Reactivity of alkynyl Pd(II) azido complexes toward organic isocyanides, isothiocyanates, and nitriles

Article abstract of DOI:10.1016/j.ica.2004.09.056

Alkynyl Pd(II) azido complexes of the type [Pd(N₃)(C≡C-R) L₂] (1-3) were obtained by reactions of aqueous NaN₃ with [Pd(Cl)(C≡C-R)L₂] (R = Ph or C(O)OMe). Treating compounds 1-3 with organic isocyanides (R-NC) afforded novel complexes, trans-[Pd(C≡C- Ph)(N=C=N-R)(PMe₃)₂] (R = 2,6-Me₂C ₆H₃ (4) or 2,6-Et₂C₆H₃ (5)) and trans-[Pd(C≡C-R)(CN₄-t-Bu)L₂] (6: L = PMe₃, R = Ph; 7: L = PEt₃, R = C(O)OMe; 8: L = PMe ₃, R = C(O)OMe), which contain either a carbodiimido or a C-coordinated tetrazolato group. Reactions of compounds 1 and 2 with R-N=C=S (R = 2,6-Me₂C₆H₃ or CH₂CH₃) and 1,4-phenylene diisothiocyanate (C₆H₄(N=C=S) ₂) smoothly proceeded to give tetrazole-thiolato complexes, trans-[Pd(C≡CPh)(SCN₄-R)L₂] (L = PMe₃, R = Et (9) or 2,6-Me₂C₆H₃ (10); L = PEt ₃, R = 2,6-Me₂C₆H₃ (11)), and a phenylene-bridged dinuclear Pd(II) tetrazole-thiolato complex, [(PEt ₃)₂(C≡CPh)Pd(SCN₄-(μ-C ₆H₄)-SCN₄)Pd(C≡CPh)(PEt₃) ₂] (12), respectively. Complexes 9-12 contain the Pd-S bond that is formed by the dipolar cycloaddition of the organic isothiocyanate to the Pd-azido bond. In contrast, the corresponding reactions of compounds 1and 2 with C₆F₅CN and Me₃SiCN (organic nitriles, R-CN) gave an N-coordinated Pd(II)-tetrazolato compound {trans-[Pd(C≡C-Ph) (N₄C-C₆F₅)(PMe₃)₂] (13)} and a mixture of Pd(II)-cyano complexes {trans-[Pd(C≡C-Ph)(CN)(PEt ₃)₂] (14) and [Pd(CN)₂(PEt₃) ₂] (15)}, respectively. Bis(phosphine) bis(cyano) complexes of Pd and Ni, [M(CN)₂L₂] (L = PEt₃, PMe₃; L₂ = DEPE), could be obtained independently by the reactions of [M(N₃)₂L₂] with excess Me₃SiCN in organic solvents.

Full text of DOI:10.1016/j.ica.2004.09.056

Inorganica Chimica Acta 358 (2005) 650–658
www.elsevier.com/locate/ica
Reactivity of alkynyl Pd(II) azido complexes toward
organic isocyanides, isothiocyanates, and nitriles
a,
a
a
a
b
Yong-Joo Kim *, Seung-Ha Lee , Sung-Hyun Lee , Sang Il Jeon , Mi S. Lim ,
b
Soon W. Lee
a
Department of Chemistry, Kangnung National University, Kangnung 120, Kangnung 210-702, Korea
Department of Chemistry, Sungkyunkwan University, Natural Science Campus, Suwon 440-746, Korea
b
Received 4 August 2004; accepted 28 September 2004
Available online 22 October 2004
Abstract
Alkynyl Pd(II) azido complexes of the type [Pd(N3)(C„CAR)L2] (1–3) were obtained by reactions of aqueous NaN3 with
[Pd(Cl)(C„CAR)L2] (R = Ph or C(O)OMe). Treating compounds 1–3 with organic isocyanides (R–NC) afforded novel complexes,
trans-[Pd(C„CAPh)(N@C@NAR)(PMe3)2] (R = 2,6-Me2C6H3 (4) or 2,6-Et2C6H3 (5)) and trans-[Pd(C„CAR)(CN4-t-Bu)L2] (6:
L = PMe3, R = Ph; 7: L = PEt3, R = C(O)OMe; 8: L = PMe3, R = C(O)OMe), which contain either a carbodiimido or a C-coordi-
nated tetrazolato group. Reactions of compounds 1 and 2 with R–N@C@S (R = 2,6-Me2C6H3 or CH2CH3) and 1,4-phenylene diis-
othiocyanate (C6H4(N@C@S)2) smoothly proceeded to give tetrazole–thiolato complexes, trans-[Pd(C„CPh)(SCN4–R)L2]
(L = PMe3, R = Et (9) or 2,6-Me2C6H3 (10); L = PEt3, R = 2,6-Me2C6H3 (11)), and a phenylene-bridged dinuclear Pd(II) tetraz-
ole–thiolato complex, [(PEt3)2(C„CPh)Pd(SCN4-(l-C6H4)–SCN4)Pd(C„CPh)(PEt3)2] (12), respectively. Complexes 9–12 contain
the Pd–S bond that is formed by the dipolar cycloaddition of the organic isothiocyanate to the Pd–azido bond. In contrast, the
vcorresponding reactions of compounds 1and 2 with C6F5CN and Me3SiCN (organic nitriles, R–CN) gave an N-coordinated
Pd(II)-tetrazolato compound {trans-[Pd(C„CAPh)(N4C–C6F5)(PMe3)2] (13)} and a mixture of Pd(II)-cyano complexes {trans-
[Pd(C„CAPh)(CN)(PEt3)2] (14) and [Pd(CN)2(PEt3)2] (15)}, respectively. Bis(phosphine) bis(cyano) complexes of Pd and Ni,
[M(CN)2L2] (L = PEt3, PMe3; L2 = DEPE), could be obtained independently by the reactions of [M(N3)2L2] with excess Me3SiCN
in organic solvents.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Azido; Cycloaddition; Alkynyl; Carbodiimide; Palladium
1. Introduction
heterocycles (C-coordinated), which were prepared by
treating bis(phosphine) metal complexes of bis(azido)
[M(N3)2(PR3)2] and mono(azido) methyl or phenyl
[M(N3)(R)(PR3)2] (R = Me or Ph) with organic isocya-
nides [19]. Although many derivatives of late transi-
tion-metal mono- or bis(azido) complexes have been
employed to study on the formation of metal complexes
containing the heterocycles mentioned above, azido me-
tal–alkynyl complexes have been relatively unexplored.
The alkynyl ligand exhibits interesting properties such
as cluster formation involving the bridging alkynyl lig-
and in multinuclear complexes [20–22], its conversion
Dipolar cycloaddition of unsaturated organic com-
pounds such as isocyanide, nitrile, and alkyne to an azi-
do ligand, which gives metal complexes containing C- or
N-coordinated heterocycles, has been an interesting sub-
ject for many decades [1–18]. We recently reported sev-
eral late transition-metal complexes containing such
*
Corresponding author. Tel.: +82 33 640 2308; fax: +82 33 647
1183.
E-mail address: yjkim@kangnung.ac.kr (Y.-J. Kim).
0020-1693/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2004.09.056

Y.-J. Kim et al. / Inorganica Chimica Acta 358 (2005) 650–658
651
to the corresponding vinylidene species [23], and its
potential optical or liquid crystalline properties as a
molecular wire having linear AC„C units [24]. We here
wish to report the preparation of alkynyl palladium(II)-
azido complexes and their reactivity toward organic iso-
cyanides and organic pseudo-halides (isothiocyanates
and nitriles).
reactions of 1–3 with tert-butyl isocyanide gave Pd(II)
complexes having a C-coordinated tetrazolato ring,
trans-Pd[(C„CAR)(CN4–t-Bu)L2] (R = Ph, L = PMe3
(6) or PEt3 (7); R = C(O)OMe, L = PMe3, (8)), as shown
in Eq. (4). Carbodiimido complexes 4–8 were isolated in
high yields and characterized by IR, NMR, and elemen-
tal analyses. Molecular structures of 5 and 6 were deter-
mined by X-ray crystallography.
R
2. Results and discussion
L
Pd
L
CN
L
Pd
L
R
R
R
Ph
N3
Ph
N=C=N
Alkynyl palladium(II) azido complexes 1–3 have been
prepared by usual coupling reactions and then subse-
quent metathetical substitution with NaN3 as shown in
Eqs. (1) and (2). These complexes have been obtained
as white crystalline solids in high yields and character-
ized by IR, NMR, and elemental analyses. Formation
of those complexes can be readily conformed by moni-
toring the stroꢀn1g absorption bands in the range of
L = PMe3, R = Me, 4
L = PMe3, R = Et, 5
ð3Þ
ð4Þ
L
Pd
L
L
CN
N
2050–2100 cm
bands.
due to the N3 and C„C stretching
R
N3
N
R
Pd
N
N
L
L
R = Ph L = PMe3, 6; PEt3, 7
R = C(O)OMe L = PMe3, 8
CuBr, Et2NH
PdCl2L2
R
ð1Þ
ð2Þ
Pd
L
Cl
H
L
R
(1eq)
No other products (for example, an imino-bonded
complex formed by the isocyanide insertion into the
Pd–C bond) were observed. The formation of carbo-
diimido Pd(II) complexes appears to involve an initial
formation of a C-coordinated tetrazolato ring by the
cycloaddition of isocyanide into the palladium–azido
bond and then the subsequent ring conversion to an
end-on NCN group with the elimination of N2 to give
a final product. In a recent work, we reported that the
formation of the carbodiimido or C-coordinated tetra-
zolato group was dependent not only on the type of
an attacking isocyanide and but also on the steric bulk
of alkyl substituents on the aryl ring that might facilitate
N2 elimination from the tetrazolato ring to give the cor-
responding carbodiimido group [19a,19b].
Figs. 1 and 2 show the molecular structures of trans-
[Pd(C„CPh)(N@C@NAC6H3-2,6-Et2)(PMe3)2] (5) and
trans-[Pd(C„CPh)(CN4-t-Bu)(PMe3)2] (6), respectively.
Crystal data are summarized in Table 1. Fig. 1 clearly
shows the square-planar geometry of complex 5, which
contains two PMe3, one alkynyl, and one end-on carbo-
diimido (NCN–C6H3-2,6-Et2) ligands. The linear phe-
nylethynyl group is located trans to the carbodiimido
group. A triplet in 13C{1H} NMR, which is coupled
with two phosphine ligands and corresponds to the alky-
nyl carbon (Ca„C or C„Cb) directly bonded to the Pd
metal, supports the trans-geometry of the complexes.
Furthermore, a singlet at ꢀ12.3 ppm in 31P{1H} NMR
also supports the trans-structure. The phenyl ring in
the carbodiimido ligand is nearly perpendicular to the
L
NaN3
R
Pd Cl
L
R
Pd
L
N3
R = Ph, L = PMe3 (1), PEt3, (2)
R = MeO(CO), L = PMe3 (3)
2.1. Reactions with isocyanides
As mentioned in Section 1, we recently reported that
bis(phosphine) group 10 metal complexes, [M(N3)2-
(PR3)2] and [M(N3)(R)(PR3)2] (R = Me or Ph), reacted
with various isocyanides to give complexes containing
carbodiimido or tetrazolato groups through cyclodaddi-
tion of isocyanides to the metal–azido bond [19]. On the
basis of these results, we have examined the reactivity of
alkynyl palladium(II) azido complexes toward isocya-
nides as shown in Eq. (3). Treatment of the isocyanide
with the azido complex caused immediate evolution of
nitrogen gas, and their reaction was monitored by the
IR spectra, which showed the disappearance of an asym-
metric stretching N3 band at ca. 2050 cmꢀ1 and the
appearance of new strong bands at ca. 2170 cmꢀ1 and
2117–2128 cmꢀ1 due to the carbodiimido (N@C@N)
and C„C groups, respectively, in the products, trans-
[Pd(C„CPh)(N@C@NAR)(PMe3)2] (R = 2,6-Me2C6H3
(4) or 2,6-Et2C6H3 (5)). On the other hand, analogous

652
Y.-J. Kim et al. / Inorganica Chimica Acta 358 (2005) 650–658
˚
Fig. 1. ORTEP drawing[34] of 5 showing the atom-labeling scheme and 50% probability thermal ellipsoids. Selected bond lengths (A) and angles (ꢁ):
Pd1–C7 1.941(3), Pd1–N1 2.035(3), Pd1–P2 2.3023(8), Pd1–P1 2.3086(8), N1–C15 1.156(4), N2–C15 1.252(4), N2–C16 1.386(4), C7–C8 1.202(4), C8–
C9 1.439(4); C7–Pd1–N1 177.0(1), P2–Pd1–P1 174.72(3), C15–N1–Pd1 160.0(3), C15–N2–C16 133.0(3), N1–C15–N2 171.7(4), C8–C7–Pd1 177.5(3),
C7–C8–C9 177.6(3).
2.2. Reactions with organic pseudo-halides
In order to examine the scope of the reactivity of
the alkynyl Pd(II) azido complexes, we have treated
them with RAN@C@S (R = 2,6-Me2C6H3 or CH2CH3)
and 1,4-phenylene diisothiocyanate (C6H4(N@C@S)2).
These reactions as shown in Eq. (5), dipolar cycloaddi-
tion of an organic RAN@C@S into the Pd–azido bond,
proceeded smoothly at room temperature to give tetraz-
ole–thiolato complexes, trans-[Pd(C„CPh)(SCN4–R)-
L2] (L = PEt3, R = 2,6-Me2C6H3 (9); L = PMe3,
R = Et (10) or 2,6-Me2C6H3 (11)). As shown in Eq.
˚
(6), the same reaction with 1,4-phenylene diisothiocya-
nate (2:1 ratio) also produced a phenylene-bridged
dinuclear Pd(II) tetrazole–thiolato complex, [(PEt3)2
(C„CPh)Pd(SCN4-(l-C6H4)–SCN4)Pd(C„CPh)(PEt3)2]
(12). Complexes 9–12 were characterized by spectro-
scopic and analytical methods. Formulation of 12 was
also confirmed by FAB(+) mass spectra. The reaction
completion can be readily confirmed by monitoring
the disappearance of m(N3) band at 2030 cmꢀ1, which
results from the dipolar cycloaddition of the isothiocy-
anates into the Pd–azido bond. Integration ratios in
each of the 1H NMR spectra of 9–12 are consistent
with the proposed structures. A signal at 161–164
ppm in 13C{1H} NMR corresponds to the carbon atom
of the tetrazolato ring, [S–(CN4–R)]. A singlet in
31P{1H} NMR also supports the proposed trans-struc-
ture. These spectral data strongly indicate the absence
of N-bonded tetrazoline compounds M[N4(R)(C@S)],
which can adopt an N1- or an N2-bonded form.
Fig. 3 shows an ORTEP drawing of trans-[Pd(C„CPh)-
(SCN4–C6H3-2,6-Me2)(PMe3)2] (11). The molecular
structure of 11 clearly shows an S-coordinated tetrazo-
lato ring.
Fig. 2. ORTEP drawing of 6. Selected bond lengths (A) and angles (ꢁ):
Pd1–C7 2.005(5), Pd1–C15 2.036(4), N1–C15 1.352(4), N1–N2
1.360(4), N2–N3 1.280(5), N3–N4 1.367(5), N4–C15 1.348(5), C7–C8
1.195(6); C7–Pd1–C15 178.2(1), C15–Pd1–P1 92.45(9), C15–Pd1–P2
93.03(9), P1–Pd1–P2 170.66(4), C15–N1–N2 110.0(3), N2–N1–C16
119.6(3), N3–N2–N1 106.5(3), N2–N3–N4 110.7(3), C15–N4–N3
107.3(3), C8–C7–Pd1 172.9(4).
equatorial plane with the dihedral angle of 84.58(9)ꢁ.
The Pd–N bond length of 5 is close to the previously re-
ported one in trans-[Pd(CN4–R)(N@C@NAR)(PMe3)2]
˚
(2.030(5) A) [19b], but it is slightly shorter than
that in trans-[Pd(Ph)(N@C@NAC6H3-2,6-Me2)(PMe3)2]
˚
(2.087(3) A) [19c], suggesting a weaker trans-influence of
the phenylethynyl group than the phenyl ring. The
asymmetric nitrogen–carbon bonds (1.156(4) and
1.252(4) A) in the carbodiimido (N@C@N) group of 5
have also been observed for those in other carbodiimido
complexes [19a]. Fig. 2 shows the structure of 6 possess-
ing the C-coordinated tetrazolato ring. A triplet signal
at 164 ppm in 13C{1H} NMR due to the carbon of the
tetrazolato ring strongly supports the C-coordination
of the ring to the Pd metal.
˚

Y.-J. Kim et al. / Inorganica Chimica Acta 358 (2005) 650–658
653
Table 1
X-ray data collection and structure refinement for 5, 6, 11, and 18
5
6
11
18
Formula
Fw
C25H36N2P2Pd
532.90
295(2)
C19H32N4P2Pd
484.83
296(2)
C23H32N4P2SPd
564.93
293(2)
C12H24N2P2Pd
364.67
293(2)
Tmperature (K)
Crystal size (mm3)
Crystal system
Space group
0.24 · 0.22 · 0.20
triclinic
0.40 · 0.24 · 0.22
monoclinic
P21/c
0.20 · 0.15 · 0.08
triclinic
0.20 · 0.18 · 0.16
monoclinic
C2/c
ꢀ
ꢀ
P1
P1
˚
a (A)
9.832(1)
12.246(2)
13.028(1)
65.519(7)
73.463(10)
87.496(8)
1363.4(3)
2
20.586(18)
9.5410(9)
12.2037(9)
9.405(2)
13.239(2)
13.321(2)
119.69(1)
97.16(2)
103.09(2)
1347.4(4)
2
18.376(2)
8.525(1)
10.255(1)
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
96.455(6)
96.402(8)
3
˚
V (A )
2381.7(4)
4
1596.4(3)
4
Z
dcalc (g cmꢀ3
)
1.298
0.811
552
1.352
0.923
1000
1.392
0.902
580
1.517
1.346
744
l (mmꢀ1
F(000)
Tmin
)
0.7891
0.8413
4927
0.4453
0.5235
4388
0.8304
0.9377
4609
0.7293
0.9273
1399
1359
1356
78
Tmax
Number of reflections measured
Number of reflections unique
4629
4081
4167
3433
4324
3080
Number of reflections with I > 2r(I)
Number of parameterꢀs3refined
272
0.435
236
280
0.293
˚
Maximum in Dq (e A
)
0.439
ꢀ0.551
1.009
0.0364
0.0962
0.0481
0.0956
0.241
ꢀ0.298
ꢀ3
˚
Minimum in Dq (e A
)
ꢀ0.399
1.021
ꢀ0.353
1.090
Goodness of fitness on F2 1.053
R
0.0300
0.0899
0.0367
0.0813
0.0455
0.0527
0.0775
0.1102
0.0202
a
wR2 0.0775
R (all data)
a
wR2 (all data)
0.0211
0.0534
P
P
2
2 1=2
a
wR2 ¼ ½wðF 2o ꢀ F c2Þ ꢁ= ½wðF 2oÞ ꢁ
.
(Eqs. (5) and (6)) also gave tetrazole–thiolato Pd(II)
complexes having alkynyl ligands. Although several
studies [5f,6,10,14,26] on the cycloaddition of organic
isothiocyanates into the transition-metal azido
complexes to give N-bonded tetrazoline-5-thione,
(M[N4(C@S)]) complexes have been reported, the
case of tetrazole–thiolato complex formation did
not appear in the literature until our recent work.
It is worth noting that Beck et al. [27] previously
prepared anionic tetrazole–thiolato Pd(II) and Pt(II)
complexes in a way different from ours: (a) by the
metathesis of metal halides with alkali metal salts
of tetrazole mercaptan or (b) by the reactions of me-
tal halides with alkyl mercaptan in the presence of
amine.
˚
Fig. 3. ORTEP drawing of 11. Selected bond lengths (A) and angles (ꢁ):
Pd1–C8 1.966(5), Pd1–P1 2.306(2), Pd1–P2 2.316(2), Pd1–S1 2.357(2),
S1–C15 1.716(5), N1–C15 1.324(6), N1–N2 1.371(6), N2–N3 1.289(6),
N3–N4 1.359(6), N4–C15 1.363(6), C7–C8 1.209(7); C8–Pd1–P1
85.1(2), C8–Pd1–P2 85.9(2), P1–Pd1–P2 170.06(5), C8–Pd1–S1
178.0(2), P1–Pd1–S1 95.99(6), P2–Pd1–S1 93.18(6), C15–S1–Pd1
106.3(2), C15–N1–N2 105.8(4), N3–N2–N1 111.6(4), N2–N3–N4
106.1(4), N3–N4–C15 108.5(4).
L
L
R
R-NCS
N
Ph
Pd
L
N3
Ph
Pd
S
N
N
N
L
L = PEt3, R = 2,6-Me2C6H3, 9
L = PMe3, R = CH2CH3, 10; 2,6-Me2C6H3, 11
Recently, we reported that reactions of bis(azido)–
Pd(II) complexes with organic isothiocyanates gave
tetrazole–thiolato complexes [25]. Our present work
ð5Þ

654
Y.-J. Kim et al. / Inorganica Chimica Acta 358 (2005) 650–658
PEt3
Pd
lato isomers were formed by the reactions of Ni(II) azi-
SCN
NCS
do complexes with benzonitrile derivatives with the
relative abundances dependent on the reaction stoichi-
ometry and that the N2-bound isomer was a sole prod-
uct in the case of p-NO2C6H5CN.
Interestingly, similar reactions of 2 with excess Me3-
SiCN at room temperature led to the formation of
unusual metal cyano complexes, trans-[Pd(C„CPh)-
(CN)(PEt3)2] (14, 85%) and [Pd(CN)2(PEt3)2] (15, trace),
as a mixture (Eq. (8)).
Ph
N3
( 2 : 1 )
PEt3
Ph
PEt3
Pd
PEt3
Pd
PEt3
S
S
Ph
N
N
N
N
N
PEt3
N
N
N
12
ð6Þ
We have also examined dipolar cycloaddition reac-
PEt3
Pd
PEt3
PEt3
Pd
PEt3
Me3SiCN
tions between alkynyl Pd(II) azido complexes and
organic nitriles such as C6F5CN and Me3SiCN. Treat-
ment of 1 with excess C6F5CN at room temperature
gave an N-coordinated tetrazolato compound, trans-
[Pd(C„CPh)(N4C–C6F5)(PMe3)2] (13), as shown in
Eq. (7). 1H and 31P{1H} NMR spectra of the crude
product, which show two virtual triplets (integration ra-
tio of 8:92) due to PMe3 ligands in the 1H NMR and two
singlets in the 31P{1H} NMR, suggest the presence of a
mixture of N1 or N2-coordinated tetrazolato isomers. By
fractional recrystallization of the crude reaction prod-
uct, a pure tetrazolato complex 13 could be isolated as
white solids in 37% yield.
Ph
N3
Ph
CN + Pd(CN)2(PEt3)2
15
14
ð8Þ
Complex 14 is soluble in diethyl ether and so can be
readily extracted from the mixture. IR spectrum of 14
shows a strong absorption band at 2108 cmꢀ1 due to
m(CN), which is overlapped with a weak m(C„C) band.
In the 13C{1H} NMR spectrum of 14, a triplet at 136.0
(J = 13 Hz) ppm due to the C„N and two triplets at
105.0 (J = 17 Hz) and 110.9 (J = 4 Hz) ppm, corre-
sponding to the Ca„C and C„Cb, respectively,
strongly support the presence of a cyano group and an
alkynyl group coordinated to the Pd center. The same
PMe3
Pd
PMe3
PMe3
C6F5CN
N
reaction with
1
also produced
a
mixture of
Ph
N3
C
C6F5
Ph
Pd
N
[Pd(C„CPh)(CN)(PMe3)2] (16) and [Pd(CN)2(PMe3)2]
(17), but quite similar solubility of these complexes
prohibited the isolation of a pure alkynyl Pd(II) cyano
complex (16).
Bis(cyano) palladium(II) complexes 15 and 17 could
be independently prepared from [Pd(N3)2L2] (L = PEt3,
PMe3, or DEPE) and two equivalent or excess Me3SiCN
as shown in Eq. (9). Furthermore, this synthetic method
could successfully apply to the preparation of a nicke-
l(II) analog Ni(CN)2(PEt3)2. Fig. 4 shows the molecular
structure of 18. Considering the structures of cyano pal-
N
N
PMe3
13
ð7Þ
IR spectrum of 13 shows a characteristic C„C band
without the N3 band of the starting material. Earlier
works by Beck and co-workers [5c,6] and several other
research groups [14b,14c,28,29] demonstrated the simi-
lar N1- or N2-coordination modes in the tetrazolato
Pd(II) or Pt(II) complexes. In particular, Paul and
Nag [14a] observed that both N1 and N2-bound tetrazo-
˚
Fig. 4. ORTEP drawing of 18. Selected bond lengths (A) and angles (ꢁ): Pd1–C6 2.034(2), Pd1–P1 2.2792(6), N1–C6 1.139(3); C6–Pd1–P1 174.03(7),
N1–C6–Pd1 177.0(2).

Y.-J. Kim et al. / Inorganica Chimica Acta 358 (2005) 650–658
655
ladium and nickel complexes 14–19, an order of trans-ef-
fect strengths among ligands appears to be azido < alky-
nyl, cyano in our reaction systems.
niques. Solvents were distilled from Na-benzophenone.
The analytical laboratory at the Kangnung National
University carried out elemental analyses using CE
instruments EA1110. IR spectra were recorded on a
Perkin–Elmer BX spectrophotometer. NMR (1H,
13C{1H}, and 31P{1H}) spectra were obtained on a
JEOL Lamda 300 MHz spectrometer. Chemical shifts
were referenced to internal Me4Si and to external 85%
H3PO4. [PdCl(C„CAR)L2] (R = Ph, C(O)OMe;
L = PMe3, PEt3)2 were prepared by the literature
method [32].
M(N3)2L2
+ 2 Me3SiCN
M(CN)2L2
M = Pd L = PEt3, 15
L = PMe3, 17
ð9Þ
L-L = DEPE, 18
M = Ni L = PEt3, 19
The formation of cyano complexes 14 and 15 (Eq.
(8)) indicates that Pd–C (alkynyl) and Pd–N bonds are
cleaved by the relatively weak nucleophile (CNꢀ) to give
metal cyano complexes. However, we could not observe
that other types of organic nitriles (R–CN) gave such
cyano complexes. There are a couple of examples dem-
onstrating the replacement of carbon-donor ligands by
the CNꢀ agent (in the form of Me3SiCN). For example,
Tsuji et al. [30] reported palladium-catalyzed cyanation
in reactions between Me3SiCN and allylic acetate or
carbonates. In this study, Me3SiCN converted a p-allyl
palladium acetate complex to a cyano Pd(II) complex.
Moreover, Butenscho¨n and co-workers recently re-
ported the transformation of a cyclopentadienyl Co(I)
ethane complex to a dicyano Co(III) complex by the
oxidative addition of Me3SiCN [31]. Generally, transi-
tion-metal cyano complexes are prepared from transi-
tion-metal halides and alkali metal cyanide by
metathesis in alcohol or aqueous media. Therefore,
the formation of the cyano complexes with Me3SiCN
(Eqs. (8) and (9)) can be an efficient way of introducing
the cyano group to metal–azido complexes in organic
solvents, and this type of cyanation may be expanded
to prepare other pseudo-halogen compounds of transi-
tion metals.
In summary, we prepared three novel alkynyl Pd(II)
azido complexes and examined their reactivity toward
organic isocyanides, isothiocyanates, and nitriles.
Depending on the organic substrates, complexes con-
taining five-membered heterocycles (C- or N-coordi-
nated tetrazolato or tetrazole–thiolato) or carbodimido
groups were formed. These results show an overall
agreement with those previously found in bis(azido)
group 10 metal complexes [19a]. One interesting finding
in this study is that Me3SiCN can serve as an efficient
agent in introducing the cyano group into the transi-
tion-metal azido complexes in organic solvents to give
cyano or bis(cyano) Pd(II) and Ni(II) complexes.
3.2. Preparation of trans-[Pd(N3)(C„CAR)L2]
(R = Ph, L = PMe3 (1), PEt3 (2); R = (CO)OMe,
L = PMe3 (3))
To a THF solution (10 ml) of [PdCl(C„CPh)-
(PMe3)2] (0.344 g, 0.87 mmol) was added an aqueous
solution of NaN3 (0.113 g, 1.74 mmol) by a cannula.
After stirring the reaction mixture for 24 h at room tem-
perature, the solvent was completely evaporated. The
residue was then extracted with CH2Cl2. The collected
extract was reduced to 3 ml under vacuum. Addition
of n-hexane (10 ml) caused separation of pale brown
solids, which were freshly chromatographed from alu-
mina (elutant, CH2Cl2) and then recrystallized from
ether to give white solids (83%) of [Pd(N3)
(C„CPh)(PMe3)2] (1). IR (KBr, cmꢀ1): 2120 (w,
1
C„C), 2046 (s, br, N3). H NMR (CDCl3, d): 1.58 (t,
18 H, J = 3.5 Hz, PMe3) 7.17–7.31 (m, 5 H, Ph).
13C{1H} NMR (CDCl3, d): 14.1 (t, J = 16 Hz,
P(CH3)3), 93.7 (t, J = 19 Hz, Ca„C), 108.0 (t, J = 5.3
Hz, C„Cb), 126.1, 127.0, 128.1, 130.9 (t, J = 1.6 Hz).
31P{1H} NMR (CDCl3, d): ꢀ14.8(s). Anal. Calc. for
C14H23N3P2Pd: C, 41.86; H, 5.77; N, 10.46. Found:
C41.97; H, 5.91; N, 9.21%.
Complexes 2 and 3 were similarly prepared. Com-
plex 2 (79 %): IR (KBr, cmꢀ1): 2117 (w, C„C),
2052 (s, br, N3). 1H NMR (CDCl3Hz, d): 1.24 (q,
18 H, J = 7.9 Hz, P(CH2CH3)3), 1.96 (m, 12 H,
P(CH2CH3)3), 7.15–7.27 (m,
5
H, Ph). 13C{1H}
NMR (CDCl3, d): 8.34 (s, P(CH2C H3)3), 15.4 (t,
J = 14 Hz, P(CH2CH3)3), 93.4 (br s, Ca„C), 108.0
(t, J = 5 Hz, C„Cb), 125.8, 127.6, 128.1, 130.7 (t,
J = 1 Hz). 31P{1H} NMR (CDCl3, d): ꢀ13.6(s). Anal.
Calc. for C20H35N3P2Pd: C, 49.44; H, 7.26; N, 8.65.
Found: C, 49.40; H, 7.20; N, 8.21%.
Complex 3 (82%): IR (KBr, cmꢀ1): 2128 (w, C„C),
1
2059 (s, br, N3), 1687 (s, br, CO). H NMR (CDCl3,
d): 1.55 (t, 18 H, J = 3.7 Hz, PMe3), 3.68 (s, 3 H, Me).
13C{1H} NMR (CDCl3, d): 13.9 (t, J = 16 Hz,
P(CH3)3), 51.9 (s, Me), 100.0 (t, J = 5.0 Hz, C„Cb),
104.2 (t, J = 19 Hz, Ca„C), 154.2 (t, J = 1.2 Hz,
CO(O)). 31P{1H} NMR (CDCl3, d): ꢀ14.2(s). Anal.
Calc. for C10H21N3O2P2Pd: C, 31.31; H, 5.52; N,
10.95. Found: C, 31.78; H, 5.45; N, 10.69%.
3. Experimental
3.1. General
All manipulations of air-sensitive compounds were
performed under N2 or Ar by standard Schlenk tech-

656
Y.-J. Kim et al. / Inorganica Chimica Acta 358 (2005) 650–658
3.3. Reactions with organic isocyanides
P(CH2CH3)3), 16.4 (t, J = 14 Hz, P(CH2CH3)3), 31.1
(s, C(CH3)3), 57.6 (s, C(CH3)3), 108.3 (t, J = 19 Hz,
Ca„C), 109.6 (t, J = 3.7 Hz, C„Cb), 125.4, 128.0,
128.1 (br t), 130.6 (t, J = 1.2 Hz), 162.8 (t, J = 10 Hz,
CN4). 31P{1H} NMR (CDCl3, d): 15.6 (s). Anal. Calc.
for C25H44N4P2Pd: C, 52.77; H, 7.79; N, 9.85. Found:
C, 52.99; H, 7.90; N, 10.32%.
To a Schlenk flask containing complex 1 (0.285 g,
0.71 mmol) were sequentially added CH2Cl2 (7 ml)
and 2,6-dimethylphenyl isocyanide (0.094 g, 0.72 mmol).
The initial colorless solution immediately turned to pale
yellow with the evolution of nitrogen. After stirring for 2
h at room temperature, the reaction mixture was com-
pletely evaporated under vacuum, and then the resulting
residue was solidified with ether. The solids were filtered
and washed with hexane (5 ml). Recrystallization from
ether gave yellow crystals of 4, trans-[Pd(C„CPh)
(N@C@NAC6H3-2,6-Me2)(PMe3)2] (0.203 g, 57%). IR
(KBr, cmꢀ1): 2175 (s, br, N@C@N), 2122 (w, br,
C„C). 1H NMR (CDCl3, d): 1.56 (t, 18 H, J = 3.5
Hz, PMe3), 2.35 (s, Me), 6.67–6.72 (m, 1 H, Ph), 6.90–
6.93 (m, 2 H, Ph), 6.93–7.31 (m, 5 H, Ph). 13C{1H}
NMR (CDCl3, d): 14.1 (t, J = 16 Hz, P(CH3)3), 18.9
(s, Me), 94.6 (s, br, Ca„C), 108.6 (t, J = 5.6 Hz, C„Cb)
119.4, 125.6, 126.6, 127.3, 127.7, 130.4, 130.6, 143.8 (s,
Ph). The carbon atom of tetrazolato ring, CN4 and of
carbodiimido ligand, NCN, was not confirmed due to
weak intensity. 31P{1H} NMR (CDCl3, d): ꢀ12.3(s).
Anal. Calc. for C23H32N2P2Pd: C, 54.72; H, 6.39; N,
5.55. Found: C, 54.32; H, 6.51; N, 5.86%.
Complex 8, trans-[Pd(C„CAC(O)OMe)(CN4-t-
Bu)(PMe3)2] (86%). IR (KBr, cmꢀ1): 2110 (s, C„C),
1
1694 (s, br, CO). H NMR (CDCl3, d): 1.34 (t, 18 H,
J = 3.7 Hz, PMe3), 1.76 (s, 9 H, C(CH3)3), 3.70 (s, 3
H, Me). 13C{1H} NMR (CDCl3, d): 15.3 (t, J = 16 Hz,
P(CH3)3), 31.2 (s, C(CH3)3), 51.8 (s, Me), 57.7 (s,
C(CH3)3), 101.4 (t, J = 3.7 Hz, C„Cb), 117.5 (t,
J = 20 Hz, Ca„C), 154.2 (s, C(O)O), 164.0 (t, J = 9.2
Hz, CN4). 31P{1H} NMR (CDCl3, d): ꢀ13.7 (s). Anal.
Calc. for C15H30N4O2P2Pd: C, 38.60; H, 6.48; N,
12.00. Found: C, 38.22; H, 6.47; N, 11.81%.
3.4. Reactions with organic isothiocyanates
To a Schlenk flask containing [Pd(N3)(C„CPh)-
(PEt3)2] (0.207 g, 0.43 mmol) were added CH2Cl2 (2
ml) and 2,6-dimethylphenyl isothiocyanate (0.076 g,
0.47 mmol) in sequential order. After stirring for 18 h
at room temperature, the reaction mixture was com-
pletely evaporated under vacuum and then the resulting
residue was solidified with hexane. The solids were
filtered and washed with hexane (5 ml · 2). Recrystalli-
zation from CH2Cl2/ether gave pale yellow crystals
of 9, trans-[Pd(C„CPh)(SCN4–C6H3-2,6-Me2)(PEt3)2]
(0.227 g, 82%). IR (KBr, cmꢀ1): 2111 (s, C„C). 1H
NMR (CDCl3, d): 1.18 (q, 18 H, J = 8.1 Hz,
P(CH2CH3)3), 1.92 (m, 12 H, P(CH2CH3)3), 2.04 (s,
CH3), 7.17–7.33 (m, 8 H, Ph). 13C{1H} NMR (CDCl3,
d): 8.38 (s, P(CH2CH3)3), 15.7 (t, J = 14 Hz,
P(CH2CH3)3), 17.7 (s, CH3), 108.1 (s, Ca„C), 125.7,
127.7, 128.1, 128.4, 129.9, 130.7 (t, J = 2 Hz), 133.7,
136.1, 163.7 (s, CN4). 31P{1H} NMR (CDCl3, d): 15.1
(s). Anal. Calc. for C29H44N4P2SPd: C, 53.66; H, 6.83;
N, 8.63. Found: C, 53.53; H, 6.74; N, 8.39%.
Complex 5, trans-[Pd(C„CPh)(N@C@NAC6H3–
2,6-Et2)(PMe3)2], was analogously prepared (52%). IR
(KBr, cmꢀ1): 2170 (s, br, N@C@N), 2122 (w, br,
1
C„C). H NMR (CDCl3, d): 1.24 (t, 6 H, J = 7.5 Hz,
CH2CH3), 1.54 (t, 18 H, J = 3.5 Hz, PMe3), 2.79 (q, 4
H, J = 7.5 Hz, CH2), 6.77–6.79 (m, 1 H, Ph), 6.81–6.93
(m, 2 H, Ph), 6.93–7.31 (m, 5 H, Ph). 13C{1H} NMR
(CDCl3, d): 14.5 (t, J = 15 Hz, P(CH3)3), 14.7 (s,
CH3), 25.5 (s, CH2), 94.9 (t, J = 19 Hz, Ca„C), 108.0
(t, J = 5.6 Hz, C„Cb), 119.4, 125.6, 126.6, 127.3,
127.7, 130.4, 130.6, 143.8 (s, Ph). The carbon atom of
tetrazolato ring, CN4, was not confirmed due to weak
intensity. 31P{1H} NMR (CDCl3, d): ꢀ12.3 (s). Anal.
Calc. for C25H36N2P2Pd: C, 56.34; H, 6.81; N, 5.26.
Found: C, 56.35; H, 6.90; N, 5.29%.
Complex 6, trans-[Pd(C„CPh)(CN4-t-Bu)(PMe3)2]
(0.227 g, 66%). IR (KBr, cmꢀ1): 2102 (w, C„C). H
Complex 10, trans-[Pd(C„CPh)(SCN4–Et)(PMe3)2]
(61%), was similarly prepared. IR (KBr, cmꢀ1): 2113
1
NMR (CDCl3, d): 1.37 (t, 18 H, J = 3.5 Hz, PMe3),
1.79 (s, 9 H, C(CH3)3), 7.16–7.35 (m, 5 H, Ph).
13C{1H} NMR (CDCl3, d): 15.6 (t, J = 16 Hz,
P(CH3)3), 31.3 (s, C(CH3)3), 57.7 (s, C(CH3)3), 108.6
(t, J = 20 Hz, Ca„C), 109.6 (t, J = 3.7 Hz, C„Cb),
125.8, 127.5 (br t), 128.1, 130.9 (t, J = 1.2 Hz), 164.0
(t, J = 9.2 Hz, CN4). 31P{1H} NMR (CDCl3, d): ꢀ13.9
(s). Anal. Calc. for C19H52N4P2Pd: C, 47.07; H, 6.65;
N, 11.56. Found: C, 47.16; H, 6.60; N, 11.58%.
Complex 7, trans-[Pd(C„CPh)(CN4-t-Bu)(PEt3)2]
(41%). IR (KBr, cmꢀ1): 2107 (s, C„C). 1H NMR
(CDCl3, d): 1.13 (q, 18 H, J = 7.9 Hz, P(CH2CH3)3),
1.71 (m, 12 H, P(CH2CH3)3), 1.79 (s, C(CH3)3), 7.15–
7.30 (m, 5 H, Ph). 13C{1H} NMR (CDCl3, d): 8.17 (s,
1
(s, C„C). H NMR (CDCl3, d): 1.49 (t, J = 7.3 Hz, 3
H, CH3), 1.51 (t, 18 H, J = 3.5 Hz, PMe3), 4.33 (q,
J = 7.3 Hz, 2 H, CH2), 7.17–7.34 (m, 5 H, Ph).
13C{1H} NMR (CDCl3, d): 14.2 (s, CH3), 14.9 (t,
J = 16 Hz, P(CH3)3), 42.1 (s, CH2), 107.8 (t, J = 5.6
Hz, C„Cb), 126.0, 128.1, 130.8, 161.6 (br s, CN4).
The carbon atom of Ca was not confirmed due to weak
intensity. 31P{1H} NMR (CDCl3, d): ꢀ12.7 (s). Anal.
Calc. for C17H28N4P2SPd: C, 41.77; H, 5.77; N, 11.46.
Found: C, 41.47; H, 5.83; N, 11.03%.
Complex 11, trans-[Pd(C„CPh)(SCN4–C6H3-2,6-
Me2)(PMe3)2] (71%): IR (KBr, cmꢀ1): 2112 (s, C„C).
1H NMR (CDCl3, d): 1.55 (t, 18 H, J = 3.7 Hz,

Y.-J. Kim et al. / Inorganica Chimica Acta 358 (2005) 650–658
657
P(CH3)3), 2.03 (s, CH3), 7.17–7.35 (m, 8 H, Ph).
13C{1H} NMR (CDCl3, d): 14.9 (t, J = 16 Hz,
P(CH3)3), 17.8 (s, CH3), 107.9 (t, J = 5.6 Hz, C„Cb),
126.0, 127.2, 128.1, 128.5, 130.1, 130.8 (t, J = 2 Hz),
133.5, 136.1, 162.6 (br s, CN4). The carbon atom of
Ca was not confirmed due to weak intensity. 31P{1H}
NMR (CDCl3, d): ꢀ13.7 (s). Anal. Calc. for
C23H32N4P2SPd: C, 48.90; H, 5.71; N, 9.92. Found: C,
48.71; H, 5.83; N, 9.56%.
7.28 (m, 5 H, Ph). 13C{1H} NMR (CDCl3, d): 8.49 (s,
P(CH2CH3)3), 17.3 (t, J = 15 Hz, P(CH2CH3)3), 105.0
(t, J = 17 Hz, Ca„C), 110.9 (t, J = 4 Hz, C„Cb),
125.8, 127.6 (t, J = 2 Hz), 128.1, 130.7 (t, J = 1.2 Hz),
136.0 (t, J = 13 Hz, CN). 31P{1H} NMR(CDCl3, d):
20.3 (s). Anal. Calc. for C21H35NP2Pd: C, 53.68; H,
7.51; N, 2.98. Found: C, 53.33; H, 7.67; N, 3.01%.
Complex 15 was independently prepared by the fol-
lowing method. To a Schlenk flask containing complex
2 (0.350 g, 0.82 mmol) were sequentially added CH2Cl2
(5 ml) and Me3SiCN (0.203g, 2.05 mmol). After stirring
for 18 h at room temperature, the reaction mixture was
fully evaporated to give white solids. The solids were fil-
tered and washed with ether (3 ml · 2) to give white sol-
ids of 15, [Pd(CN)2(PEt3)2] (0.300 g, 93% ). IR (KBr,
Complex 12, [(PEt3)2(C„CPh)Pd(SCN4-(l-C6H4)–
SCN4)Pd(C„CPh)(PEt3)2] (37%): IR (KBr, cmꢀ1):
1
2113 (s, C„C). H NMR (CDCl3, d): 1.19 (q, 36 H,
J = 8.3 Hz, P(CH2CH3)3), 1.90 (m, 24 H, P(CH2CH3)3),
2.04 (s, CH3), 7.17–7.33 (m, 10 H, Ph), 8.23 (s, 4 H, Ph).
13C{1H} NMR (CDCl3, d): 8.37 (s, P(CH2CH3)3), 15.7
(t, J = 14 Hz, P(CH2CH3)3), 98.5 (br, Ca„C), 108.0 (s,
t, J = 5.6 Hz, C„Cb), 123.7, 125.8, 127.7, 128.1, 130.7
(t, J = 2 Hz), 135.6, 162.6 (s, CN4). 31P{1H} NMR
(CDCl3, d): 17.9 (s). Anal. Calc. for C48H74N8P4S2Pd2:
C, 49.53; H, 6.41; N, 9.63. Found: C, 49.27; H, 6.33;
N, 10.06%. FAB mass spectrum: m/z 1164 (M+).
1
cmꢀ1): 2123 (s, C„N). H NMR (CDCl3, d): 1.21 (q,
18 H, J = 8 Hz, P(CH2CH3)3), 2.08 (m, 12 H,
P(CH2CH3)3). 13C{1H} NMR (75 MHz, CDCl3, d):
8.41 (s, P(CH2CH3)3), 17.6 (t, J = 15 Hz, P(CH2CH3)3),
130.8 (t, J = 15 Hz, CN). 31P{1H} NMR (CDCl3, d):
20.0 (s). Anal. Calc. for C14H30N2P2Pd: C, 42.59; H,
7.66; N, 7.10. Found: C, 42.83; H, 7.85; N, 7.25%.
Complexes 17–19 were analogously prepared. Com-
plex 17, [Pd(CN)2(PMe3)2] (94%). IR (KBr, cmꢀ1):
3.5. Reactions with organic nitriles
1
To a Schlenk flask containing complex 1 (0.258 g,
0.64 mmol) were sequentially added CH2Cl2 (3 ml)
and C6F5CN (0.372 g, 1.92 mmol). After stirring for
14 h at room temperature, the reaction mixture was
completely evaporated under vacuum, and then the
resulting residue was solidified with ether. The solids
were filtered and washed with hexane (3 ml · 2). Re-
peated recrystallization from CH2Cl2/hexane gave white
crystals of 13, trans-[Pd(C„CPh)(N4C–C6F5)(PMe3)2]
(0.142 g, 37%). IR (KBr, cmꢀ1): 2125 (s, C„C). 1H
NMR (CDCl3, d): 1.42 (t, J = 3.8Hz, PMe3), 7.20–7.35
(m, Ph). 13C{1H} NMR (CDCl3, d): 14.1 (t, J = 16 Hz,
P(CH3)3), 109.0 (t, J = 3.7 Hz, C„Cb), 126.3, 128.1,
128.2, 130.9 (t, J = 2 Hz). The carbon atom (CN4) of
the tetrazolato ring was not confirmed due to its weak
intensity. 31P{1H} NMR (CDCl3, d): ꢀ12.6 (s). Anal.
Calc. for C21H23N4F5P2Pd: C, 42.41; H, 3.90; N, 9.42.
Found: C, 42.56; H, 4.14; N, 9.15%.
To a Schlenk flask containing complex 2 (0.150 g,
0.31 mmol) were added CH2Cl2 (4 ml) and Me3SiCN
(0.092 g, 0.62 mmol) in sequential order. After stirring
for 18 h at room temperature, the reaction mixture
was fully evaporated, treated with diethyl ether, and
then stored at freezer to give white solids. The solids
were filtered and washed with ether (3 ml · 2) to give
white solids of [Pd(CN)2(PEt3)2] (15) in a trace amount.
The collected filtrate was evaporated to give white sol-
ids. Recrystallization from diethyl ether/hexane gave
white crystals of 14, trans-[Pd(C„CPh)(CN)(PEt3)2]
(0.124 g, 85 %). IR (KBr, cmꢀ1): 2108 (s, C„N and
C„C). 1H NMR (CDCl3, d): 1.21 (q, 18 H, J = 7.9
Hz, P(CH2CH3)3), 2.06 (m, 12 H, P(CH2CH3)3), 7.15–
2123 (CN). H NMR (CDCl3, d): 1.70 (br s, PMe3).
13C{1H} NMR (CDCl3, d): 16.4 (s, P(CH3)3), 131.2 (s,
CN). 31P{1H} NMR (CDCl3, d): ꢀ14.8 (s). Anal. Calc.
for C8H18N2P2Pd: C, 30.93; H, 5.84; N, 9.02. Found:
C,31.05; H, 5.88; N, 8.87%.
Complex 18, [Pd(CN)2(depe)] (87%). IR (KBr, cmꢀ1):
2127 (CN). 1H NMR (CDCl3, d): 1.28 (dt, 12 H, J = 7.6
Hz, P(CH2CH3)2) 2.13 (m, 12 H, PCH2). 13C{1H} NMR
(CDCl3, d): 9.09 (s, P(CH2CH3)3), 19.3 (dd, J = 2 Hz, 30
Hz, PCH2), 24.0 (d, J = 43 Hz, PCH2), 24.0 (dd, J = 11
Hz, 9.0 Hz, PCH2), 130.9 (dd, J = 128 Hz, 19 Hz, CN).
31P{1H} NMR (CDCl3, d): 9.09 (s). Anal. Calc. for
C12H24N2P2Pd: C, 39.52; H, 6.63; N, 7.68. Found: C,
39.86; H, 6.75; N, 7.62%.
Complex 19, [Ni(CN)2(PEt3)2] (86 %). IR (KBr,
1
cmꢀ1): 2104 (CN). H NMR (CDCl3, d): 1.24 (q, 18
H, J = 8 Hz, P(CH2CH3)3), 2.01 (m, 12 H,
P(CH2CH3)3). 13C{1H} NMR (CDCl3, d): 8.38 (s,
P(CH2CH3)3), 17.0 (t, J = 15 Hz, P(CH2CH3)3), 133.6
(t, J = 35 Hz, CN). 31P{1H} NMR (CDCl3, d): 24.8
(s). Anal. Calc. for C14H30N2P2Ni: C, 48.45; H, 8.71;
N, 8.07. Found: C, 48.78; H, 8.51; N, 7.86%.
3.6. X-ray structure determination
All X-ray data were collected with a Siemens P4 dif-
fractometer equipped with a Mo X-ray tube and a
graphite-crystal monochromator. Intensity data were
empirically corrected for absorption with w-scan data.
All calculations were carried out with the use of SHEL-
XTL programs [33]. All structures were solved by
direct methods. All non-hydrogen atoms were refined

658
Y.-J. Kim et al. / Inorganica Chimica Acta 358 (2005) 650–658
(c) A.P. Gaughan, K.S. Bowman, Z. Dori, Inorg. Chem. 3 (1972)
601;
anisotropically. All hydrogen atoms were generated in
ideal positions and refined in a riding mode.
(d) Z. Dori, R.F. Ziolo, Chem. Rev. 73 (1973) 248.
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4. Supplementary material
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Crystallographic data for the structural analysis have
been deposited at the Cambridge Crystallographic Data
Centre, CCDC Nos. 232839–232842 for compounds 5,
6, 11, and 18. Copies of this information may be
obtained free of charge from: The director, CCDC, 12
Union Road, Cambridge, CB2 1EZ, UK (fax: +44-
1223-336-033; e-mail: deposit@ccdc.cam.ac.uk or
www: http://www.ccdc.cam.ac.uk).
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Acknowledgement
[16] H. Gorth, M.C. Henry, J. Organomet. Chem. 9 (1967) 117.
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[18] C.-W. Chang, G.-H. Lee, Organometallics 22 (2003) 3107.
[19] (a) Y.-J. Kim, Y.-S. Kwak, Y.-S. Joo, S.W. Lee, J. Chem. Soc.,
Dalton Trans. (2002) 144;
This work was supported by Grant R05-2002-000-
00559-0 from the Basic Research Program of the Korea
Science and Engineering Foundation.
(b) Y.-J. Kim, Y.-S. Joo, J.-T. Han, W.S. Han, S.W. Lee, J.
Chem. Soc., Dalton Trans. (2002) 3611;
(c) Y.-J. Kim, Y.-S. Kwak, S.W. Lee, J. Organomet. Chem. 603
(2000) 152;
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