Synthesis of a novel pyridine-diamino bridged diphosphine ligand and its macrocyclic metal complexes

Article abstract of DOI:10.1016/j.ica.2005.01.008

A novel long chain diphosphine ligand with a pyridine-diamino bridge, 2,6-bis(N-benzyl-N-diphenylphosphinomethylamino)pyridine (PNP1), was prepared conveniently using the Mannich reaction of HPPh₂ with paraformaldehyde and 2,6-bis(N-benzylamino)pyridine in high yield. Reactions of the ligand with metal complexes, M(COD)Cl₂ (M = Pd, Pt), M(CH ₃CN)₄ClO₄ (M = Cu, Ag) and M(CO)₆ (M = Mo, W) afforded the corresponding 10-numbered monometallic macrocyclic complexes with an uncoordinated pyridyl bridge. The monometallic chelate PdCl₂(PNP1) continued to react with Ag⁺ or Cu⁺ giving the μ-Cl bridged bicyclic metallic complex (μ-Cl) ₂[PdCl(PNP1)]₂. The diphenylphosphine group coordinated with metal ion in cis-form in all the 10-numbered macrocyclic metal complexes. Ligand PNP1 and another known analogous 2,6-bis(N-diphenylphosphinoamino) pyridine (PNP2) reacted with Au(SMe₂)Cl giving the corresponding bimetallic Au₂Cl₂(PNP1) and Au₂Cl ₂(PNP2), respectively. The latter bimetallic complexes continued to react with Ag⁺ and diphosphine ligand to give the corresponding bimetallic macrocyclic complexes Au₂(ligand)₂(ClO ₄)₂. All the complexes were characterized and the structures of some complexes were confirmed by X-ray single crystallography determination.

Full text of DOI:10.1016/j.ica.2005.01.008

Inorganica Chimica Acta 358 (2005) 2283–2291
www.elsevier.com/locate/ica
Synthesis of a novel pyridine-diamino bridged diphosphine ligand
and its macrocyclic metal complexes
*
Qing-Shan Li , Chong-Qing Wan, Feng-Bo Xu, Hai-Bin Song, Zheng-Zhi Zhang
*
State Key Laboratory of Element-Organic Chemistry, Nankai University, Tianjin 300071, PR China
Received 20 August 2004; accepted 11 January 2005
Abstract
A novel long chain diphosphine ligand with a pyridine-diamino bridge, 2,6-bis(N-benzyl-N-diphenylphosphinomethylamino)pyr-
idine (PNP1), was prepared conveniently using the Mannich reaction of HPPh2 with paraformaldehyde and 2,6-bis(N-benzyla-
mino)pyridine in high yield. Reactions of the ligand with metal complexes, M(COD)Cl2 (M = Pd, Pt), M(CH3CN)4ClO4
(M = Cu, Ag) and M(CO)6 (M = Mo, W) afforded the corresponding 10-numbered monometallic macrocyclic complexes with an
uncoordinated pyridyl bridge. The monometallic chelate PdCl2(PNP1) continued to react with Ag+ or Cu+ giving the l-Cl bridged
bicyclic metallic complex (l-Cl)2[PdCl(PNP1)]2. The diphenylphosphine group coordinated with metal ion in cis-form in all the 10-
numbered macrocyclic metal complexes. Ligand PNP1 and another known analogous 2,6-bis(N-diphenylphosphinoamino)pyridine
(PNP2) reacted with Au(SMe2)Cl giving the corresponding bimetallic Au2Cl2(PNP1) and Au2Cl2(PNP2), respectively. The latter
bimetallic complexes continued to react with Ag+ and diphosphine ligand to give the corresponding bimetallic macrocyclic com-
plexes Au2(ligand)2(ClO4)2. All the complexes were characterized and the structures of some complexes were confirmed by X-ray
single crystallography determination.
ꢀ 2005 Published by Elsevier B.V.
Keywords: Diphosphine; P,N-ligand; Macrocyclic metal complexes; Bimetallic complexes; Crystal structures
1. Introduction
both with N and P atoms, but also some scare cases
[2,3] functioned as a diphosphine ligand with an unco-
ordinated pyridyl group. Thus, the uncoordinated pyr-
idyl groups in diphosphine ligand should have some
ability in relation with recognition to metal ions or
organic molecules.
The rigid pyridine-diphosphine ligand 2,6-diphosphi-
nopyridine (A) was first synthesized by Newkome and
Hager [4] and its coordination with metal species to
form various binuclear and polynuclear metal com-
plexes was extensively studied [5]. The rigidity of ligand
A governs the P–N–P ligand bite distance and the two P
donors could not bind to a single metal atom. Therefore,
ligand A could coordinate to metal in several bridging
modes as shown in Scheme 1(a)–(d): (a) two P atoms
coordinate to two metal atoms with a pyridyl-N atom
Recently, there has been continuing interest in the
synthesis and chemistry of hemilabile ligands in view
of their wide use in coordination, organometallic and
catalytic chemistry, in which the tridentate ligands with
PXP (X = C, N, O, S, and As) donor sets [1–3] have
attracted particular attention for their coordinative
extensibility and structural diversity with transition
metals. The functionalized diphosphine ligands with
pyridyl as a bridge usually coordinated with metal ions
*
Corresponding author. Tel.: +86 22 2350 4235; fax: +86 22 2350
3438.
E-mail addresses: qli@nankai.edu.cn, qingshanli2004@yahoo.
com.cn (Q.-S. Li).
0020-1693/$ - see front matter ꢀ 2005 Published by Elsevier B.V.
doi:10.1016/j.ica.2005.01.008

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Ph2P
PPh2
PPh2
Ph2P
N
Bz
N
Bz
Ph2P
N
H
N
H
N
PPh2
N
Ph2P
N
PPh2
N
A
B
PNP2
PNP1
Ph2P
M
N
PPh2
M
Ph2P
N
PHPh2
Ph2P
M
N
PPh2
Ph2P
N
PPh2
M
M
M
M
M
M
(a)
(b)
(c)
(d)
Bz
N
Bz
N
N
N
NH
N
HN
PPh2
PPh2
Ph2P
Ph2P
M
M
Ph2P
PPh2
M
(e)
(f)
(g)
Scheme 1.
uncoordinated; (b) a P atom and the pyridyl-N atom
chelate to one metal and the other P atom coordinates
with a second metal atom; (c) one P and the pyridyl-N
atom bond to two metal atoms, respectively, with the
other P atom uncoordinated, (d) each atom of the three
donors bonds to a separate metal atom. The pyridyl
bridged longer chain diphosphine, 2,6-bis(diphenylphos-
phinomethyl)pyridine (B), which was more flexible,
could coordinate to metal with three donor atom bond-
ing to a single metal [6], its complexes had a favorite
configuration of two abutted five-member cycle as
shown in Scheme 1(e). An analog of ligand B, 2,6-
2. Results and discussion
2.1. Preparation of ligand PNP1 and its 10-numbered
macrocyclic metal complexes and the X-ray structure
determination
The ligand PNP1 was synthesized conveniently using
the Mannich reaction of HPPh2 with paraformaldehyde
and 2,6-bis(N-benzylamino)pyridine in high yield. PNP1
reacted with metal complexes M(COD)Cl2 (M = Pd, Pt),
M(CH3CN)4ClO4 (M = Cu, Ag) and M(CO)6 (M = Mo,
W) to afford the corresponding 10-numbered monome-
tallic macrocyclic complexes (1–6) with an uncoordi-
nated pyridyl bridge (Scheme 2). The monometallic
chelate PdCl2(PNP1) (1) continued to react with Ag+
or Cu+ giving the l-Cl bridged bicyclic metallic complex
[Pd(PNP1)]2(l-Cl)2(ClO4)2 (7).
The two arms in ligand PNP1 are longer than its ana-
log 2,6-bis(diphenylphosphinoamino)pyridine (PNP2).
For ligand PNP2, the two P atoms and one N atom in
pyridyl could bond to a same metal atom (such as
Mo, W, Pd, Ni and Pt) [7] to form the abutted bis-pen-
ta-cycle structure of monometallic complexes [Scheme
1(f)]. But for ligand PNP1, when the two P atoms che-
late to one metal, the N atom in pyridyl could not bond
to the same metal due to the tension of bis-hexa-cycle
bis(diphenylphosphinoamino)pyridine
(PNP2)
[7],
bridged with a similar chain in length, but with two
NH groups instead of two CH2 in B, was first studied
in coordination chemistry by Haupt and co-workers in
1987. Less metal complexes of PNP2 were observed in
the literature [7] because of its lower flexibility compared
with those of ligand B and the metal complexes had the
structure of bi-five-member cycle configuration as
shown in Scheme 1(f). For the attempt to synthesize
the macrocyclic metal complexes and to study on their
unique catalytic properties, herein a much longer pyridyl
chain bridged diphosphine was prepared and its coordi-
nated macrocyclic metal complexes with structure as
shown in Scheme 1(g) were studied.
CH2Ph
N
PhCH2
N
N
Ph2P
PPh2
M
M = PdCl2, 1; PtCl2, 2; Cu(NCCH3)2ClO4, 3; Ag(NCCH3)2ClO4, 4; Mo(CO)4, 5; W(CO)4,
6
Scheme 2.

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2285
with three N atoms and one metal atom in one plane.
Therefore, all the monometallic complexes of ligand
PNP1 take the structure with two P atoms chelating to
metal atom and the pyridine-N atom uncoordinated
(Scheme 2). The structures of these complexes adopt
an endo-configuration to form a boat shape of the mol-
ecule and the two P atoms are all in cis-form, which is
confirmed by the X-ray crystal structure determination
of some complexes (Figs. 2–5).
(Ph)NHPh)] [9]. The distance of Pd(1) to N(2) is
˚
3.175(4) A. The angles of P(1)–Pd(1)–P(2), P(2)–Pd(1)–
Cl(1) and Cl(2)–Pd(1)–Cl(1) are 96.16(5), 83.72(5) and
91.39(5), respectively, making the Pd plane slightly dis-
torted. Positions of the two benzyls and the two methyl-
enes changed from trans- to cis-form of the pyridyl plane
compared with those in free ligand PNP1. The whole
The structures of ligand PNP1 and complexes 1, 3, 5,
7 are shown in Figs. 1–5, while the important bond dis-
tances and angles are listed in Table 2. In complex 1, the
Pd atom adopted a planar square configuration with a
cis-form of two P and two Cl atoms. The P–Pd bond dis-
˚
tance of 2.2517(14) A is very compatible to those re-
ported in the literature, but longer than those of
˚
2.212(2) A for cis-Re2(m-O2C6H4-4-PPh2)2Cl2(dppm)2
˚
(Pd2Cl4) [8] and 2.1969(15) A for [PdCl2(Ph2PCH2CH
ꢀ
Fig. 3. Perspective drawing of the cation part in complex 3 with ClO4
omitted for clarity. Thermal ellipsoids are shown at the 30%
probability level.
Fig. 1. Perspective drawing of ligand PNP1. Thermal ellipsoids are
shown at the 30% probability level.
Fig. 2. Perspective drawing of complex 1 Æ CH2Cl2 with solvent
molecule omitted for clarity. Thermal ellipsoids are shown at the
30% probability level.
Fig. 4. Perspective drawing of complex 5. Thermal ellipsoids are
shown at the 30% probability level.

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gle of P(1)–C(17)–N(1) is 114.9(4)ꢁ, which is lesser than
that of P(2)–C(37)–N(3) [117.3(3)ꢁ]. The P–Mo bond
distances in 5 of 2.5752(15) and 2.5942(16) A are similar
˚
to Mo2Cl4(l-L)2 (L = 2-chloro-6-(diphenylphosphino)
˚
pyridine) of 2.550(5) A [11] (Fig. 5).
Complex 1 reacted with Ag+ or Cu+ to afford com-
plex 7. In 7, the two subunits of formule adopted
trans-fashion. The two pyridyl rings in trans-form were
parallel to each other and deposited on the two sides
of the bridge plane. The corresponding bond distances
and bond angles in 7 were extraordinarily compatible
with those in 1.
In 1H NMR spectra of these macrocyclic monometal-
lic complexes, the signal of CH2 group linked with PPh2
was shifted downfield to 4.65–4.97 ppm compared with
that in free ligand PNP1 of 4.34 ppm. The signals of
PPh2 were also shifted downfield. However, the other
CH2 in benzyl group showed a high-field shift to about
3.44–4.26 ppm from 4.50 ppm in free ligand, especially
to 3.44 ppm in complex 5. The electronic absorptions
of all complexes in dichloromethane showed a strong
absorption band at ca. 262 nm and a weak band at ca.
334 nm, which underwent a slight red shift in the UV–
Vis spectrum compared with the corresponding band
of free PNP1 at 254 and 326 nm. All these phenomena
were consistent with the coordination of phosphine li-
gand with transition metal.
Fig. 5. Perspective drawing of thꢀe cation part in complex
7 Æ 1.5CH2ClCH2Cl with solvent, ClO4 and phenyl ring omitted for
clarity. Thermal ellipsoids are shown at the 30% probability level.
molecule structure adopts a boat fashion to form a 10-
membered macrocycle (Fig. 3).
Complexes of Cu(I) and Ag(I) were obtained by the
same procedure as those of Pt and Pd, except that prep-
aration and manipulation of complex 4 in dark environ-
ment because of photosensitivity of Ag complex. In 3,
the Cu atom adopted a tetrahedron configuration with
two P atoms and two CH3CN coordinated. The P–Cu
˚
bond distance of 2.2608(12) A is similar to those re-
˚
2.2. Preparation of Au–Au bond containing bicyclic
complexes of pyridine-bridged diphosphine
ported in the literature, such as those of 2.23–2.27 A
for [Cu(NN0)2(DPEphos)]BF4 (DPEphos = bis[2-(diph-
enylphosphino)phenyl]ether
and
NN0 = bidentate
The macrocyclic bimetallic complexes of Au–Au
bond were synthesized as shown in Scheme 3. First, li-
gands PNP1 and PNP2 reacted with Au(SMe2)Cl giving
the corresponding bimetallic Au2Cl2(PNP1) (8) and
Au2Cl2(PNP2) (10), respectively, with a simple strategy
used to generate R3PAuCl (R = aryl or alkyl) in the lit-
erature [12,13]. Then, the latter bimetallic complexes
continued to react with Ag+ and another diphosphine li-
gand to give the corresponding bimetallic macrocyclic
complexes Au2(l-L)2(ClO4)2 (9 and 11) (Scheme 3).
The molecular structure of complex 8 is shown in
Fig. 6 and the selected bond distances and bond angles
N-ligand) [10]. The angles of N(4)–Cu(1)–N(5), P(1)–
Cu(1)–P(2) and N(4)–Cu(1)–P(1) are 98.42(17)ꢁ,
113.66(4)ꢁ and 117.51(11)ꢁ, respectively. Complex 3
had a space group of P1, and also adopted a boat shape
configuration, with a symmetric mirror existing through
the plane of N(2)–N(4)–N(5)–Cu(1) (Fig. 4).
Complexes 5 and 6 were prepared by the thermal
reaction of PNP1 with Mo(CO)6 and W(CO)6, respec-
tively. In 5, the center Mo atom adopted an octahedron
configuration with two cis-P atoms and four carbonyls.
The full molecule took a distorted boat fashion. The an-
ꢀ
X
X
N
N
PPh2
PPh2
Ph2P
Ph2P
Ag(CH3CN)4ClO4
Au+
Au+
Ph2P
PPh2
AuCl
X
X
N
ClAu
same ligand
X
X
X = NH, 8
X = N(CH2Ph)CH2, 10
X = NH, 9
X = N(CH2Ph)CH2, 11
Scheme 3.

Q.-S. Li et al. / Inorganica Chimica Acta 358 (2005) 2283–2291
2287
idine (5.78 g, 20 mmol) and paraformaldehyde (1.5 g,
30 mmol) in toluene (50 mL) at 70–80 ꢁC. The mixture
was stirred at 70–80 ꢁC until all of paraformaldehyde
had completely disappeared (about 24 h). The solution
was cooled and then filtered through Celite. The solvent
was removed under vacuum and the residue was recrys-
tallized with CH2Cl2/CH3OH to give 5.70 g (41.6%) of
PNP1 as a white powder. m.p. 112–114 ꢁC. The sample
for analysis was further purified by recrystallization
from CH2Cl2/n-hexane. Anal. Calc. for C45H41N3P2: C,
78.81; H, 6.03; N, 6.13. Found: C, 78.73; H, 6.08; N,
1
6.19%. H NMR (CDCl3, d, ppm): 7.02–7.41 (m, 31H,
6Ph and Py-H4), 5.86 (d, 2H, Py-H3/H5), 4.50 (s, 4H,
2CH2Ph), 4.34 (d, 4H, 2CH2PPh2). 31P NMR (CDCl3,
d, ppm): ꢀ23.5.
Fig. 6. Perspective drawing of complex 8 with solvent omitted for
clarity. Thermal ellipsoids are shown at the 30% probability level.
3.2. Preparation of PdCl2(PNP1) Æ CH2Cl2 (1 Æ CH2Cl2)
in Table 2. The space group of crystal molecule of 8 is
ꢀ
P1. Because of the single crystal suit for X-ray determi-
The solid of Pd(COD)Cl2 (0.171 g, 0.60 mmol) was
added to the solution of PNP1 (0.411 g, 0.6 mmol) in
CH2Cl2 (30 ml) and the mixture was stirred for 0.5 h
at room temperature. The solvent was removed under
vacuum and the residue was recrystallized with
CH2Cl2/Et2O to give 0.482 g (82%) of 1 as a yellow pow-
der. m.p. 224–226 ꢁC. The sample for analysis was
further purified by recrystallization from CH2Cl2/n-hex-
ane and was found to be formule of PdCl2(PNP1) Æ
CH2Cl2. Anal. Calc. for C46H43Cl4PdN3P2: C, 58.28;
H, 4.57; N, 4.43. Found: C, 58.19; H, 4.55; N, 4.46%.
1H NMR (CDCl3, d, ppm): 7.53–7.05 (m, 31H, 6Ph
and Py-H4), 5.88 (d, 2H, Py-H3/H5), 4.97(d, 4H,
2CH2PPh2), 4.18 (s, 4H, 2CH2Ph), 31P NMR (CDCl3,
d, ppm): 21.27(s).
nation grown by recrystallization in a mixture solvent of
DMSO, CH3COCH3 and Et2O, there are two molecules
of DMSO solvent existing in one molecular of 7 in the
crystal structure. The bond lengths of Au–P and Au–
˚
Cl are 2.222(2) and 2.293(3) A, respectively, and the
bond angles of P(1)–Au(1)–Cl(1) and P(2)–Au(2)–Cl(2)
are 177.54(10)ꢁ and 175.25(9)ꢁ, respectively. The main
bond distances and angles were consistent with those
in the literature [12,13].
3. Experimental
Ligands PNP2 [7] and 2,6-bis(N-benzylamino)pyri-
dine were prepared as reported in the literature. All
other reagents and organic solvents were purchased
from commercial sources. All reactions were carried
out under a prepurified nitrogen atmosphere using stan-
dard Schlenk techniques on vacuum line. All solvents
were thoroughly dried and deoxygenated by standard
3.3. Preparation of PtCl2(PNP1) Æ CH2Cl2 (2 Æ CH2Cl2)
The same procedure as that for 1 was followed, but
Pt(COD)Cl2 (0.112 g, 0.3 mmol) and PNP1 (0.2055 g,
0.6 mmol) were used to afford 0.268 g (84%) of 2 as a
bright yellow powder. m.p. 256–260, Anal. Calc. for
C46H43Cl4PtN3P2: C, 53.29; H, 4.18; N, 4.05. Found:
C, 53.25; H, 4.26; N, 4.07%. 1H NMR (CDCl3, d,
ppm): 7.54–7.07 (m, 31H, 6Ph and Py-H4), 5.90 (d,
2H, Py-H3/H5), 4.83 (d, 4H, 2CH2PPh2), 4.17 (s, 4H,
1
methods and distilled immediately before use. H and
31P NMR spectra were recorded on a Bruker AC-300
NMR spectrometer. IR spectra were recorded on a Bru-
ker FT-IR Equinox-55 infrared spectrophotometer in
the range of 4000–400 cmꢀ1 using KBr disks. The UV
spectra were conducted on a Shimadzu UV-1601PC
spectrophotometer. Elemental analyses were performed
on a Yanaco MT-3 analyzer. Melting points were deter-
mined on a Yanaco micromelting point apparatus
MP-500.
CH2Ph), 31P NMR (CDCl3, d, ppm): 2.99 (t, JPt–P
=
3880 ppm).
3.4. Preparation of Cu(CH3CN)2(PNP1)ClO4 (3)
Similarly, Cu(CH3CN)4ClO4 (0.096 g, 0.3 mmol) and
PNP1 (0.205 g, 0.6 mmol) were used to afford 0.244 g
(81%) of 3 as a white powder. m.p. 196–200 ꢁC. Anal.
Calc. for C49H47ClCuN5P2O4: C, 63.22; H, 5.09; N,
7.52. Found: C, 63.00; H, 4.97; N, 7.60%. H NMR
(CDCl3, d, ppm): 7.53–6.98 (m, 31H, 6Ph and Py-H4),
5.81 (d, 2H, Py-H3/H5), 4.73 (d, 4H, 2CH2PPh2), 4.26
3.1. Preparation of PNP1
2,6-Bis(N-diphenylphosphinomethyl-N-benzyl)
aminopyridine (PNP1) was prepared by the Mannich
reaction of HPPh2. HPPh2 (7.44 g, 40 mmol) was added
with stirring to a solution of 2,6-bis(N-benzylamino)pyr-
1

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Q.-S. Li et al. / Inorganica Chimica Acta 358 (2005) 2283–2291
1
(s, 4H, 2CH2Ph), 4.07(s, 6H, 2CH 3CN), 31P NMR
(CDCl3, d, ppm): ꢀ10.10.
Found: C, 56.10; H, 4.01; N, 4.36%. H NMR (CDCl3,
d, ppm): 7.05–7.55 (m, 62H, 12Ph and 2Py-H4), 5.70 (d,
4H, 2Py-H3/H5), 3.99 (s, 8H, 4CH2Ph), 4.49 (d, 8H,
4CH2PPh2), 31P NMR (CDCl3, d, ppm): 25.00.
3.5. Preparation of Ag(CH3CN)2(PNP1)ClO4 (4)
Similarly, Ag(CH3CN)4ClO4 (0.111 g, 0.3 mmol) and
PNP1 (0.205 g, 0.6 mmol) were used to afford 0.268 g
(84%) of 4 as a white powder. m.p. 158–160 ꢁC. Anal.
Calc. for C49H47ClAgN5P2O4: C, 60.35; H, 4.86; N,
3.9. Preparation of Au2Cl2(PNP2) (8)
Similarly, Au(SMe2)Cl (0.236 g, 0.8 mmol) and PNP2
(0.195 g, 0.4 mmol) were stirred in CH2Cl2 (30 ml) for
0.5 h at room temperature to afford 0.355 g (82%) of 8
as a white powder. m.p. 232–234 ꢁC. Anal. Calc. for
C29H25Au2Cl2N3P2: C, 36.96; H, 2.67; N, 4.46. Found:
C, 37.11; H, 2.31; N, 4.65%. 1H NMR (CDCl3, d,
ppm): 7.22–7.34 (m, 21H, 4Ph and Py-H4), 6.34 (d,
2H, Py-H3/H5). 31P NMR (CDCl3, d, ppm): 52.34.
1
7.18. Found: C: 60.93; H, 4.83; N, 6.98%. H NMR
(CDCl3, d, ppm): 7.53–7.92 (m, 31H, 6Ph and Py-H4),
5.89 (d, 2H, Py-H3/H5), 4.67(d, 4H, 2CH2PPh2), 4.16
(s, 4H, 2CH2Ph), 3.97(s, 6H, 2CH 3CN), 31P NMR
(CDCl3, d, ppm): ꢀ11.61 [J(P–107Ag) = 478.0,
J(P–109Ag) = 586.4 ppm].
3.6. Preparation of Mo(CO)4(PNP1) (5)
3.10. Preparation of Au2(PNP2)2(ClO4)2 (9)
The same procedure as that for 1 was followed, but
Mo(CO)6 (0.132 g, 50 mmol) and PNP1 (0.348 g,
50 mmol) were reacted in CH3CN (10 ml) to reflux for
3 h, 0.307 g (62%) of 5 was obtained as a gray powder.
m.p. 174–176 ꢁC. Anal. Calc. for C49H41MoN3O4P2: C,
65.85; H, 4.62; N, 4.70. Found: C, 65.79; H, 4.58; N,
Similarly, 8 (0.188 g, 0.2 mmol) and Ag(CH3CN)4-
ClO4 (0.148 g, 0.4 mmol) were reacted in CH2Cl2
(30 ml) for 0.5 h at room temperature. Then, ligand
PNP2 (0.098 g, 0.2 mmol) was added and the mixture
was continued to react for 1 h, 0.210 g (82%) of 9 was
obtained as a white powder. m.p. 206–208 ꢁC. Anal.
Calc. for C58H50Au2Cl2N6O8P4: C, 45.01; H, 3.26; N,
1
4.69%. IR (KBr disk, cmꢀ1): m 1859–2017 (m(CO)). H
1
NMR (CDCl3, d, ppm): 7.51–7.11 (m, 31H, 6Ph and
Py-H4), 5.71 (d, 2H, Py-H3/H5), 4.65 (s, 4H, 2CH2PPh2),
3.44 (d, 4H, 2CH2Ph), 31P NMR (CDCl3, d, ppm):
16.62.
5.43. Found: C, 44.97; H, 3.51; N, 5.61%. H NMR
(CDCl3, d, ppm): 7.12–7.44 (m, 42H, 8Ph and 2Py-
H4), 6.55 (d, 4H, 2Py-H3/H5). 31P NMR (CDCl3, d,
ppm): 65.59.
3.7. Preparation of W(CO)4(PNP1) (6)
3.11. Preparation of Au2Cl2(PNP1) (10)
Similarly, W(CO)6 (0.141 g, 0.4 mmol) and PNP1
(0.274 g, 0.4 mmol) were reacted in THF (20 ml) to re-
flex for 10 h, 0.230 g (55.6%) of 6 was obtained as a yel-
low powder. m.p. 112–114 ꢁC. Anal. Calc. for
C49H41WN3O4P2: C, 59.95; H, 4.21; N, 4.28. Found:
C, 59.89; H, 4.17; N, 4.27%. IR: (KBr disk, cmꢀ1): m
Similarly, Au(SMe2)Cl (0.059 g, 0.2 mmol) and PNP1
(0.068 g, 0.1 mmol) were reacted in CH2Cl2 (30 ml) to
give 0.071 g (56%) of 10 as a white powder. m.p. 160–
162 ꢁC. Anal. Calc. for C45H41Cl2Au2N3P2: C, 46.97;
H, 3.59; N, 3.65. Found: C, 47.10; H, 3.51; N, 3.74%.
1H NMR (CDCl3, d, ppm): 7.62–7.10 (m, 31H, 6Ph
and Py-H4), 5.88 (d, 2H, Py-H3/H5), 5.19 (s, 4H,
2CH2PPh2), 4.16 (d, 4H, 2CH2Ph), 31P NMR (CDCl3,
d, ppm): 19.96.
1
1864–2016 (m(CO)). H NMR (CDCl3, d, ppm): 7.60–
7.00 (m, 31H, 6Ph and Py-H4), 5.89 (d, 2H, Py-H3/
H5), 4.78 (s, 4H, 2CH2PPh2), 3.54 (d, 4H, 2CH2Ph),
31P NMR (CDCl3, d, ppm): 25.5.
3.12. Preparation of Au2(PNP1)2(ClO4)2 (11)
3.8. Preparation of [Pd(PNP1)]2(l-Cl)2(ClO4)2 Æ
1.5CH2ClCH2Cl (7 Æ 1.5CH2ClCH2Cl)
Similarly, 10 (0.115 g, 0.1 mmol) and Ag(CH3CN)4-
ClO4 (0.074 g, 0.2 mmol) were reacted in CH2Cl2
(30 ml) for 0.5 h at room temperature. Then, ligand
PNP1 (0.068 g, 0.1 mmol) was added and the mixture
was continued to react for 1 h, 0.130 g (86%) of 11
was obtained as a green powder. m.p. 160–164 ꢁC.
Anal. Calc for C90H82Cl2Au2N6O8P4: C, 55.02; H,
4.21; N, 4.28. Found: C, 55.09; H, 4.22; N, 4.10%.
1H NMR (CDCl3, d, ppm): 7.53–6.93 (m, 62H, 12Ph
and 2Py-H4), 5.86 (d, 4H, 2Py-H3/H5), 4.30 (s, 8H,
4CH2PPh2), 3.47 (d, 8H, CH2Ph), 31P NMR (CDCl3,
d, ppm): 34.45.
Similarly, Cu(CH3CN)4ClO4 (0.065 g, 0.2 mmol) and
1 (0.190 g, 0.2 mmol) were reacted in CH2Cl2 (30 ml) for
1 h, 0.200 g (87%) of 7 was obtained as a yellow powder.
m.p. 140–142 ꢁC. The crystal sample for analysis was
further
purified
by
recrystallization
from
CH2ClCH2Cl/cyclohexane. Analysis and subsequent
refinement of the X-ray structure of a crystal of 7
showed
that
it
had
the
composition
of
C90H82Cl2N6P4Pd2(ClO4)2 Æ 2CH2ClCH2Cl. Anal. Calc.
for C93H88Cl7N6O8P4Pd2: C, 55.78; H, 4.43; N, 4.20.

Table 1
Crystal data and refinement parameters
PNP1
45H41N3P2
685.75
1 Æ CH2Cl2
3
5
7 Æ 1.5CH2ClCH2Cl
8 Æ 2DMSO
Formula
C
C46H43Cl4N3P2Pd
947.97
C49H47ClCuN5O4P2
930.85
triclinic
C49H41MoN3O4P2
893.73
C93H88Cl7N6O8P4Pd2
2002.52
monoclinic
P21/n
C33H37Au2Cl2N3O2P2S2
1096.53
triclinic
Formula weight
Crystal system
Space group
triclinic
ꢀ
monoclinic
P21/n
monoclinic
P21/c
ꢀ
ꢀ
P1
P1
P1
˚
a (A)
8.854(5)
11.231(6)
18.955(11)
91.231(9)
91.336(9)
90.954(10)
1883.6(18)
2
13.785(4)
17.298(5)
18.139(5)
90
10.457(3)
11.483(3)
20.210(6)
98.813(4)
92.920(5)
104.144(5)
2315.4(11)
2
18.889(6)
10.183(3)
22.019(7)
90
12.926(4)
17.962(5)
20.793(6)
90
11.852(5)
12.840(5)
13.476(5)
92.762(7)
106.749(6)
96.649(7)
1943.4(13)
2
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
92.825(5)
90
91.168(6)
90
107.186(5)
90
3
˚
V (A )
4320(2)
4
1.458
4234(2)
4
1.402
4612(2)
2
1.442
Z
Dcalcd (g cmꢀ3
)
1.209
0.151
724
1.335
0.648
968
1.874
7.900
1048
l (mmꢀ1
F(0 0 0)
Crystal size (mm)
)
0.788
1936
0.434
1840
0.720
2046
0.22 · 0.20 · 0.16
0.71073
1.07–26.40
293(2)
0.18 · 0.16 · 0.08
0.71073
1.63–26.42
293(2)
0.26 · 0.22 · 0.20
0.71073
1.02–26.46
293(2)
0.18 · 0.16 · 0.14
0.71073
1.08–25.01
293(2)
0.30 · 0.22 · 0.12
0.71073
1.66–26.47
293(2)
0.20 · 0.18 · 0.18
0.71073
1.58–25.01
293(2)
˚
k (A)
hmin–hmax (ꢁ)
T (K)
Number of data collected
10 352
7434
24 672
8832
13 528
9407
21 383
7459
26 469
9500
10 125
6814
Number of unique data
Rint
0.0327
451
1.070
0.0863
505
1.009
0.0224
607
1.017
0.1040
532
0.981
0.0650
586
1.046
0.0298
451
1.012
Number of refined parameters
Goodness-of-fit on F2a
Final R indicesb
R1
wR2
0.0674
0.1585
0.0530
0.0995
0.0592
0.1380
0.0562
0.0977
0.0636
0.1481
0.0392
0.0815
R indices (all data)
R1
0.1327
0.1884
0.1221
0.1267
0.1013
0.1636
0.1363
0.1274
0.1328
0.1841
0.0772
0.0977
wR2
Final difference map (e A
Refinement method
ꢀ3
˚
)
0.299, ꢀ0.304
0.506, ꢀ0.463
1.638, ꢀ1.083
0.409, ꢀ0.424
1.006, ꢀ0.546
1.060, ꢀ1.287
full-matrix least-squares on F2
P
2
Goodness-of-fit ¼ ½ xðF 2o ꢀ F c2Þ =ðn ꢀ pÞꢁ1=2, where n is the number of reflections and p is the number of parameters refined.
a
P
P
b
R1 ¼ ðjjF oj ꢀ jF cjÞ= jF oj; wR2 ¼ 1=½r2ðF o2Þ þ ð0:0691PÞ þ 104100Pꢁ; where P ¼ ðF o2 þ 2F 2c Þ=3.

2290
Q.-S. Li et al. / Inorganica Chimica Acta 358 (2005) 2283–2291
Table 2
tained CH2Cl2, CH2ClCH2Cl and DMSO solvent
molecules, respectively. The data collections were car-
ried out at 293(2) K on a Bruker SMART 1000 CCD
˚
Selected bond distances (A) and angles (ꢁ) with estimated standard
deviations
Ligand PNP1
˚
diffractometer using Mo Ka radiation (0.71073 A). Data
P(1)–C(13)
P(2)–C(33)
1.860(4)
1.864(3)
121.9(3)
114.2(2)
N(1)–C(13)
N(2)–C(33)
1.452(4)
1.447(4)
121.4(3)
114.3(2)
collection at 293 K and reduction were performed using
the SMART and SAINT software with frames of 0.3ꢁ oscil-
lations. An empirical absorption correction was applied
using the SADABS program. An empirical absorption
correction was applied using w-scan data. The structures
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.
Non-hydrogen atoms were subjected to anisotropic
refinement. All hydrogen atoms were generated geomet-
C(21)–N(1)–C(13)
N(1)–C(13)–P(1)
C(25)–N(2)–C(33)
N(2)–C(33)–P(2)
Complex 1
Pd(1)–P(1)
2.2517(14)
2.2610(15)
2.3442(15)
2.3584(15)
96.16(5)
P(1)–C(6)
P(2)–C(26)
1.868(5)
1.852(5)
1.445(6)
1.454(6)
175.25(5)
83.72(5)
91.39(5)
Pd(1)–P(2)
Pd(1)–Cl(2)
Pd(1)–Cl(1)
N(1)–C(6)
N(3)–C(26)
P(1)–Pd(1)–P(2)
P(1)–Pd(1)–Cl(2)
P(2)–Pd(1)–Cl(2)
P(1)–Pd(1)–Cl(1)
P(2)–Pd(1)–Cl(1)
Cl(2)–Pd(1)–Cl(1)
89.57(5)
168.62(5)
˚
rically (C–H bond lengths fixed at 0.95 A), assigned
Complex 3
Cu(1)–N(4)
appropriate isotropic thermal parameters and included
in structure factor calculations. Details of the crystals,
data collections, and structure refinements are summa-
rized in Table 1.
2.017(4)
2.155(4)
P(1)–C(13)
P(2)–C(38)
2.2608(12) 0 N(1)–C(13)
1.856(4)
1.858(3)
1.455(5)
1.452(5)
108.29(13)
113.66(4)
119.7(3)
119.9(3)
Cu(1)–N(5)
Cu(1)–P(1)
Cu(1)–P(2)
2.2620(12)
98.42(17)
N(3)–C(38)
N(4)–Cu(1)–N(5)
N(4)–Cu(1)–P(1)
N(5)–Cu(1)–P(1)
N(4)–Cu(1)–P(2)
N(5)–Cu(1)–P(2)
P(1)–Cu(1)–P(2)
C(21)–N(1)–C(13)
C(25)–N(3)–C(38)
117.51(11)
104.39(12)
112.59(11)
4. Supplementary material
Complex 5
Mo(1)–P(2)
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC Nos. 243659–243663 and 244406
for compounds PNP1, 1, 3, 7, 5 and 8, respectively. Cop-
ies of this information may be obtained free of charge
from The Director, CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK /(fax:+44 1223 336033; e-mail: deposit@
ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
2.5752(15)
2.5942(16)
1.885(5)
P(2)–C(37)
N(1)–C(17)
N(3)–C(37)
1.862(5)
1.436(6)
1.456(6)
124.81(17)
120.8(5)
117.3(4)
114.9(4)
117.3(3)
Mo(1)–P(1)
P(1)–C(17)
P(2)–Mo(1)–P(1)
C(3)–Mo(1)–P(2)
C(2)–Mo(1)–P(2)
C(3)–Mo(1)–P(1)
C(2)–Mo(1)–P(1)
C(17)–P(1)–Mo(1)
96.41(5)
C(37)–P(2)–Mo(1)
C(25)–N(1)–C(17)
C(29)–N(3)–C(37)
N(1)–C(17)–P(1)
N(3)–C(37)–P(2)
88.66(17)
173.73(18)
174.64(17)
87.54(17)
123.14(18)
Complex 7
Pd(1)–P(2)
2.2523(16)
2.2714(16)
2.3606(16)
1.846(6)
P(2)–C(33)
1.863(6)
2.3916(16)
1.444(8)
1.432(8)
111.0(2)
Pd(1)–P(1)
Pd(1)–Cl(1)
P(1)–C(13)
Cl(1)–Pd(1A)
N(2)–C(13)
N(3)–C(33)
Acknowledgment
This work was supported by the National Science/
Foundation of China (Project Grant No. 20102003).
P(2)–Pd(1)–P(1)
P(2)–Pd(1)–Cl(1)
P(1)–Pd(1)–Cl(1)
P(2)–Pd(1)–Cl(1A)
P(1)–Pd(1)–Cl(1A)
95.71(6)
95.07(6)
C(33)–P(2)–Pd(1)
Pd(1)–Cl(1)–Pd(1A) 97.29(6)
167.98(6)
173.77(7)
87.09(6)
C(21)–N(2)–C(13)
C(25)–N(3)–C(33)
N(2)–C(13)–P(1)
N(3)–C(33)–P(2)
118.9(5)
120.2(5)
117.1(4)
114.8(4)
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Cl(1)–Pd(1)–Cl(1A) 82.71(6)
C(13)–P(1)–Pd(1)
110.8(2)
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