexes with the dpa li-
W, one chelate and other monodentate dpa) and also in the gand, and also the palladium derivative [PdCl2(dpa)]. The
more recently reported [W(dpa)(CO)5].[4] The copper com- structure of compound [Ag(NHPy2)(PPh3)]OTf shows
plexes of this ligand have been the most widely studied, at weak interactions which produce bands of molecules paral-
first as models for copper-containing plant hormone bind- lel to the z axis. Other hydrogen bonds of the type CϪH···O
ing sites,[1d,5] and also because of their interesting electro- serve to link the ribbons.
chemical behavior.[6] The blue-light emission of organoalu-
minium() and ZnII complexes with dpa is well known.
Results and Discussion
The chelating effect of dpa in these complexes seems to be
the origin of the enhancement and shift from UV to blue
of the intraligand π Ǟ π* transition of dpa upon
coordination.[7Ϫ10] Nevertheless, the thermal instability or
the low emission quantum yields in the solid state make the
use of these complexes for practical applications impossible.
Recent investigations in this area have involved polymeric
or polynuclear complexes.[1c] Interesting trinuclear com-
plexes in which the dpa acts as a bridging ligand have been
described. They show variable-temperature magnetic sus-
ceptibility, which ranges from strong antiferromagnetic
coupling (tricopper, trinickel)[11Ϫ13] to spin crossover (trico-
balt),[14,15] via Curie law behavior (trichromium).[2e,16] The
coordination to coinage metals other than copper remains
The reaction of [Py2NH] with AgOTf in a 1:1 or 2:1 mo-
lar ratio affords the three coordinate [Ag(OTf)(Py2NH)] (1)
or four coordinate [Ag(Py2NH)2]OTf (2) species
(Scheme 1). Their IR spectra show the vibrations corre-
sponding to NϪH deformation and CϭN, CϭC stretching
modes of the pyridine rings at 1586, 1540 cmϪ1 (1) or 1601,
1524 cmϪ1 (2) and the band corresponding to the NϪH
stretching vibration at 3320 (1) or 3340 (2).[1c,20,21] Those
bands corresponding to covalent (1, 1240 and 1119 cmϪ1
)
or anionic (2, 1272 and 1154 cmϪ1) trifluoromethanesulfon-
ate anion are also present.[22] The conductivity of com-
pound 1 in acetone solution shows a higher value than ex-
pected for a non-electrolyte. This can be explained by
taking into account the lability of the trifluoromethane-
sulfonate anion, which, in solution, is probably highly dis-
[a]
´
´
Departamento de Quımica Inorganica, Instituto de Ciencia de
´
Materiales de Aragon, Universidad de Zaragoza-CSIC,
1
50009 Zaragoza, Spain
sociated. In the H NMR spectra the pyridine protons ap-
[b]
Institut für Anorganische und Analytische Chemie, Technische
Universität Braunschweig,
pear as four signals in the range δ ϭ 7.16Ϫ8.20 (1) and
6.88Ϫ8.11 ppm (2). In 1, one signal at δ ϭ 11.30 ppm (br. s)
Postfach 3329, 38023 Braunschweig, Germany
2170
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejic.200200666
Eur. J. Inorg. Chem. 2003, 2170Ϫ2174

Gold, Silver and Palladium Complexes with the 2,2Ј-Dipyridylamine Ligand
FULL PAPER
Scheme 1. i) 1/2 AgOTf, ii) AgOTf, iii) PPh3, iv) [AgOTf(PPh3)], v) 2 [Au(C6F5)(tht)], vi) PPN[Au(acac)2], vii) [PdCl2(PhCN)2]
corresponds to the NH hydrogen atom, whereas in 2 it is found in [Ag(dppf)(PPh3)]OTf [dppf ϭ 1,1Ј-bis(diphenyl-
overlapped with the resonances of the pyridinic protons. In phosphanyl)ferrocene][25] [2.4244Ϫ2.4802(12) A]. The silver
˚
˚
the LSIMS (ϩ) mass spectra the cationic molecular peaks center lies 0.30 A out of the plane formed by the N11, N21
appear at m/z ϭ 428 (6%) for 1 and m/z ϭ 450 (9%) for 2. and P atoms, associated with a contact to a triflate oxygen,
˚
The displacement of the OTf ligand by PPh3 in 1, or the AgϪO3 2.725(3) A. This value is somewhat longer than the
[26]
˚
reaction of NHPy2 with [Ag(OTf)(PPh3)] in a 1:1 molar ra- 2.601(4) A in [Ag4{µ-SC2B10H10}2(µ-O3SCF3)2(PPh3)4],
tio, affords the derivative [Ag(NHPy2)(PPh3)]OTf (3). The but both values can be considered to lie in a typical range
characteristic vibrations of the dpa ligand appear in the IR for triflate-silver contacts. The same oxygen atom acts as an
spectrum at 1640, 1581 and 3330 cmϪ1; those correspond- acceptor for a hydrogen bond from the NH group [NϪO
ing to the OTf anion appear at 1283 and 1097 cmϪ1. The 3.021(4), HϪO 2.20(2) A] (Table 2). The overall effect of
˚
1H NMR spectrum displays a broad resonance at δ ϭ the two weaker interactions is to produce bands of mol-
9.64 ppm, which corresponds to the NH hydrogen atom. ecules parallel to the z axis (Figure 2). Other ‘‘weak’’ hydro-
Three signals are observed in the δ ϭ 5.5Ϫ8 ppm region, gen bonds of the type CϪH···O play a role in the crystal
one of which involves the phenyl group and two the pyrid- packing; two H···O distances from para-H atoms of the
inic protons. A broad signal at δ ϭ 14.46 ppm is observed phosphane phenyl rings are particularly short (2.31, 2.32
in the 31P{1H} NMR spectrum at room temperature. When A), and these H bonds serve to link the ribbons.
˚
the spectrum is recorded at Ϫ50 °C, the signal is split into
two doublets, centered at δ ϭ 17.6 ppm, due to the coupling
of the phosphorus atom with the two silver isotopomers
(J109
ϭ 773.2, J107
ϭ 678.4 Hz). The LSIMS (ϩ)
AgP
AgP
mass spectrum shows the cationic molecular peak at m/z ϭ
541 (53%).
The molecular structure of 3 has been determined by X-
ray diffraction studies. The geometry at the silver atom is
distorted trigonal (Figure 1, Table 1). The major distortion
comes from the restricted bite angle of the bidentate ligand
[N11ϪAgϪN21 82.82(9)°], with concomitantly wide values
for the other two angles [N11ϪAgϪP 139.80(7)°;
N21ϪAgϪP 131.22(7)°]. The AgϪN distances [AgϪN11
˚
2.264(2), AgϪN21 2.283(3) A] are in the range of those
observed
in
[Au2Ag2{µ-(PPh2)2N}(OClO3)(PPh3)2][23]
˚
[2.239(4) A], in which the silver centers show trigonal geo-
metries. Longer distances have been found in other silver
complexes in which the silver atom is three-coordinate,
such as [Ag{1,2-(C5H4NS)2-1,2-C2B10H10}(PPh3)]OTf
Figure 1. Structure of compound 3; thermal ellipsoids are drawn
with surfaces at the 50% probability level; hydrogens and solvent
have been omitted for clarity
[24]
˚
[2.345(2), 2.350(2) A].
The AgϪP distance of 2.3414(8)
Gold() complexes have also been obtained by the reac-
˚
A is similar to that found in [Ag{1,2-(C5H4NS)2-1,2- tion of Py2NH with very different starting products
˚
C2B10H10}(PPh3)]OTf (2.33832(7) A] or to the shortest (Scheme 1). Thus, the reaction of the ligand with
Eur. J. Inorg. Chem. 2003, 2170Ϫ2174
www.eurjic.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2171

M. Burgos, O. Crespo, M. C. Gimeno, P. G. Jones, A. Laguna
FULL PAPER
appears at δ ϭ 8.57 ppm. The 19F NMR spectrum shows
three signals, which correspond to the ortho, metha and para
fluorine atoms. In the LSIMS (ϩ) mass spectrum the mo-
lecular peak appears at m/z ϭ 899 (68%).
˚
Table 1. Selected bond lengths [A] and angles [°] for 3
AgϪN(11)
AgϪN(21)
AgϪP
AgϪO(3)
PϪC(51)
PϪC(41)
PϪC(31)
2.264(2)
2.283(3)
N(1)ϪC(22)
N(1)ϪC(12)
2.3414(8) N(11)ϪC(12)
1.377(4)
1.393(4)
1.335(4)
1.349(4)
1.333(4)
1.357(4)
When the reaction is carried out with PPN[Au(acac)2] in
a 2:1 molar ratio, the ligand is deprotonated and the homo-
leptic derivative PPN[Au(Py2N)2] (5) obtained. The IR and
1H NMR spectra confirm the deprotonation of the coordi-
2.725(3)
1.811(3)
1.820(3)
1.825(3)
N(11)ϪC(16)
N(21)ϪC(22)
N(21)ϪC(26)
1
nated ligands. In the H NMR spectrum, once again, one
N(11)ϪAgϪN(21) 82.82(9) C(41)ϪPϪAg
116.19(10)
110.36(11)
of the signals belonging to the pyridinic protons is over-
lapped, in this particular case with the broad signal from
the phenyl groups of the PPN cation. The anionic molecu-
lar peak at m/z ϭ 537 (35%) is present in the LSIMS(Ϫ)
mass spectrum. No crystal suitable for X-ray analyses has
been obtained. Tentatively we propose three- or four-coor-
dination at gold, involving coordination to the depro-
tonated nitrogen atoms and one or two of the pyridinic ni-
trogen atoms (see Scheme 1).
N(11)ϪAgϪP
N(21)ϪAgϪP
N(11)ϪAgϪO(3)
N(21)ϪAgϪO(3)
PϪAgϪO(3)
C(51)ϪPϪC(41)
C(51)ϪPϪC(31)
C(41)ϪPϪC(31)
C(51)ϪPϪAg
139.80(7) C(31)ϪPϪAg
131.22(7) C(22)ϪN(1)ϪC(12) 135.1(3)
94.01(8) C(12)ϪN(11)ϪC(16) 117.2(3)
95.48(8) C(12)ϪN(11)ϪAg
101.64(6) C(16)ϪN(11)ϪAg
104.46(16) C(22)ϪN(21)ϪC(26) 117.4(3)
104.61(15) C(22)ϪN(21)ϪAg
104.35(14) C(26)ϪN(21)ϪAg
115.66(12) SϪO(3)ϪAg
126.8(2)
113.2(2)
127.3(2)
114.8(2)
130.65(1)
We have also obtained the palladium complex
[PdCl2(Py2NH)2] by displacement of the PhCN ligands in
[PdCl2(PhCN)2] by Py2NH. In the IR spectrum the charac-
teristic vibrations of dpa appear at 3490, 1634 and 1587
cmϪ1. Four resonances for the pyridinic hydrogen atoms,
and the signal corresponding to the NH proton at δ ϭ
9.50 ppm, appear in the H NMR spectrum. The LSIMS
(ϩ) mass spectrum shows the molecular peak at m/z ϭ
348 (11%).
˚
Table 2. Hydrogen bonds [A and °] for 3
DϪH···A[a]
d(DϪH) d(H···A) d(D···A) Ͻ(DHA)
N(1)ϪH(01)···O(3)#1
C(34)ϪH(34)···O(1)#2
C(54)ϪH(54)···O(2)#3
C(46)ϪH(46)···O(3)
C(99)ϪH(99A)···O(1)
C(23)ϪH(23)···O(3)#1
0.841(18) 2.20(2) 3.021(4) 166(3)
1
0.95
0.95
0.95
0.99
0.95
2.32
2.31
2.58
2.65
2.68
3.262(5) 169.9
3.224(5) 162.1
3.400(5) 144.5
3.554(8) 152.5
3.446(4) 138.2
[a]
Symmetry transformations used to generate equivalent atoms:
#1 x, Ϫy ϩ 1/2, z ϩ 1/2; #2 x ϩ 1, y, z ϩ 1; #3 Ϫx ϩ 1, Ϫy, Ϫz
ϩ 1.
Experimental Section
General Remarks: AgOTf, Py2NH, PPh3 and [PdCl2(PhCN)2] were
purchased from Aldrich and used as received. The starting prod-
ucts [Au(C6F5)(tht)],[27] PPN[Au(acac)2][28] and [Ag(OTf)(PPh3)][29]
were synthesized according to literature methods.
Infrared spectra were recorded in the range 4000Ϫ200 cmϪ1 on a
PerkinϪElmer FT-IR Spectrum 1000 spectrophotometer as Nujol
mulls between polyethylene sheets. Conductivities were measured
in ca. 5 ϫ 10Ϫ4  acetone solutions with a Jenway 4010 conductim-
eter. C, H, N, S analysis was carried out with a PerkinϪElmer 240C
microanalyser. Mass spectra were recorded on a VG Autospec
using the LSIMS techniques and nitrobenzyl alcohol as matrix and
on a HP59987 A ELECTROSPRAY. 1H, 19F and 31P NMR spectra
were recorded on a Bruker ARX 300 in CDCl3 solutions. Chemical
shifts are quoted relative to SiMe4 (1H, external), CFCl3 (19F, exter-
nal) and H3PO4 (85%) (31P, external).
Figure 2. Crystal structure of 3; hydrogens have been omitted for
clarity; secondary interactions Ag···O and N···O are indicated by
dashed lines
Synthesis of [Ag(OTf)(Py2NH)] (1): Py2NH (0.1 mmol, 0.017 g)
was added to a diethyl ether solution (20 mL) of Ag(OTf)
(0.1 mmol, 0.025 g). The solution was stirred for 30 min. Upon
concentration to ca. 5 mL compound 1 precipitated as a white solid
(31 mg, yield 76%). C11H9AgF3N3O3S (428.1): calcd. C 30.85, H
2.10, N 9.8, S 7.45; found C 30.85, H 2.10, N 9.8, S 7.60. ΛM 107
[Au(C6F5)(tht)] in a 1:2 molar ratio affords the dinuclear
Ω
Ϫ1cm2molϪ1. 1H NMR: δ ϭ 7.16 (dd, JH,H ϭ 6.53, 6.51 Hz, 2H-
complex [Au2(C6F5)2(µ-Py2NH)] (4). Apart from the
characteristic bands of dpa at 1610, 1532 and 3296 cmϪ1
,
Py), 7.52 (d, JH,H ϭ 8.74 Hz, 2H-Py), 7.90 (dd, JH,H ϭ 7.94,
7.20 Hz, 2H-Py), 8.20 (br. m, 2H-Py), 11.30 (br. s, 1H-NH) ppm.
the IR spectrum of 4 shows the vibrations of the penta-
fluorophenyl ring bonded to gold() at 1507 and 961 cmϪ1
In the H NMR spectrum, three of the signals come from
the pyridinic protons, one of which integrates for double
.
Synthesis of [Ag(Py2NH)2]OTf (2): Py2NH (0.2 mmol, 0.034 g) was
added to a diethyl ether solution (20 mL) of Ag(OTf) (0.1 mmol,
0.025 g). The solution was stirred for 30 min. Upon concentration
1
the value of the others. The NH hydrogen atom resonance to ca. 5 mL compound 2 precipitated as a white solid (45 mg, yield
2172  2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.eurjic.org
Eur. J. Inorg. Chem. 2003, 2170Ϫ2174

Gold, Silver and Palladium Complexes with the 2,2Ј-Dipyridylamine Ligand
76%). C21H18AgF3N6O3S (599.3): calcd. C 42.05, H 3.0, N 14.0, S CB2 1EZ, UK; fax: (internat.) ϩ44Ϫ1223/336Ϫ033; E-mail:
FULL PAPER
5.35; found C 41.65, H 2.7, N 14.1, S 5.15. ΛM 119 ΩϪ1cm2molϪ1
.
deposit@ccdc.cam.ac.uk].
1H NMR: δ ϭ 6.88 (br. m, 4H-Py), 7.3 (br. m, 4H-Py), 7.64 (br.
m, 4H-Py), 8.11(br. m, 4H-Py) ppm.
Acknowledgments
Synthesis of [Ag(Py2NH)(PPh3)]·OTf (3). Method (a): Py2NH
(0.1 mmol, 0.017 g) was added to a dichloromethane solution
(20 mL) of [Ag(OTf)(PPh3)] (0.1 mmol, 0.052 g). After stirring for
30 min, the solution was concentrated to ca. 5 mL Addition of di-
ethyl ether afforded 3 as a white solid. Method (b): PPh3 (0.1 mmol,
0.026 g) was added to a dichloromethane solution (20 mL) of [Ag(-
OTf)(Py2NH)] (0.1 mmol, 0.043 g). After stirring for 30 min, the
solution was concentrated to ca. 5 mL. Addition of diethyl ether
afforded 3 as a white solid (64 mg, yield 94%). C29H24AgF3N3O3PS
(690.4): calcd. C 50.45, H 3.5, N 6.0, S 4.65; found C 50.2, H 3.2,
´
´
We thank the Direccion General de Investigacion (D.G.I) (n°
BQU2001-2409-C02-01), the Fonds der Chemischen Industrie, and
the Caja de Ahorros de la Inmaculada for financial support.
[1]
[1a]
See for example:
B. Yan, Y. Xu, X. Bu, N. K. Goh, L. S.
Chia, G. D. Stucky, J. Chem. Soc., Dalton Trans. 2001,
[1b]
2009Ϫ2014.
S. Youngme, W. Somjitsripunya, K. Chinnak-
ali, S. Chantsraproma, H.-K. Fun, Polyhedron 1999, 18,
1
N 6.25, S 4.7. ΛM 102 ΩϪ1cm2molϪ1. H NMR: δ ϭ 6.82 (br. m,
[1c]
857Ϫ862.
H. Zhu, M. Strobele, Z. Yu, Z. Wang, H. J.
[1d]
2H-Py), 7.38Ϫ7.54 (br. m, 2H-Pyϩ 15H-Ph), 7.63 (br. m, 2H-Py),
7.93 (br. m, 2H-Py), 9.64 (br. s, 1H-NH) ppm.
Meyer, X. You, Inorg. Chem. Commun. 2001, 4, 557Ϫ581.
J. S. Thompson, J. F. Whitney, Inorg. Chem. 1984, 23,
2813Ϫ2819. [1e] K.-Y. Ho, W.-Y. Yu, K.-K. Cheung, C.-M. Che,
[1f]
Synthesis of [Au2(C6F5)2(µ-Py2NH)] (4): Py2NH (0.1 mmol,
0.017 g) was added to a solution of [Au(C6F5)(tht)] (0.2 mmol,
0.091 g) in dichloromethane (20 mL). The solution was stirred for
30 min. Concentration to ca. 5 mL and addition of diethyl ether
afforded 4 as a white solid (59 mg, yield 66%). C22H9Au2F10N3
(899.2): calcd. C 29.35, H 1.0, N 4.65; found C 29.4, H 1.45, N
5.15. ΛM 22 ΩϪ1cm2molϪ1. 1H NMR: δ ϭ 7.0 (br. m, 2H-Py), 7.77
(br. m, 4H-Py), 8.29 (br. m, 2H-Py), 8.57 (br. s, 1H-NH) ppm. 19F
NMR: δ ϭ Ϫ117 (m, 4F, o-F), Ϫ159.3 (t, 2F, p-F, 3J(FF) 19.64 Hz),
Ϫ163.1 (m, 4F, m-F) ppm.
J. Chem. Soc., Dalton Trans. 1999, 1581Ϫ1586.
ueva, J. L. Mesa, M. K. Urtiaga, R. Cortes, L. Lezama, M. J.
M. Villan-
´
[1g]
Arriortua, T. Rojo, Eur. J. Inorg. Chem. 2001, 1581Ϫ1586.
P. Naumov, G. Jovanovski, M. G. B. Drew, S. W. Ng, Inorg.
Chim. Acta 2001, 314, 154Ϫ162. [1h] C.-M. Liu, S. Gao, H.-M.
[1i]
Hu, Z.-M. Wang, Chem. Commun. 2001, 1636Ϫ1637.
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[2]
[2a]
See for example:
G. B. Deacon, S. J. Faulks, B. M. Gate-
house, A. J. Jozsa, Inorg. Chim. Acta 1977, 21, L1. [2b] J. Ashen-
hurst, L. Brancaleon, S. Gao, W. Liu, H. Schmider, S. Wang,
[2c]
G. Wu, Q. G. Wu, Organometallics 1998, 17, 5334Ϫ5341.
Synthesis of PPN[Au(Py2N)2] (5): Py2NH (0.1 mmol, 0.017 g) was
added to a solution of PPN[Au(acac)2] (0.05 mmol, 0.047 g) in di-
chloromethane (20 mL). The solution was stirred for 30 min and
then concentrated to ca. 5 mL. Addition of hexane afforded 5 as a
white solid (33 mg, yield 31%). C56H46AuN7P2 (1075.9): calcd. C
62.5, H 4.3, N 9.1; found C 62.7, H 4.1, N 9.45. ΛM 73
M. Tayebani, S. Gambarotta, G. Yap, Organometallics 1998,
17, 3639Ϫ3641. [2d] F. A. Cotton, L. M. Daniels, C. A. Murillo,
I. Pascual, Inorg. Chem. Commun. 1998, 1, 1Ϫ3. [2e] R. Clerac,
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[2f]
Pascual, Inorg. Chem. 2000, 39, 752Ϫ756.
F. A. Cotton, C.
A. Murillo, X. Wang, J. Chem. Soc., Dalton Trans. 1999,
[2g]
3327Ϫ3328.
R. Clerac, F. A. Cotton, L. M. Daniels, K. R.
Ω
Ϫ1cm2molϪ1. 1H NMR: δ ϭ 6.84 (br. m, 2H-Py), 7.41Ϫ7.6 (br. m,
Dunbar, K. Kirschbaun, C. A. Murillo, A. A. Pinkerton, A. J.
2H-Pyϩ 30H-Ph), 7.67 (br. m, 2H-Py), 8.26 (br. m, 2H-Py) ppm.
Schultz, X. Wang, J. Am. Chem. Soc. 2000, 122, 6226Ϫ6236.
[2h]
H. Gornitzka, D. Stalke, Eur. J. Inorg. Chem. 1998,
Synthesis of [PdCl2(Py2NH)] (6): Py2NH (0.1 mmol, 0.017 g) was
added to a solution of [PdCl2(PhCN)2] (0.1 mmol, 0.035 g) in di-
chloromethane (20 mL). The solution was stirred for 30 min and
then concentrated to ca. 5 mL Addition of diethyl ether afforded 5
as a yellow-orange solid (49 mg, yield 95%). C10H9Cl2N3Pd (348.5):
calcd. C 34.45, H 2.6, N 12.05; found C 34.15, H 2.65, N 11.80.
1H NMR: δ ϭ 6.92 (br. m, 2H-Py), 7.33 (br. m, 2H-Py), 7.62 (br.
m, 2H-Py), 8.65 (br. m, 2H-Py), 9.50 (br. m, 1H-NH) ppm.
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X-ray Crystallographic Study of Compound 3·CH2Cl2: Colorless
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˚
˚
28.699(3), c ϭ 9.6308(9) A, β ϭ 102.311(3)°, V ϭ 3245.1(6) A
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Received December 5, 2002
2174
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