A new stable intermediary mode between η3-2-aminoallyl complexes and metallacyclobutanimines. Synthesis and structural characteristic of η3-azatrimethylenemethane and N-protonated, N-alkylated, N-arylated η3-azatrimethylenemethane complexes of Pt and Pd

Article abstract of DOI:10.1016/S0022-328X(98)00772-4

Regioselective addition of ammonia, primary or secondary amines, aniline, or amino derivatives either to a neutral (η¹-allenyl)platinum complex trans-Pt(Br)(PPh₃)₂(η¹-CHCCH₂) (1) or to a cationic η³-allenyl/propargyl platinum complex [Pt(PPh₃)₂(η³-C₃H ₃)](BF₄) (2) provide the synthesis of cationic N-protonated, N-alkylated, and N-arylated η³-azatrimethylenemethane complexes {Pt(PPh₃)₂(η³-CH ₂C(NRR′)CH₂]}(X) (R=H R′=H (3a), Me (3b), Et (3c), ⁱPr (3d), ^tBu (3e), c-C₆H₁₁ (3f), Ph (3g), CH₂CH₂OH (3h), R=R′=Et (3i), c-C₃H₆ (from azetidine 3j), Ph (3k), R=Me R′=Ph (3l); X=Br, BF₄), respectively. Addition of amides to 1 gave a neutral η³-azatrimethylenemethane complex Pt(PPh₃)₂[η³-CH₂C(NSO ₂Ph)CH₂] (4m). Similar reactions using palladium complexes yield {Pd(PPh₃)₂[η³-CH ₂C(NRR′)CH₂]}(X) (R=H R′=ⁱPr (7d), Ph (7g), R=R′=Et (7i); X=Br, BF₄, OTf), Pd(Br)(PPh₃)[η³-CH₂C(NEt ₂)CH₂] (8i) and Pd(PPh₃)₂[η³-CH₂C(NR)CH ₂] (R=SO₂Ph (9m), p-SO₂C₆H₄Me (9n)). Synthesis of three complexes, {M(PPh₃)₂[η³-CH₂C(NHR)CH ₂]}⁺ (M=Pt R=SO₂Ph (3m); M=Pd R=SO₂Ph (7m), p-SO₂C₆H₄Me (7n)), can not be done by hydroamination reactions, but has been successful using protonation of η³-N-TMM complexes 4m, 9m, and 9n, respectively. Spectroscopic and crystallographic characterizations indicate that these N-TMM complexes exhibit intermediary structural features between η³-2-aminoallyl and metallacyclobutanimine complexes.We designate η³-O-TMM to stand for the η³-oxatrimethylenemethane complexes M[η³-CH₂C(=O)CH₂]; η³-N-TMM to stand for the η³-azatrimethylenemethane complexes M[η³-CH₂C(=NR)CH₂]. Accordingly, N-protonated η³-N-TMM complexes are referred to M[η³-CH₂C(NH₂)CH₂]; and N-alkylated or N-arylated η³-N-TMM complexes are referred to M[η³-CH₂C(NHR)CH₂] or M[η³-CH₂C(NRR′)CH₂] (R, R′=alkyl or aryl).

Full text of DOI:10.1016/S0022-328X(98)00772-4

Journal of Organometallic Chemistry 569 (1998) 39–54
A new stable intermediary mode between p3-2-aminoallyl complexes
and metallacyclobutanimines. Synthesis and structural characteristic of
p3-azatrimethylenemethane and N-protonated, N-alkylated, N-arylated
p3-azatrimethylenemethane complexes of Pt and Pd1
Ai-Jan Chen, Chung-Chi Su, Fu-Yu Tsai, Jen-Jeh Lee, Tsang-Miao Huang,
Ching-Shuenn Yang, Gene-Hsiang Lee, Yu Wang, Jwu-Ting Chen *
Department of Chemistry, National Taiwan Uni6ersity, Taipei 106, Taiwan, ROC
Received 20 February 1998
Abstract
Regioselective addition of ammonia, primary or secondary amines, aniline, or amino derivatives either to a neutral (p1-al-
lenyl)platinum complex trans-Pt(Br)(PPh3)2(p1-CHCCH2) (1) or to
a
cationic p3-allenyl/propargyl platinum complex
[Pt(PPh3)2(p3-C3H3)](BF4) (2) provide the synthesis of cationic N-protonated, N-alkylated, and N-arylated p3-azatrimethylen-
emethane complexes {Pt(PPh3)2(p3-CH2C(NRR%)CH2]}(X) (R=H R%=H (3a), Me (3b), Et (3c), Pr (3d), Bu (3e), c-C6H11 (3f),
Ph (3g), CH2CH2OH (3h), R=R%=Et (3i), c-C3H6 (from azetidine 3j), Ph (3k), R=Me R%=Ph (3l); X=Br, BF4), respectively.
Addition of amides to 1 gave a neutral p3-azatrimethylenemethane complex Pt(PPh3)2[p3-CH2C(NSO2Ph)CH2] (4m). Similar
reactions using palladium complexes yield {Pd(PPh3)2[p3-CH2C(NRR%)CH2]}(X) (R=H R%=iPr (7d), Ph (7g), R=R%=Et (7i);
X=Br, BF4, OTf), Pd(Br)(PPh3)[p3-CH2C(NEt2)CH2] (8i) and Pd(PPh3)2[p3-CH2C(NR)CH2] (R=SO2Ph (9m), p-SO2C6H4Me
(9n)). Synthesis of three complexes, {M(PPh3)2[p3-CH2C(NHR)CH2]}+ (M=Pt R=SO2Ph (3m); M=Pd R=SO2Ph (7m),
p-SO2C6H4Me (7n)), can not be done by hydroamination reactions, but has been successful using protonation of p3-N-TMM
complexes 4m, 9m, and 9n, respectively. Spectroscopic and crystallographic characterizations indicate that these N-TMM
complexes exhibit intermediary structural features between p3-2-aminoallyl and metallacyclobutanimine complexes.2 © 1998
Elsevier Science S.A. All rights reserved.
i
t
Keywords: p3-Azatrimethylenemethane complexes; Pt; Pd; Structural characteristic
1. Introduction
emethanes in the form of M[CH2C(X)CH2]. The
hetero-TMM compounds which contain the hetero-
atoms X as O, S, or Si have been examined [1–3].
Four types of mononuclear bonding modes in p1-,
p2-, p3- or p4-form have been structurally character-
ized [4].
There has been increasing research interest in tran-
sition metal complexes of heteronuclear trimethylen-
* Corresponding author. Fax:+ 886 2 23636359.
1 JTC dedicates this article to Professor Akira Nakamura of Osaka
University on his retirement.
2 We designate p3-O-TMM to stand for the p3-oxatrimethylen-
emethane complexes M[p3-CH2C(ꢀO)CH2]; p3-N-TMM to stand for
the p3-azatrimethylenemethane complexes M[p3-CH2C(ꢀNR)CH2].
Accordingly, N-protonated p3-N-TMM complexes are referred to
M[p3-CH2C(NH2)CH2]; and N-alkylated or N-arylated p3-N-TMM
complexes are referred to M[p3-CH2C(NHR)CH2] or M[p3-
CH2C(NRR%)CH2] (R, R%=alkyl or aryl).
0022-328X/98/$ - see front matter © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00772-4

40
A.-J. Chen et al. / Journal of Organometallic Chemistry 569 (1998) 39–54
The TMM species of the p3-form are relatively less
investigated, although some have been found useful in
organic synthesis [5]. Among them, the p3-O-TMM
complexes of palladium and platinum are the most
extensively studied heterotrimethylene methane species
[6]. Both experimental and theoretical data indicate that
the p3-O-TMM complexes have the resonance structure
between a zwitterionic p3-2-oxyallyl form (A) and a
metallacyclobutanone form (B).
Scheme 1.
The isoelectronic species of p3-O-TMM, p3-N-TMM
complexes, were virtually unexplored until we reported
the first isolable cationic N-alkylated p3-N-TMM com-
plexes of platinum in prior preliminary communications
[7]. Later on, the N-protonated and alkylated p3-N-
TMM complexes of iridium were also prepared [8]. In
the mean time, Wojcicki and Murai published their
independent work on the neutral p3-N-TMM com-
plexes [9]. These N-TMM complexes constitute a class
of new heterotrimethylenemethane species. We report
here our complete studies of the title complexes includ-
ing synthesis, characterization, structure, and reaction
scope.
The N-alkylated and N-arylated p3-N-TMM com-
plexes of palladium are prepared using the same
methodology as for preparing the platinum analogs,
but the lability of the palladium system makes some-
what distinct reactivity. Equimolar amounts (0.27
mmol) trans-Pd(Br)(PPh3)2(p1-CHCCH2) (5) and
Et2NH were allowed to react in CH2Cl2 (15 ml) at 25°C
for 2 h. A neutral N-alkylated p3-N-TMM complex
Pd(Br)(PPh3)[p3-CH2C(NEt2)CH2] (8i) was obtained in
70% isolated yields. Treating 8i with PPh3 gave an ionic
species
as
a
bromide
salt
{Pd(PPh3)2[p3-
CH2C(NEt2)CH2]}(Br) (7i). The cation of 7i with other
counter-anions could be prepared by more facile reac-
tions of [Pd(PPh3)2(p3-C3H3)](X) (X=PF6 (6), BF4 (6%),
OTf (6¦)) and Et2NH. Hydroamination of 5 or 6 with
NH3 or MeNH2 could be achieved below 0°C, but the
resulting N-TMM products decomposed when the tem-
2. Results and discussion
2.1. Synthesis of p3-N-TMM platinum and palladium
complexes
i
perature was raised to 25°C. Addition of PrNH2 or
PhNH2 to 5 was successful, when reactions were carried
out with the presence of large excess amines. The
products are cationic complexes {Pd(PPh3)2[p3-
CH2C(NHR)CH2]}(Br) (R=iPr (7d), Ph (7g)) instead
of the neutral species, presumably the polar environ-
ment favors the ionic species (Scheme 2).
Synthesis of N-protonated, N-alkylated and N-ary-
lated p3-N-TMM complexes is established by regiose-
lective hydroamination of metal allenyl or metal
propargyl complexes. The reactions of trans-
Pt(Br)(PPh3)2(p1-CHCCH2) (1) and equimolar amounts
of ammonia, primary or secondary amines, aniline, and
other amino derivatives produce {Pt(PPh3)2(p3-
CH2C(NRR%)CH2]}(Br) (R=H R%=H (3a), Me (3b),
Et (3c), iPr (3d), tBu (3e), c-C6H11 (3f), Ph (3g),
CH2CH2OH (3h), R=R%=Et (3i), c-C3H6 (from aze-
tidine, 3j), Ph (3k), R=Me R%=Ph (3l)). The yields are
generally excellent. The BF4 salts of 3 (3a% and 3g%) can
be obtained either by anionic exchange using AgBF4, or
alternatively by the reactions of a cationic p3-allenyl/
propargyl complex [Pt(PPh3)2(p3-C3H3)](BF4) (2) with
the corresponding amino compounds (Scheme 1). In a
typical case, the reaction of 1 and aqueous ammonia
(0.2 mmol for each) in CH2Cl2 (20 ml) at 25°C would
take over a day to completion. The hydroamination
reactions of the cationic 2 with similar molar mass are
accomplished instantaneously at −10°C.
Scheme 2.

A.-J. Chen et al. / Journal of Organometallic Chemistry 569 (1998) 39–54
41
dppe)[p3-CH2C(NSO2Ph)CH2] (14) by heating at 60°C
(Scheme 5).
The formation of amido complexes 11 and 13 strongly
supports that the mechanism of hydroamination of the
p1-allenyl complexes likely involves a preceding coordi-
nation step of amide [10]. In another word, the metal
center plays a crucial role to mediate the addition of the
N–H bond across the allenyl CꢀC bond [11]. From the
mechanistic viewpoint, tranformation of the alleny-
l(amido) complexes into p3-N-TMM complexes may
have two possible pathways. The amination step may be
achieved via intramolecular C–N bond formation. Al-
ternatively, amide dissociation will give rise to an p3-al-
lenyl/propargyl intermediate which then undergoes
intermolecular C–N bond formation (Scheme 6).
More evidences are obtained from the competitive
kinetic experiments which afford relative reactivity of
hydroamination of 1 toward different amines. In a
typical case, to a CDCl3 solution (0.5 ml) containing 1
(20 mg) was injected a mixture of MeNH2 and EtNH2
with each having 10-fold equivalents. At the end of the
reaction, the NMR integration gave the relative yields of
3b and 3c as 1.7:1. Table 1 collects the results measured
for a series primary amines and aniline. The relative
reactivity is estimated as MeNH2:EtNH2:iPrNH2:c-
C6H11NH2:tBuNH2=24:14:8:8:1. These data indicate
the importance of the steric effect and show consistency
with the mechanism involving amine coordination. On
the other hand, the relative reactivity between c-
C6H11NH2 and PhNH2 is 2:1, and the qualitative obser-
Scheme 3.
The isoelectronic nitrogen derivatives of p3-O-TMM
are p3-N-TMM complexes. Wojcicki reported the first
structurally characterized p3-N-TMM complexes
Pt(PPh3)2[p3-CH2C(NR)CHPh], prepared from depro-
tonation of {Pt(PPh3)2[p3-CH2C(NHR)CHPh]}+. We
found that addition of amide to the allenyl complexes
can also generate the neutral p3-N-TMM complexes
readily. The reactions of trans-Pd(Br)(PPh3)2[p1-
CHCCH2) (5) with Na(NHAr) in CH2Cl2 at 25°C
produce Pd(PPh3)2[p3-CH2C(NR)CH2] (R=SO2Ph
(9m), p-SO2C6H4Me (9n)) in good yields. The NMR
studies show that protonation of 9m and 9n instanta-
neously gives {Pd(PPh3)2(p3-CH2C(NHR)CH2]}(BF4)
(R=SO2Ph (7m), p-SO2C6H4Me (7n)). Treating 7m and
7n with NaH recovers 9m and 9n respectively. Weak
amine like PhSO2NH2 or p-MeC6H4–SO2NH2 fails to
add to 5 (Scheme 3).
i
vations showed EtNH2BEt2NH and PrNH2BnPr2NH
in reaction rates, suggesting that the electronic factor
should not be negligible. This is also reasonable since
better nucleophilicity would facilitate coordination and
the addition as well. Amines with poor coordinating
ability and nucleophilicity such as PhSO2NH2 or
MeC6H4SO2NH2 indeed fail hydroamination to 1 and 5.
2.2. Reaction mechanism of hydroamination of
p1-allenyl complexes
2.3. Spectroscopic and structural characteristic of
p3-N-TMM complexes
We have further examined the reactions of p1-allenyl
complexes with amide. Adding AgOAc to 1 resulted in
ligand substitution, giving trans-Pt(PPh3)2(OAc)(p1-
CHCCH2) (10). Treatment of 10 with Na(NHSO2Ph)
gave another p1-allenyl complex trans-Pt(PPh3)2-
(NHSO2Ph)(p1-CHCCH2) (11). The NMR studies sug-
gest that the two phosphine ligands in 11 are in trans
arrangement, and the acetate ligand is displaced pre-
sumably by amide. The identification of 11 is evidenced
by its transformation into Pt(PPh3)2(p3-CH2C-
(NSO2Ph)CH2] (4m) (Scheme 4). Protonation of 4m
gives {Pt(PPh3)2(p3-CH2C(NHSO2Ph)CH2]}(BF4) (3m).
Hydroamination of a cis p1-allenylplatinum complex
has also been studied. cis-Pt(dppe)(Cl)(p1-CHCCH2)
(12) was prepared by treating trans-Pt(PPh3)2(Cl)(p1-
CHCCH2) with diphenylphosphinoethane (dppe) in ben-
zene. The reaction of Na(NHSO2Ph) and 12 first yields
a cis p1-allenyl(amido) complex cis-Pt(dppe)(NHSO2Ph)
(p1-CHCCH2) (13) which then transforms into cis-Pt(-
The spectral characteristic of p3-N-TMM complexes
resemble those of central-carbon-substituted p3-allyl
1
complexes [12]. As collected in Table 2, the H-NMR
resonances of syn- and anti-hydrogens of p3-N-TMM
complexes are diastereotopic. The anti-protons are at
high field and usually better resolved. The syn-protons
appear as a broadened singlet. In the cases of alkylated
p3-N-TMM complexes such as 3b, 3c, 3e, 3f, and 3h,
four allyl hydrogens well split. These data evidence the
C–N double bond in these p3-N-TMM complexes. The
13C-NMR resonances of the cener-carbon of p3-N-
TMM complexes appear at l150 which are down-field
compared those of the common p3-allyl complexes. In
addition, the values of JC–Pt of p3-N-TMM complexes,
which are in the region of 100–110 Hz, are distinctly
larger than those of p3-allyl complexes (20–40 Hz), and
are useful parameters for characterization.

42
A.-J. Chen et al. / Journal of Organometallic Chemistry 569 (1998) 39–54
The 31P-NMR spectra of complexes 3 show two
2.4. Base-catalyzed hydrolysis of p3-N-TMM complexes
magnetically non-equivalent phosphines and support a
p3-N-TMM rather than a p3-allyl structure. We exam-
ined 31P-NMR coalescence for 3d and 3e, which oc-
curred at 318 and 305 K, respectively. The coalescence
temperature (Tc) allows to estimate the rotational en-
ergy barrier (DG) along the C–N bond. The calculated
DG is 15.9 kcal mol−1 for 3d and 14.6 kcal mol−1 for
3e [13]. The palladium analog 7d shows relatively lower
Tc at 283 K which affords DG=13.4 kcal mol−1. These
thermodynamic data also support the C–N double
bond character.
Unlike the deprotonation of {Pt(PPh3)2[p3-
CH2C(NHSO2Ph)CH2]}+, which gives Pt(PPh3)2[p3-
CH2C(NSO2Ph)CH2], reaction of {Pt(PPh3)2(p3-CH2C-
(NH2)CH2]}+(3a) with a methanol solution of KOH
yields a new dicationic complex of 1,5-diplatinacy-
cloocta-3,7-diimine
{cis-Pt(PPh3)2(v-CH2CMeNH)2}
(Br)2 (15). The molecular structure of 15 has been
confirmed unequivocally by X-ray crystallography. Its
ORTEP drawing in Fig.
3
shows that two
–CH2C(Me)ꢀNH– bridging ligands link the two plat-
inum centers to form an eight-member metallacycle.
The cyclic framework is in a boat form and the two
C–N double bonds are nearly parallel. Complex 15 is
the first example of diplatina metallacycle containing
bridging imines [14].
The usage of alkaline appears to be essential to the
dimerization of 3a, since adding NaOPh to 3a fails to
generate 15. The transformation of 3a into 15 is similar
to enamine–imine tautomerization via a course of de-
protonation-protonation as illustrated in Scheme 7. In
The X-ray diffractions for single crystals provide
structural understanding for these p3-N-TMM com-
plexes. Crystallographic analysis for 3a%, 3d, 3g%, 3h, 3i,
3j, 4m, 7d, 7g, 7i, and 8i have been done and the
ORTEP drawings of 3a% and 4m are shown in Figs. 1
and 2, respectively, as the representatives. Complex 4m
which is a neutral p3-N-TMM complex and 3a% which is
the prototype of cationic N-protonated p3-N-TMM
complex are generally alike. Both show that
CH2C(N)CH2 moieties use three carbon atoms to bond
with the metal. The C3N atoms are nearly coplanar.
The central carbon is only slightly out of plane to the
opposite side of the metal. As a result, the distance of
Pt–Cc is longer than the Pt–Ct distances. The impor-
tant bond parameters are listed in Table 3. One of the
most characteristic features of a p3-N-TMM complex is
that the lengths of two Ct–Cc bond and the Cc–N bond
are within the double bond range. It is worth to note
that the dihedral angles (q) defined by the Ct–M–Ct%
and Ct–Cc–C%t planes of these complexes are 6094°
which are smaller than those of the p3-allyl complexes
but much larger than those of metallacyclobutanes. The
values of D(C–N) and q can serve pragmatic character-
izing criteria for such p3-N-TMM complexes. In addi-
tion, the angles of Ct–Cc–C%t are 110° which are smaller
than those of p3-allyl complexes (115–120°) [12]. In
similarity to the isoelectronic p3-O-TMM complexes,
the neutral p3-N-TMM complexes have the resonance
structures of p3-2-amidoallyl (C) and metallacyclobuta-
nimine (D); and the protonated, alkylated, and arylated
p3-N-TMM cations have the resonance structures of
p3-2-aminoallyl (E) and metallacyclobutaniminium (F).
another
reaction
treating
1
with
excess
HOCH2CH2NH2, cis-{(Ph3P)2Pt[NH2CH2CH2O]}(Br)
(16) and acetone were recovered. The same products
were acquired from the reaction with equimolar
amounts of 3h and Et3N. We propose that 1 first
undergoes hydroamination to give 3h. The following
step is similar to the formation of 15 from 3a. The
N-alkylated p3-N-TMM complex 3h proceeds base-cat-
alyzed enamine-imine tautomerization followed by hy-
drolysis of imine moiety. Complex 16 is thus formed
along with acetone (Scheme 8).
3. Concluding remarks
Platinum and palladium complexes of p3-N-TMM
M[p3-CH2C(NR)CH2],
N-protonated
p3-N-TMM
M[p3-CH2C(NH2)CH2], and N-alkylated (or N-ary-
lated) p3-N-TMM M[p3-CH2C(NRR%)CH2] are success-
fully prepared by regioselective addition of amides,
ammonia, amines, or amino derivatives to the p1-al-
lenyl or p3-allenyl/propargyl complexes. Spectroscopic

A.-J. Chen et al. / Journal of Organometallic Chemistry 569 (1998) 39–54
43
Scheme 4.
C3H3)](BF4) (2) (0.2 mmol) and ammonia (0.5 M in
dioxane) in chloroform instantaneously resulted in the
BF4 salt of 3a% over 90% yield. Selected spectral data:
IR (KBr pallet) wCꢀN 1513 cm–1, wN-H 3446, 3359, 3255
and X-ray crystallographic analyses provide the instru-
mentation for characterization. The p3-N-TMM metal
complexes make a class of new organometallic species
with intermediary structural characteristic between p3-
aminoallyl and metallacyclobutanimine complexes. The
common moiety of p3-CH2C(N)CH2 is subjected to
base-catalyzed enamine–imine tautomerization.
cm−1
;
31P-NMR (CDCl3, 81.015 MHz) l 19.0 (JP–Pt
=
1
3356 Hz); H-NMR (CDCl3, 300 MHz) l 1.93 (2H, dd
with 195Pt satellites, JH–P=4.7, 10.3 Hz, JH–Pt=62.8
Hz, Hanti), 2.83 (2H, br, Hsyn), 6.50 (2H, s with 195Pt
satellites, JH–Pt=18.0 Hz, NH6
); 13C-NMR (CDCl3,
50.32 MHz) l 44.8 (dd with 195Pt satellites, JC–P=4.6,
47.6 Hz, JC–Pt=169.2 Hz, Ct), 127.6–134.9 (phenyl C),
4. Experimental section
4.1. General
153.1 (td with 195Pt satellites, JC–P=4.2 Hz, JC–Pt
=
88.5 Hz, Cc). Anal. Calc. for PtC39H36NP2Br: C, 54.74;
H, 4.24; N, 1.64. Found: C, 54.02; H, 4.32; N, 1.61.
Solvents were dried by standard procedures. IR
spectra were recorded on a Bio-Rad FTS-40 spec-
trophotometer. The NMR spectra were recorded on
either a Bruker AC-E200 or a Brucker ACE-300 spec-
trometer. For the 31P-NMR spectra, the spectrometer
frequency at 81.015 or 121.49 MHz was employed,
and chemical shifts are given in ppm (l) relative to
85% H3PO4 in CDCl3. Values upfield of the standard
are defined as negative. Mass spectrometric analyses
were collected on a JEOL SX-102A spectrometer. Ele-
mental analyses were done on a Perkin-Elmer 2400
CHN analyzer.
4.2.2. {Pt(PPh3)2[p3-CH2C(NHMe)CH2]}(Br) (3b)
Complex 1 (360 mg, 0.43 mmol) and MeNH2 (40 ml
40% aqueous solution, 0.52 mmol) were allowed to
react in CH2Cl2 (20 ml) at 25°C for 4 h. The yield of
white 3b was 92% (344 mg). IR (KBr pallet) wC=N 1579
cm−1 31P-NMR (CDCl3, 81.0 MHz) l 18.4 (d, JP–P
; =
8.7 Hz, JP–Pt=3196 Hz), 19.7 (d, JP–P=8.7 Hz, JP–Pt
=3317 Hz); 1H-NMR (CDCl3, 300 MHz, 275 K) l
1.65 (1H, dd with 195Pt satellites, JH–H=6.7 Hz, JH–P
=11.2 Hz, JH–Pt=67 Hz, Hanti), 1.97 (1H, dd with
195Pt satellites, JH–H=6.7 Hz, JH–P=11.2 Hz, JH–Pt
=
67 Hz, Hanti), 2.31 (1H, br, Hsyn), 2.64 (3H, d with 195Pt
satellites, JH–H=4.7 Hz, JH–Pt=22.8 Hz, CH3), 3.23
(1H, br, Hsyn), 7.1–7.5 (30H, phenyl H), 8.57 (1H, d,
H–P=4.9 Hz, NH
); 13C-NMR (CDCl3, 50.3 MHz) l
28.8 (d with 195Pt satellites, JC–P=6.2 Hz, JC–Pt=11.6
Hz, C
H3), 40.1 (dd with 195Pt satellites, JC–P=4.8, 44.9
Hz, JC–Pt=176.4 Hz, Ct), 41.5 (d with 195Pt satellites,
C–P=49.7 Hz, JC–Pt=201 Hz, Ct), 127–135 (phenyl
C), 156.5 (dd with 195Pt satellites, JC–P=4.6, 9.9 Hz,
4.2. Synthesis and characterization
6
4.2.1. {Pt(PPh3)2[p3-CH2C(NH2)CH2]}(X) (X=Br 3a,
BF4 3a%)
J
6
To a two-necked round-bottom flask, was charged
with trans-Pt(Br)(PPh3)2(p1-CHCCH2) (1) (165 mg, 0.2
mmol) and aqueous ammonia (17 ml of 25% aqueous
solution) in CH2Cl2 (20 ml). The solution was strred for
1 day and was then concentrated. Addition of diethyl
ether to the solution resulted in the precipitation of the
white product. The yield was 89%. Alternatively, the
reaction of equimolar amounts of [Pt(PPh3)2(p3-
6
J
J
C–Pt=110.7 Hz, Cc); Anal. Calc. for PtC40H38N-
P2Br.H2O C, 54.12; H, 4.54; N. 1.58. Found: C, 53.47;
H, 4.58; N, 1.56.
Scheme 5.

44
A.-J. Chen et al. / Journal of Organometallic Chemistry 569 (1998) 39–54
Scheme 6.
4.2.3. {Pt(PPh3)2[p3-CH2C(NHEt)CH2]}(Br) (3c)
Refer to the paragraph for 3a for the detailed proce-
dure. The reaction of complex 1 (156 mg, 0.19 mmol)
and EtNH2 (16.5 ml 70% aqueous solution, 2.1 mmol)
gave white solid 3c in 91% yield (151 mg). 31P-NMR
(KBr) wCꢀN 1585 cm−1 31P-NMR (CDCl3, 81.015
;
MHz) l 19.0 (d, JP–P=8.4 Hz, JP–Pt=3256 Hz), 19.6
1
(d, JP–P=8.4 Hz, JP–Pt=3215 Hz); H-NMR (CDCl3,
300 MHz) l 1.24 (6H, d, JH–H=6.3 Hz, CH3
br, Hsyn and Hanti), 3.27 (1H, m, JH–H=6.3, 8.2 Hz,
H–P=4 Hz, CH), 7.1–7.4 (30H, phenyl H), 8.75 (1H,
d with 195Pt satellites, JH–H=8.2 Hz, JH–Pt=27.1 Hz,
6 ), 2.2 (4H,
(CDCl3, 81.015 MHz) l 19.0 (d, JP–P=8.4 Hz, JP–Pt
=
J
6
3224 Hz), 19.7 (d, JP–P=8.4 Hz, JP–Pt=3275 Hz);
1H-NMR (CDCl3, 300 MHz, 273 K) l 1.04 (3H, t,
NH6 6 H3),
); 13C-NMR (CDCl3, 75.469 MHz) l 22.6 (s, C
6
), 1.60 (1H, dd with 195Pt satel-
39.6 (d with 195Pt satellites, JC–P=46.9 Hz, JC–Pt=187
Hz, Ct), 41.0 (d with 195Pt satellites, JC–P=48.9 Hz,
J
H–H=6.7 Hz, CH2CH3
lites, JH–H=6.6 Hz, JH–P=10.9 Hz, JH–Pt=68 Hz,
anti), 1.96 (1H, dd with 195Pt satellites, JH–H=6.6 Hz,
H–P=10.9 Hz, JH–Pt=68 Hz, Hanti), 2.24 (1H, br,
syn), 2.91, 3.10 (1H, 1H, q, q, JH–H=6.7 Hz,
CH2CH3), 3.21 (1H, br, Hsyn), 7.0-7.3 (30H, phenyl H),
8.48 (1H, br, JH–P=4.9 Hz, NH
); 13C-NMR (CDCl3,
50.32 MHz) l 15.0 (t, JC–P=5.3 Hz, CH2CH3), 37.3 (t,
H2CH3), 39.6 (d with 195Pt satellites,
C–P=46.8 Hz, JC–Pt=178 Hz, Ct), 41.1 (dd with 195Pt
H
J
H
JC–Pt=198 Hz, Ct), 45.2 (dd, JC–P=5.8, 14.2 Hz, C6 H),
128–133 (phenyl C), 155.6 (dd, JC–Pt=101 Hz, Cc);
Anal. Calc. for PtC42H42NP2Br-H2O C, 55.09; H, 4.84;
N. 1.53. Found: C, 54.44; H, 4.84; N, 1.53.
6
6
4.2.5. {Pt(PPh3)2[p3-CH2C(NHtBu)CH2]}(Br) (3e)
Refer to the paragraph for 3a for the detailed proce-
dure. The reaction of complex 1 (201 mg, 0.24 mmol)
6
J
J
C–P=6.4 Hz, C6
satellites, JC–P=4.4, 45.3 Hz, JC–Pt=197 Hz, Ct), 128–
134 (phenyl C), 156.1 (t with 195Pt satellites, JC–P=4.3
Hz, JC–Pt=110.3 Hz, Cc).
t
and BuNH2 (25 ml, 0.24 mmol) for 2 days gave 3e in
86% yield (184 mg). IR (KBr) wCꢀN 1585 cm−1 31P-
;
NMR (CDCl3, 81.015 MHz, 283 K) l 19.6 (d, JP–P
=
8.2 Hz, JP–Pt=3264 Hz), 20.4 (d, JP–P=8.2 Hz,
4.2.4. {Pt(PPh3)2[p3-CH2C(NHiPr)CH2]}(Br) (3d)
Refer to the paragraph for 3a for the detailed proce-
dure. The reaction of complex 1 (150 mg, 0.18 mmol)
1
J
P–Pt=3235 Hz); H-NMR (CDCl3, 300 MHz, 283 K)
l 1.24 (9H, s, CH3
), 1.64 (1H, dd with 195Pt satellites,
H–H=6.5 Hz, JH–P=10.7 Hz, JH–Pt=61 Hz, Hanti),
6
J
i
and PrNH2 (18 ml) gave 3d in 92% yield (148 mg). IR
2.20 (1H, dd, JH–H=5.5 Hz, JH–P=11.6 Hz, Hanti),
2.36, 3.42 (1H, 1H, br, br, Hsyn), 7.1–7.3 (30H, phenyl
H), 7.76 (1H, s with 195Pt satellites, JH–Pt=27 Hz,
Table 1
Relative yields of the N-alkylated p3-N-TMM complexes formed
from reactions of trans-Pt(Br)(PPh3)2(p1-CHCCH2) (1) with amines
NH
42.5 (d with 195Pt satellites, JC–P=45 Hz, JC–Pt=190
Hz, Ct), 52.1 (t, JC–P=5.7 Hz, Me3C), 127–134 (phenyl
C), 156.8 (t with 195Pt satellites, JC–P=4 Hz, JC–Pt
6 6 H3),
); 13C-NMR (CDCl3, 50.32 MHz) l 29.2 (s, C
Amines
Relative yields of the products (%)
6
=
3b
3c
3d
3e
3f
3g
105.6 Hz, Cc); Anal. Calc. for C43H44NP2PtBr C, 56.65;
H, 4.86; N. 1.54. Found: C, 56.65; H, 4.70; N, 1.45.
MeNH2/EtNH2
EtNH2/iPrNH2
iPrNH2/tBuNH2
iPrNH2/PhNH2
c-C6H11NH2/PhNH2
63
37
64
36
89
11
67
4.2.6. {Pt(PPh3)2[p3-CH2C(NHC6H12)CH2]}(Br) (3f)
Refer to the paragraph for 3a for the detailed proce-
dure. The reaction of complex 1 (200 mg, 0.24 mmol)
and c-C6H12NH2 (31 ml, 0.25 mmol) gave 3f in 87%
33
33
67
In a typical case, 1 (20 mg) and a mixture of amines (or aniline) with
each in 10-fold equivalents were allowed to react in 0.5 ml of CDCl3.
The relative yields of the products were measured using NMR
spectroscopy.
yield (196 mg). IR (KBr) wCꢀN 1577 cm−1 31P-NMR
;
(CDCl3, 81.015 MHz) l 19.3 (d, JP–P=8.9 Hz, JP–Pt
=

A.-J. Chen et al. / Journal of Organometallic Chemistry 569 (1998) 39–54
45
195Pt satellites, JC–P=4.2 Hz, JC–Pt=110.4 Hz, Cc);
Anal. Calc. for PtC45H46NP2Br C, 57.63; H, 4.94; N.
1.49. Found: C, 56.02; H, 4.92; N, 1.36.
Table 2
Selected NMR data of p3-N-TMM complexes and N-protonated,
N-alkylated, N-arylated p3-N-TMM complexes of Pt and Pd
R, R%
Hanti(JH–Pt
)
Hsyn Ct(JC–Pt
)
Cc(JC–Pt)
4.2.7. {Pt(PPh3)2[p3-CH2C(NHPh)CH2]}(Br 3g, BF4,
3g%)
{Pt(PPh3)2[p3-CH2C(NRR%)CH2]}+
H, H (3a)
H, Me (3b)
1.93(62.8)
1.65(67)
1.97(67)
1.60(68)
1.96(68)
2.06
2.83 44.8(169.2)
2.31 40.1(176.4)
3.23 41.5(201)
2.24 39.6(177.9)
3.21 41.1(196.6)
2.41 39.6(186.8)
41.0(197.6)
2.36 42.5(190)
3.42
2.76 40.2(184.2)
153.1(88.5)
156.5(110.7)
Refer to the paragraph for 3a for the detailed proce-
dure. The reaction of complex 1 (150 mg, 0.18 mmol)
and PhNH2 (18 ml, 0.20 mmol) took 96 h to give 3g in
78% yields (130 mg). Alternatively, complex 2 was first
prepared from 1 (250 mg, 0.30 mmol) and AgBF4 (58
mg) in situ. After AgBr was removed by filtration, the
filtrate was allowed to react with PhNH2 (0,33 mmol)
for 1 h at 25°C. The yield of 3g% was 85% (234 mg). For
H, Et (3c)
156.1(110.3)
155.6(101)
i
H, Pr (3d)
t
H, Bu (3e)
1.64(61)
2.20
—
156.8(105.6)
155.2(110.4)
H, c-C6H11
(3f)
3g: IR (KBr) wCꢀN 1551 cm−1 31P-NMR (CDCl3,
;
1.99(68.9)
2.09(62.5)
1.75
3.44 40.8
3.40 44.9(176.4)
2.32 41.8
81.015 MHz) l 19.0 (JP–Pt=3361 Hz); 1H-NMR
(CDCl3, 300 MHz, 283K) l 2.09 (2H, br with 195Pt
satellites, JH–Pt=62.5 Hz, Hanti), 3.40 (2H, br, Hsyn),
7.0-7.5 (35H, phenyl H), 10.1 (1H, s with 195Pt satellites,
H, Ph (3g)
H, C2H4OH
(3h)
150.8
154.7(105.6)
2.01
2.33
2.05(73.2)
2.62(60)
2.34(69.2)
2.26(42.3)
2.99 42.5
Et, Et (3i)
C3H6 (3j)
Ph, Ph (3k)
Me, Ph (3l)
H, SO2Ph
(3m)
2.33 40.0(187.8)
2.23 39.3(181.3)
2.83 48.9
2.51 44.8
3.49 52.6(103.4)
157.7(110.4)
154.3(106.3)
151.4
154.3(95.3)
138.3
J
H–Pt=19.3 Hz, NH
6
); 13C-NMR (CDCl3, 75.469 MHz)
),
l 44.9 (d, JC–P=43.9 Hz, Ct), 123.5, 124.9 (NCipso
128–138 (phenyl C), 150.8 (s, Cc); Anal. Calc. for
C44H40NP2PtBr C, 57.46; H, 4.38; N. 1.52. Found: C,
6
1
58.11; H, 4.29; N, 1.36. For 3g%: H-NMR (CDCl3, 200
{Pd(PPh3)2[p3-CH2C(NRR%)CH2]}+
MHz, 283K) l 2.2 (2H, dd with 195Pt satellites, JH–P
=
i
H, Pr (7d)
H, Ph (7g)
Et, Et (7i)
H, SO2Ph
(7m)
2.23
2.53
2.51
2.79
2.72 50.6
3.38 55.2
2.62 50.0
3.63
152.1
148.5
154.0
4.6, 8.8 Hz, JH–Pt=68 Hz, Hanti), 3.12 (2H, br, Hsyn),
7.1–7.6 (35H, phenyl H), 8.4 (1H, s with 195Pt satellites,
J
H–Pt=20 Hz, NH6 ).
H,
2.82
3.59
4.2.8. {Pt(PPh3)2[p3-CH2C(NHCH2CH2OH)CH2]}(Br)
(3h)
SO2C6H4Me
(7n)
Pd(PPh3)(Br)[p3-CH2C(NRR%)CH2]
Refer to the paragraph for 3a for the detailed proce-
dure. The reaction of complex 1 (200 mg, 0.24 mmol)
and HOCH2CH2NH2 (14 vL, 0.24 mmol) gave 3h in
Et, Et (8i)
2.12
2.28
2.50 43.0
3.17 49.1
148.2
90% yield. IR (KBr) wCꢀN 1539 cm−1
;
31P-NMR
M(PPh3)2[p3-CH2C(NR)CH2]
M=Pt, R= 2.05(51.2)
SO2Ph (4m)
M=Pd, R= 2.26
SO2Ph (9m)
3.23 50.7(174.5)
3.31 61.3
158.9(88.9)
154.5
(CDCl3, 81.015 MHz) l 18.1 (d, JP–P=9 Hz, JP–Pt
=
1
3270 Hz), 19.3 (d, JP–P=9 Hz, JP–Pt=3348 Hz); H-
NMR (CDCl3, 300 MHz) l 1.75, 2.01 (1H, 1H, br, br,
Hanti), 2.32, 2.99 (1H, 1H, br, br, Hsyn), 3.14 (2H, br,
M=Pd, R= 2.25
SO2C6H4Me
3.31 61.2
154.8
NCH2CH2
t, JH–H=12 Hz, OH
(1H, s, JH–P=9.7 Hz, NH
MHz) l 41.8 (d, JC–P=47.3 Hz, Ct), 42.5 (d JC–P
49.5 Hz, Ct), 45.6 (s, NCH2CH2OH), 59.2 (s,
6
OH), 3.70 (2H, br, NCH2
), 7.1-7.4 (30H, phenyl H), 8.11
); 13C-NMR (CDCl3, 50.32
6 CH2OH), 4.69 (1H,
(9n)
6
6
=
6
3235 Hz), 19.7 (d, JP–P=8.9 Hz, JP–Pt=3251 Hz);
1H-NMR (CDCl3, 300 MHz) l 0.88–1.73 (11H, m,
NC6 H2CH2OH), 128–134 (phenyl C), 154.7 (d with
195Pt satellites, JC–P=4.0 Hz, JC–Pt=105.6 Hz, Cc).
CH2
6
and Hanti), 1.99 (1H, dd with 195Pt satellites,
J
H–H=6.3 Hz, JH–P=10.6 Hz, JH–Pt=68.9 Hz, Hanti),
4.2.9. {Pt(PPh3)2[p3-CH2C(NEt2)CH2]}(BF4) (3i%)
Refer to the paragraph for 3g% for the detailed proce-
dure. The reaction of complex 1 (150 mg, 0.18 mmol)
and Et2NH (21 ml) gave 3i% in 93% yield (151 mg). IR
2.19 (1H, br, Cy), 2.76, 3.44 (1H, 1H, br, br, Hsyn),
7.0–7.7 (30H, phenyl H), 8.66 (1H, d with 195Pt satel-
lites, JH–P=8.1 Hz, JH–Pt=27 Hz, NH
6
); 13C-NMR
H2), 40.2
(CDCl3, 50.32 MHz) l 4.8, 25.0, 31.8, 33.2 (C
6
(KBr) wCꢀN 1555 cm−1
l 17.9 (JP–Pt=3256 Hz); H-NMR (CDCl3, 300 MHz)
;
31P-NMR (CDCl3, 81.02 MHz)
(d with 195Pt satellites, JC–P=48.7 Hz, JC–Pt=184.2
Hz, Ct), 40.8 (d, JC–P=7.5, 45.2 Hz, Ct), 52.9 (t,
1
J
C–P=8 Hz, C
6
N), 127–134 (phenyl C), 155.2 (t with
l 1.04 (6H, t, JH–H=7.1 Hz, CH6 3CH2), 2.33 (4H, br,

46
A.-J. Chen et al. / Journal of Organometallic Chemistry 569 (1998) 39–54
Fig. 1. ORTEP drawings of {Pd(PPh3)2[p3-CH2C(NH2)CH2]}(BF4) (3a%) with 50% ellipsoid probability. (a) Top-view, all hydrogen atoms are
omitted for clarity. (b) Side-view, phosphino phenyls and all hydrogen atoms (except amino hydrogens) are omitted for clarity.
1
Hsyn and Hanti), 3.12 (4H, q with 195Pt satellites, JH–H
7.1 Hz, JH–Pt=6.6 Hz, CH3CH2), 7.1–7.8 (30H, phenyl
H); 13C-NMR (CDCl3, 50.32 MHz) l 12.85 (s with
=
(CDCl3, 300 MHz) l 17.0 (JP–Pt=3298 Hz); H-NMR
(CDCl3, 300 MHz, 285 K) l 2.05 (2H, d with 195Pt
satellites, JH–H=8.1 Hz, JH–Pt=73.2 Hz, Hanti), 2.23
6
195Pt satellites, JC–Pt=9.6 Hz, C
6 H3CH2), 39.96 (dd with
(2H, br, Hsyn), 2.35 (2H, JH–H=7 Hz, NCH2CH2
(2H, m, NCH2-endo), 3.82 (2H, m, NCH2-exo), 7.1-7.4
(30H, phenyl H); 13C-NMR (CDCl3, 50.32 MHz) l 15.6
(s, NCH2C
H2), 39.3 (dd with 195Pt satellites, JC–P=5.1,
51 Hz, JC–Pt=181.3 Hz, Ct), 50.2 (s with 195Pt satel-
6 ), 3.75
195Pt satellites, JC–P=4.4, 51.0 Hz, JC–Pt=187.8 Hz,
Ct), 43.95 (s with 195Pt satellites, JC–Pt=12.0 Hz,
6
6
CH3C
6
H2), 128–133 (phenyl C), 157.7 (t with 195Pt
6
satellites, JC–P=4.0 Hz, JC–Pt=110.4 Hz, Cc); Anal.
Calc. for PtC43H44NP2–BrH2O C, 56.65; H, 4.86; N.
1.54. Found: C, 55.90; H, 4.84; N, 1.66.
lites, JC–Pt=5.3 Hz, NC6 H2C6 H2), 127–134 (phenyl C),
154.3 (t with 195Pt satellites, JC–P=4.2 Hz, JC–Pt
=
106.3 Hz, Cc).
4.2.10. {Pt(PPh3)2[p3-CH2C(NC3H6)CH2]}(Br) (3j)
Refer to the paragraph for 3a for the detailed proce-
dure. The reaction of complex 1 (305 mg, 0.364 mmol)
and azetidine (25 ml, 0.37 mmol) gave 3j in 91% yield
4.2.11. {Pt(PPh3)2[p3-CH2C(NPh2)CH2]}(BF4) (3k)
Refer to the paragraph for 3g% for the detailed proce-
dure. The reaction of 2 prepared from 1 (210 mg, 0.25
mmol) and AgBF4 (48 mg) in situ, with Ph2NH (45 mg,
(297 mg). IR (KBr) wCꢀN 1534 cm−1
;
31P-NMR

A.-J. Chen et al. / Journal of Organometallic Chemistry 569 (1998) 39–54
47
Fig. 2. ORTEP drawings of Pd(PPh3)2[p3-CH2C(NSO2Ph)CH2] (4m) with 50% ellipsoid probability. (a) Top-view, all hydrogen atoms are omitted
for clarity. (b) Side-view, phosphino phenyls and all hydrogen atoms are omitted for clarity.
cm−1
;
31P-NMR (CDCl3, 81.015 MHz) l 17.1 (JP–Pt
=
0.28 mmol) gave 3k in 73% yield (185 mg). IR (KBr)
1
wCꢀN 1590 cm−1
;
31P-NMR (CDCl3, 81.015 MHz) l
3384 Hz); H-NMR (CDCl3, 300 MHz) l 2.34 (2H, br
with 195Pt satellites, JH–Pt=69.2 Hz, Hanti), 2.51 (2H,
br, Hsyn), 3.07 (3H, s with 195Pt satellites, JH–Pt=18.8
1
17.6 (JP–Pt=3464 Hz); H-NMR (CDCl3, 300 MHz) l
2.62 (2H, dd with 195Pt satellites, JH–H=4.6, JH–P=9.4
Hz, JH–P=60 Hz, Hanti), 2.83 (2H, br, Hsyn), 7.0–7.6
(40H, phenyl H); 13C-NMR (CDCl3, 50.32 MHz) l
48.93 (dd, JC–Pcis=15 Hz, JC–Ptrans=32 Hz, Ct), 117.8,
120.9, 126–134, 142.6, 143.1 (phenyl C), 151.3 (s with
195Pt satellites, JC–Pt=58 Hz, Cc).
Hz, C
50.32 MHz) l 39.6 (s with 195Pt satellites, JC–Pt=11.7
Hz, CH3), 44.8 (unresolved, Ct), 125.7, 127.6, 128–134,
143.1 (phenyl C), 154.3 (t with 195Pt satellites, JC–P
8.5 Hz, C–Pt=95.3 Hz, Cc); Anal. Calc. for
6
H3), 7.1-7.6 (35H, phenyl H); 13C-NMR (CDCl3,
6
=
J
PtC46H42NP2BF4 C, 58.00; H, 4.44; N. 1.47. Found: C,
57.55; H, 4.50; N, 1.51.
4.2.12. {Pt(PPh3)2[p3-CH2C(NMePh)CH2]}(BF4) (3l)
Refer to the paragraph for 3g% for the detailed proce-
dure. The reaction of 2 prepared from 1 (250 mg, 0.30
mmol) and AgBF4 (58 mg) in situ, with MePhNH (33
ml) gave 3l in 78% yield (223 mg). IR (KBr) wCꢀN 1598
4.2.13. {Pt(PPh3)2[p3-CH2C(NHSO2Ph)CH2]}(BF4)
(3m)
The reaction of 4m (92 mg, 0.1 mmol) and HBF4

48
A.-J. Chen et al. / Journal of Organometallic Chemistry 569 (1998) 39–54
Table 3
Selected bond parameters of p3-N-TMM complexes, N-protonated, N-alkylated, N-arylated p3-N-TMM complexes of Pt and Pd
qa (°)
˚
˚
˚
˚
R, R%
{Pt(PPh3)2[p3-CH2C(NRR%)CH2]}+
M–Ct (A)
M–Cc (A)
Ct–Cc (A)
Cc–N (A)
Cc–Ct–Cc% (°)
H, H (3a%)
2.12(1)
2.19(3)
2.17(2)
2.19(2)
2.150(8)
2.176(8)
2.16(1)
2.21(1)
2.11(2)
2.13(2)
2.16(1)
2.21(1)
2.329(9)
2.36(1)
2.303(7)
2.30(1)
2.35(2)
2.30(1)
1.43(1)
1.43(1)
1.45(2)
1.49(3)
1.41(1)
1.42(1)
1.39(2)
1.44(2)
1.40(3)
1.42(3)
1.39(2)
1.44(2)
1.33(1)
1.47(2)
1.40(1)
1.37(2)
1.34(2)
1.37(2)
112.8(9)
111(2)
113.3(8)
116(1)
109(2)
116(1)
56(1)
57(2)
62(1)
58(4)
62.6(6)
60(2)
i
H, Pr (3d)
H, Ph (3g%)
H, C2H4OH (3h)
Et, Et (3i%)
C3H6 (3j)
Pt(PPh3)2[p3-CH2C(NR)CH2]
SO2Ph (4m) 2.141(4)
2.147(4)
2.333(4)
1.435(6)
1.439(6)
1.342(6)
109.9(4)
58.5(4)
{Pd(PPh3)2[p3-CH2C(NRR%)CH2]}+
i
H, Pr (7d)
H, Ph (7g)
Et, Et (7i)
2.166(7)
2.168(7)
2.14(1)
2.20(1)
2.156(7)
2.156 (7)
2.326(7)
2.28(1)
1.41(1)
1.43(1)
1.42(2)
1.43(2)
1.41(1)
1.43(1)
1.32(1)
1.38(2)
1.35(1)
112.6(7)
116(1)
58.7(7)
60(1)
2.327(7)
111.8(6)
58.2(7)
Pd(PPh3)(Br)[p3-CH2C(NRR%)CH2]
Et, Et (8i)
2.089(3)
2.144(4)
2.292(3)
1.409(5)
1.414(5)
1.343(5)
110.2(3)
59.2(4)
a The dihedral angle q is defined by the planes Ct–Cc–Ct% and Ct–M–Ct%.
4.2.15. trans-Pd(Br)(PPh3)2[p1-CHCCH2) (5)
(85% etherate solution, 0.1 mmol) gave 3m in 74% yield
(75 mg). 31P-NMR (CDCl3, 81.015 MHz) l 18.1 (JP–Pt
To a 30 ml of THF solution that contained 2.5 g of
Pd(PPh3)4, was added 0.24 ml (1.1 equivalents) of
propargyl bromide under dry N2. The yellow reaction
solution turned to colorless after 20 min. Further stir-
ring for 30 min caused a whitish yellow precipitate of 5.
The solution was then concentrated to 15 ml and was
filtered. Solid product in 90% yield (1.46 g) was recov-
ered after being washed by Et2O. IR (KBr pellet) wCꢀCꢀC
1
=3729 Hz); H-NMR (CDCl3, 300 MHz) l 2.26 (2H,
d with 195Pt satellites, JH–P=8.8 Hz, JH–Pt=42.3 Hz,
Hanti), 3.49 (2H, br, Hsyn), 6.64 (1H, br, NH6 ), 7.2-7.5
(33H, phenyl H), 7.72 (2H, d, JH–H=7.9 Hz, o-H);
13C-NMR (CDCl3, 50.3 MHz) l 52.6 (dd with 195Pt
satellites, JC–P=4.8, 39.2 Hz, JC–Pt=103.4 Hz, Ct),
127–134 (phenyl C), 138.3 (t, JC–P=3.7 Hz, Cc), 138.6
(Cipso).
1915 cm−1
1H-NMR (CDCl3, 300 MHz) l 3.12 (2H, dt, JH–H=6.1
HZ, JH–P=1.3 HZ, CHCCH2), 4.67 (1H, tt, JH–H=6.1
HZ, JH–P=6.4 HZ, CHCCH2), 7.7–7.2 (30H, m,
phenyl H); 13C-NMR (CDCl3, 50.32 MHz, 273 K) l
66.9 (s, CHCCH2), 87.4 (t, JC–P=5.1 HZ, CHCCH2),
128–135 (phenyl C), 199.8 (t, C–P=3.5 HZ,
CHC
CH2); FAB MS (m/z) 750 (M+ +1); Anal. Calc.
;
31P-NMR (CDCl3, 81.015 MHz) l 24.2 (s);
6
4.2.14. Pt(PPh3)2[p3-CH2C(NSO2Ph)CH2] (4m)
6
Refer to the paragraph for 9m for the detailed proce-
dure. IR (KBr) wCꢀN 1479 cm−1, wSꢀO 1137, 1393 cm−1
;
6
6
31P-NMR (CDCl3, 300 MHz) l 21.6 (JP–Pt=3315 Hz);
1H-NMR (CDCl3, 81.015 MHz) l 2.05 (2H, d with
195Pt satellites, JH–P=7.7 Hz, JH–Pt=51.2 Hz, Hanti),
3.23 (2H, br, Hsyn), 7.18–7.28 (33H, phenyl H), 7.73
(2H, d, JH–H=6.0 Hz, o-H); 13C-NMR (CDCl3, 50.32
MHz) l 50.7 (dd with 195Pt satellites, JC–P=4.0, 46.3
Hz, JC–Pt=174.5 Hz, Ct), 127–134 (phenyl C), 145.0
(Cipso), 158.9 (t with 195Pt satellites, JC–P=4.1 Hz,
J
6
for PdC39H33P2Br: C, 62.46; H, 4.44. Found: C, 62.53;
H, 4.50.
4.2.16. [Pd(PPh3)2[p3-C3H3)](X) (X=PF6 6, BF4 6%,
OTf 6%%)
To a mixture containing 5 (208 mg, 0.28 mmol) and
AgPF6 (75 mg, 0.3 mmol) was added N2-degassed
CH2Cl2 (20 ml) at −75°C. The reaction solution was
stirred for 40 min to allow the complete precipitation of
JC–Pt=88.9 Hz, Cc); Anal. Calc. for PtC45H39NO2SP2
C, 59.08; H, 4.30; N. 1.53. Found: C, 59.11; H, 4.40; N,
1.55.

A.-J. Chen et al. / Journal of Organometallic Chemistry 569 (1998) 39–54
49
Fig. 3. ORTEP drawing of {[cis-Pt(PPh3)2(v-CH2CMeNH)]2}(Br)2 (15) with 50% ellipsoid probability. All hydrogen atoms and phosphino
phenyls are omitted for clarity.
50.6 (m, JC–P=47.4 Hz, Ct), 128–134 (phenyl C), 152.1
(t, JC–P=5.5 Hz, Cc); MS (FAB) 728 (M+ –OTf).
AgBr. After AgBr was removed by filtration, the solu-
tion was concentrated and addition of degassed Et2O to
the solution resulted in whitish yellow solids. The
product contains small amounts of silver salts. The
purification would cause the decomposition of the de-
sired compound. Analogous reactions of 5 with AgBF4
or AgOTf at −50°C generate the p3-allenyl/propargyl
palladium cation as well. The products are identified
with NMR because the isolation of 6% and 6%% is difficult.
For further synthetic purpose, complex 6 are usually
prepared in situ. Selected spectral data for 6: 31P-NMR
4.2.18. {Pd(PPh3)2[p3-CH2C(NHPh)CH2]}(OTf ) (7g)
Refer to the paragraph for 7i for the detailed proce-
dure. The reaction of 6%% prepared from 5 (155 mg, 0.21
mmol) and AgOTf (53.1 mg, 0.21 mmol) in situ with
PhNH2 (19 ml) gave 7g. The isolated yield was 96 mg
(50%). The single crystals were grown from CHCl3/
Et2O cosolvent at 0°C. IR (KBr pellet) wCꢀN 1550 cm−1
;
31P-NMR (CDCl3, 81.015 MHz) l 26.1; 1H-NMR
(CDCl3, 300 MHz) l 2.53 (2H, m, Hanti), 3.38 (2H, br,
(CDCl3, 81.015 MHz, 198 K) l 26.7, 28.0 (d, JP–P
41.5 Hz); H-NMR (CDCl3, 300 MHz) l 3.40 (ddd,
=
Hsyn), 7.14-7.41 (30H, m, phenyl H), 8.60 (1H, s, NH6 );
1
13C-NMR (CDCl3, 50.32 MHz) l 55.2 (m, Ct), 122–139
(phenyl C), 148.5 (t, JC–P=5.4 Hz, Cc).
2H, JH–H=2.1 Hz, JP–H=1.7, 7.7 Hz, CH2
6
), 4.65 (tdd,
), 7.15–7.38
1H, JH–H=2.1 Hz, JP–H=1.6, 9.0 Hz, CH
6
(30 H, m, phenyl H); 13C-NMR (CDCl3, 50.32 MHz,
4.2.19. {Pd(PPh3)2[p3-CH2C(NEt2)CH2]}(OTf ) (7i)
To a two-neck round bottle which contained 5 (150
mg, 0.2 mmol) and AgOTf (51.4 mg, 0.2 mmol), was
charged dried N2-degassed CH2Cl2 (15 ml) at −40°C.
After 40 min, white AgBr precipitate was removed by
filtration. Diethyl amine (21 ml) was injected. The solu-
tion was stirred for another 30 min, and then was
concentrated to 5 ml by vacuo. Addition of diethyl
ether (25 ml) resulted in a light yellow product in 80%
yield. The single crystals were grown from CHCl3/Et2O
198 K) l 57.6 (d, JC–P=38.7 Hz, C
C–P=48.8 Hz, CH2CCH), 100.6 (dd, JC–P=5.8, 8.0
Hz, CH2CCH), 128–134 (phenyl C).
6 H2CCH), 91.3 (d,
J
6
6
4.2.17. {Pd(PPh3)2[p3-CH2C(NHiPr)CH2]}(Br) (7d)
Refer to the paragraph for 7i for the detailed proce-
dure. The reaction of 5 (150 mg, 0.20 mmol) and
i
AgOTf (51.4 mg, 0.2 mmol) in situ with PrNH2 (17 ml)
gave 7d. The isolated yield was 114 mg (65%). The
single crystals were grown from CHCl3/Et2O cosolvent
cosolvent at 0 °C. IR (KBr pellet) wCꢀN 1550 cm−1
;
at 0°C. IR (KBr pellet) wCꢀN 1555 cm−1 31P-NMR
;
31P-NMR (CDCl3, 81.015 MHz) l 24.9; 1H-NMR
(CDCl3, 300 MHz) l 0.94 (6H, t, JH–H=7.1 Hz,
(CDCl3, 300 MHz, 253K) l 25.1, 26.5 (JP–P=29.0 Hz);
1H-NMR (CDCl3, 300 MHz) l 1.13 (6H, d, JH–H=6.3
CH2CH3
(4H, q, JH–H=7.1 Hz, CH2
phenyl H); 13C-NMR (CDCl3, 50.32 MHz) l 12.8 (s,
CH2CH3), 43.9 (s, CH2CH3), 50.0 (m, Ct), 128.8, 130.9,
133.4 (phenyl C), 154.0 (t, JC–P=4.9 Hz, Cc).
6
), 2.51 (2H, m, Hanti), 2.62 (2H, br, Hsyn), 2.95
Hz, CH3
(1H, m, JH–H=6.3, 7.8 Hz, CH
7.1 Hz, NH
), 7.15-7.38 (30H, m, phenyl H); 13C-NMR
(CDCl3, 50.32 MHz) l 22.5 (s, CH3), 44.8 (s, CHMe2),
6
), 2.23 (2H, br, Hanti), 2.72 (2H, br, Hsyn), 3.01
6
CH3), 7.15–7.38 (30H, m,
6
), 6.41 (1H, d, JH–H
=
6
6
6
6
6

50
A.-J. Chen et al. / Journal of Organometallic Chemistry 569 (1998) 39–54
Scheme 7.
4.2.20. {Pd(PPh3)2[p3-CH2C(NHSO2Ph)CH2]}(BF4)
(7m)
in 70% yield (105 mg). The single crystals were grown
from CHCl3/Et2O cosolvent at 0°C. IR (KBr pellet)
wCꢀN 1527 cm−1
22.9; H-NMR (CDCl3, 300 MHz) l 1.03 (6H, t, JH–
;
31P-NMR (CDCl3, 81.015 MHz) l
The reaction of 9m (150 mg, 0.18 mmol) and HBF4
(85% etherate solution, 33 ml) in CH2Cl2 at 25°C gave
7m in 98% yield (161 mg). IR (KBr pellet) wCꢀN 1500
1
H=7.0 Hz, CH2CH6 3), 2.12 (1H, d, JH–H=4.2 Hz,
Hanti), 2.28 (1H, ddd, JH–H=4.2, 5.1 Hz, JH–P=4.2
Hz, Hanti), 2.50 (1H, dd, JH–H=3.3 Hz, JH–P=11.2
cm−1 31P-NMR (CDCl3, 81.015 MHz) l 25.8; 1H-
;
NMR (CDCl3, 300 MHz) l 2.79 (2H, br, Hanti), 3.63
Hz, Hsyn), 3.02 (4H, q, JH–H=7.1 Hz, CH6 2CH3), 3.17
(2H, s, Hsyn), 7.18–7.68 (34H, phenyl H), 8.38 (1H, s,
NH6 ).
(1H, ddd, JH–H=3.3, 5.1 Hz, JH–P=5.9 Hz, Hsyn),
7.35-7.69 (15H, m, phenyl H); 13C-NMR (CDCl3, 50.32
4.2.21. {Pd(PPh3)2[p3-CH2C(p-NHSO2C6H4Me)CH2]}
(BF4) (7n)
MHz) l 13.0 (s, CH2C
6 H3), 43.0 (s, Ct trans to Br), 44.2
(s, CH2CH3), 49.1 (d, JC–P=47.4 Hz, Ct trans to PPh3),
6
128.1, 128.3, 130.0, 134.1 (phenyl C), 148.2 (s, Cc); MS
(FAB) 560 (M+); Anal. Calc. for PdC25H29NPBr.0.5
CH2Cl2: C, 50.77; H, 5.01; N. 2.32. Found: C, 51.16; H,
4.94; N, 2.35.
The reaction of 9n (150 mg, 0.18 mmol) and HBF4
(85% etherate solution, 30 ml) in CH2Cl2 at 25 °C gave
7n in 98% yield (164 mg). IR (KBr pellet) wCꢀN 1520
cm−1 31P-NMR (CDCl3, 81.015 MHz) l 25.8; 1H-
;
NMR (CDCl3, 300 MHz) l 2.15 (3H, s, CH3
(2H, br, Hanti), 3.59 (2H, s, Hsyn), 7.18-7.68 (35H,
phenyl H), 8.32 (1H, s, NH).
6 ), 2.82
4.2.23. Pd(PPh3)2[p3-CH2C(NSO2Ph)CH2] (9m)
Refer to the paragraph for 7i for the detailed proce-
dure. The reaction of 5 (250 mg, 0.33 mmol) and
NaNHSO2Ph (80% mineral oil, 90 mg, 0.40 mmol) in
CH2Cl2 at 25°C gave 9m in 70% yield (190 mg). IR
6
4.2.22. Pd(Br)(PPh3)[p3-CH2C(NEt2)CH2] (8i)
To a round-bottom flask containing 5 (200 mg, 0.27
mmol), was charged dried N2-degassed CH2Cl2 (15 ml)
at 25°C, followed by the injection of diethylamine (two
equivalents). The solution was vigorously stirred for 2
h, and then was concentrated to 5 ml by vacuo. Addi-
tion of diethyl ether (15 ml) resulted in a white product
(KBr pellet) wCꢀN 1480 cm−1, wSꢀO 1161, 1382 cm−1
;
31P-NMR (CDCl3, 81.015 MHz) l 27.0; 1H-NMR
(CDCl3, 300 MHz) l 2.26 (2H, m, Hanti), 3.31 (2H, s,
H
syn), 7.18–7.68 (35H, phenyl H); 13C-NMR (CDCl3,
50.32 MHz) l 61.3 (m, Ct), 126–134 (phenyl C), 154.5
(s, Cc); MS (FAB) 825 (M+).
4.2.24. Pd(PPh3)2[p3-CH2C(p-NSO2C6H4Me)CH2] (9n)
Refer to the paragraph for 7i for the detailed proce-
dure. The reaction of 5 (250 mg, 0.33 mmol) and
NaNHSO2C6H4Me (97 mg, 0.40 mmol) gave 9n in 72%
yield (200 mg). IR (KBr pellet) wCꢀN 1480 cm−1, wSꢀO
1161, 1382 cm−1
27.0; H-NMR (CDCl3, 300 MHz) l 2.25 (5H, m, CH3
;
31P-NMR (CDCl3, 81.015 MHz) l
1
6
and Hanti), 3.31 (2H, s, Hsyn), 7.15–7.65 (34H, phenyl
H); 13C-NMR (CDCl3, 50.32 MHz) l 21.3 (s, C
6
H3),
61.2 (m, Ct), 128–134 (phenyl C), 154.8 (s, Cc); MS
(FAB) 839 (M+).
Scheme 8.

A.-J. Chen et al. / Journal of Organometallic Chemistry 569 (1998) 39–54
51

52
A.-J. Chen et al. / Journal of Organometallic Chemistry 569 (1998) 39–54
Table 5
˚
Selected bond distances (A) and angles (°) of 3a, 4m, and 15
{(PPh3)2Pt[p3-CH2C(NH2)CH2]}(BF4) (3a)
Pt–P1
Pt–C2
C2–C3
2.272(3)
2.329(9)
1.43(1)
Pt–P2
Pt–C3
C2–N
2.300(3)
2.12(1)
1.33(1)
Pt–C1
C1–C2
2.19(3)
1.43(1)
P1–Pt–P2
P1–Pt–C3
P2–Pt–C3
C2–Pt–C3
Pt–C2–C3
C1–C2–C3
101.4(1)
96.9(3)
161.5(3)
37.1(4)
63.5(5)
112.8(9)
P1–Pt–C1
P2–Pt–C1
C1–Pt–C2
Pt–C1–C2
Pt–C3–C2
C1–C2–N
163.3(3)
94.5(3)
36.8(4)
76.9(6)
79.4(6)
123.3(9)
P1–Pt–C2
P2–Pt–C2
C1–Pt–C3
Pt–C2–C1
Pt–C2–N
C3–C2–N
130.2(3)
126.5(3)
67.1(4)
66.3(6)
126.0(7)
122(1)
(PPh3)2Pt[p3-CH2C(NSO2Ph)CH2] (4m)
Pt–P1
Pt–C2
C2–C3
S–O1
2.286(1)
2.333(4)
1.435(6)
1.441(3)
Pt–P2
Pt–C3
C2–N
S–O2
2.274(1)
2.147(4)
1.342(6)
1.439(3)
Pt–C1
C1–C2
S–N
2.141(4)
1.439(6)
1.599(4)
1.782(5)
S–C4
P1–Pt–P2
P1–Pt–C3
P2–Pt–C3
C3–Pt–C2
Pt–C3–C2
C1–C2–C3
C2–N–S
104.10(5)
165.7(1)
90.0(1)
37.1(2)
78.5(3)
109.9(4)
120.6(3)
106.4(2)
106.3(2)
P1–Pt–C1
P2–Pt–C1
C1–Pt–C2
Pt–C1–C2
Pt–C2–C3
C1–C2–N
N–S–O1
99.3(1)
156.5(1)
37.2(2)
78.7(2)
64.4(2)
130.0(4)
114.2(2)
116.5(2)
P1–Pt–C2
P2–Pt–C2
C1–Pt–C3
Pt–C2–C1
Pt–C2–N
C3–C2–N
N–S–O2
131.1(1)
121.8(1)
66.5(2)
64.1(2)
125.6(3)
117.9(4)
105.9(2)
106.9(2)
N–S–C4
O2–S–C4
O2–S–O1
O1–S–C4
{[cis-Pt(PPh3)2(v-CH2CmeNH)]2}(Br)2 (15)

A.-J. Chen et al. / Journal of Organometallic Chemistry 569 (1998) 39–54
53
Table 5 (continued)
Pt1–P1
Pt1–C5
Pt2–N2
N2–C4
C4–C5
2.310(3)
2.15(1)
2.04(1)
1.30(2)
1.43(2)
Pt1–P2
Pt2–P3
Pt2–C2
C1–C2
C4–C6
2.266(4)
2.260(4)
2.13(1)
1.47(2)
1.49(2)
Pt1–N1
Pt2–P4
N1–C1
C1–C3
2.052(9)
2.313(4)
1.28(2)
1.48(2)
P1–Pt1–P2
P2–Pt1–N1
Pt1–N1–C1
C2–C1–C3
P3–Pt2–N2
P4–Pt2–C2
N2–C4–C5
Pt2–C2–C1
98.3(1)
170.1(3)
131.0(8)
116(1)
169.1(3)
169.5(3)
120(1)
P1–Pt1–N1
P2–Pt1–C5
N1–C1–C2
Pt1–C5–C4
P3–Pt2–C2
N2–Pt2–C2
N2–C4–C6
88.2(3)
85.9(3)
124(1)
112.6(8)
84.9(3)
88.1(4)
120(1)
P1–Pt1–C5
N1–Pt1–C5
N1–C1–C3
P3–Pt2–P4
P4–Pt2–N2
Pt2–N2–C4
C5–C4–C6
173.1(3)
88.4(4)
120(1)
99.5(1)
88.8(3)
131.7(8)
120(1)
115.4(8)
4.2.25. trans-Pt(PPh3)2(O2CMe)(p1-CHCCH2) (10)
The reaction of trans-Pt(Br)(PPh3)2(p3-CHCCH2) (1)
(50 mg, 0.063 mmol) and equimolar AgOAc gave the
product quantitatively based on NMR measurements.
dtd with 195Pt satellites, JH–H=6.7 Hz, JH–P=5.3, 6.6
Hz, JH–Pt=116.5 Hz, CH), 7.1-7.5 (phenyl H)
6
4.2.28. cis-Pt(Ph2PCH2CH2PPh2)(NHSO2Ph)(p1-
CHCCH2) (13)
31P-NMR (CDCl3, 81.015 MHz) l 23.2 (JP–Pt=3165
1
Hz); H-NMR (CDCl3, 300 MHz) l 0.85 (s, CH3
6
), 2.71
To a CDCl3 solution containing 12 (30 mg), was
added equimolar NaNHSO2Ph. The NMR spectra were
then taken. 31P-NMR (CDCl3, 81.015 MHz) l 39.5 (d,
JP–P unresolved, JP–Pt=3521 Hz), 45.5 (d, JP–P unre-
solved, JP–Pt=2205 Hz); 1H–NMR (CDCl3, 50.32
MHz) l 2.0–2.5 (4H, m, C2H4), 3.76 (2H, t with 195Pt
(2H, dt with 195Pt satellites, JH–H=6.5 Hz, JH–P=3.9
Hz, JH–Pt=52.0 Hz, CH
), 4.96 (1H, tt, with 195Pt
satellites, JH–H=6.5 Hz, JH–P=2.5 Hz, JH–Pt=123.6
Hz, CH
2), 7.1–7.5 (phenyl H); 13C-NMR (CDCl3, 50.32
MHz) l 23.1 (s with 195Pt satellites, JC–Pt=17.7 Hz,
H3), 59.7 (t with 195Pt satellites, JC–P=10.6 Hz, JC–
Pt=848.9 Hz, C
H), 65.9 (s with 195Pt satellites, JC–Pt
58.6 Hz, C
H2), 128–134 (phenyl C), 175.6 (s with 195Pt
satellites, JC–Pt=22.1 Hz, CO), 206.1 (t, JC–P=3.9 Hz,
ꢀCꢀ).
6
6
C
6
satellites, JH–H=6.6 Hz, JH–Pt=36.8 Hz, CH2
6
), 4.29
), 5.37
6
=
(1H, s with 195Pt satellites, JH–Pt=23.0 Hz, NH
6
6
(1H, dtd, with 195Pt satellites, JH–H=6.6 Hz, JH–P
=
6
1.5, 6.2 Hz, JH–Pt=81 Hz, CH6 ), 7.1–7.5 (phenyl H)
6
4.2.29. Pt(Ph2PCH2CH2PPh2)[p3-CH2C(NSO2Ph)CH2]
(14)
The solution of 13 from above was heated at 60°C
for 12 h to give complex 14 as the only noticeable
product based on the NMR measurements. 31P-NMR
(CDCl3, 81.015 MHz) l 46.7 (JP–Pt=3160 Hz); 1H-
NMR (CDCl3, 50.32 MHz) l 2.33 (6H, m, C2H4 and
4.2.26. trans-Pt(PPh3)2(NHSO2Ph)(p1-CHCCH2) (11)
To the CDCl3 solution of 10 from above, was added
equimolar NaNHSO2Ph. The NMR spectra were then
taken. 31P-NMR (CDCl3, 81.015 MHz) l 21.3 (JP–Pt
=
1
3064 Hz); H-NMR (CDCl3, 300 MHz) l 2.74 (2H, dt
with 195Pt satellites, JH–H=6.0 Hz, JH–P=2.0 Hz, JH–Pt
=48.4 Hz, CH
H–H=6.0 Hz, JH–P=3.8 Hz, JH–Pt=96.1 Hz, CH6 2),
6
), 4.63 (1H, tt, with 195Pt satellites,
H
anti), 4.30 (2H, br, Hsyn), 7.1–7.5 (phenyl H).
J
7.1–7.5 (phenyl H).
4.2.30. {[cis-Pt(PPh3)2(v-CH2CMeNH)]2}(Br)2 (15)
Complex 1 (0.18 mmol) and ammonia (0.2 mmol)
were allowed to react in chloroform for 1 day, followed
with methanolated KOH (14mg KOH in 1 ml MeOH)
to the reaction solution. The solution was dried by
vacuo after 5 min. Dichloromethane was added and the
potassium salt was filtered off. A white product was
precipitated and was washed by acetone. The yield was
64%. Single crystals were grown from CH2Cl2/acetone.
31P-NMR (CDCl3, 81.015 MHz) l 12.9 (d, JP–P=16.5
4.2.27. cis-Pt(Cl)(Ph2PCH2CH2PPh2)(p1-CHCCH2)
(12)
To
a
round-bottom flask containing trans-
Pt(Cl)(PPh3)2(p3-CHCCH2) (262 mg, 0.33 mmol), was
introduced a benzene solution containing equimolar
dppe dropwise into 15 ml benzene. The reaction solu-
tion was vigorously stirred for 20 min. Adding hexane
resulted in the product in 91% yield (200 mg). 31P-
NMR (CDCl3, 300 MHz) l 41.8 (d, JP–P unresolved,
Hz, JP–Pt=3420 Hz), 22.9 (d, JP–P=16.5 Hz, JP–Pt
=
J
P–Pt=4087 Hz), 43.0 (d, JP–P unresolved, JP–Pt=1994
1
1
2243 Hz); H-NMR (CDCl3, 300 MHz) l 1.73 (6H, s,
CH3), 2.42 (4H, dd, JH–P=9.2 Hz, unresolved J%
CH2), 8.74 (2H, br, NH
Hz); H-NMR (CDCl3, 300 MHz) l 2.0-2.5 (4H, m,
C2H4), 3.33 (2H, t with 195Pt satellites, JH–H=6.7 Hz,
6
H–P%
J
H–P=1.7, 5.3 Hz, JH–Pt=33.3 Hz, CH2
6
), 5.67 (1H,
6
6 ).

54
A.-J. Chen et al. / Journal of Organometallic Chemistry 569 (1998) 39–54
108 (1986) 508. (c) B.M. Trost, S. Schnider, J. Am. Chem. Soc.
111 (1989) 4430. (d) M.D. Jones, R.D.W. Kemmit, Adv.
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T.A. Albright, Organometallics 8 (1989) 1991 and references
therein. (f) M. Frey, T.A. Jenny, H. Stoeckli-Evans,
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4.2.31. cis-{(PPh3)2Pt[NH2CH2CH2O]}(Br) (16)
Complex (20 mg, 0.024 mmol) reacts with
H2NCH2CH2OH (30 ml, 0.048 mmol) in CH2Cl2 for 96
h to yield 16 quantitatively. 31P-NMR (CDCl3, 81.015
MHz) l 8.4 (d, JP–P=22.2 Hz, JP–Pt=3674 Hz), 11.5
(d, JP–P=22.2 Hz, JP–Pt=3132 Hz); 1H-NMR (CDCl3,
1
300 MHz) l 2.7 (2H, br, OCH
4.9 (2H, br, NH
2), 7.2–7.6 (30H, phenyl H); 13C-NMR
(CDCl3, 50.32 MHz) l 50.4 (OCH2), 73.1 (NCH2),
6 2), 3.99 (2H, tt, NCH6 2),
6
6
6
128–133 (phenyl C).
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Organometallics 15 (1996) 3480.
4.3. X-ray crystallographic analysis
Diffraction data were measured at 300 K on a Non-
ius CAD-4 diffractometer with graphite-monochroma-
tized Mo–Kh radiation. Cell parameters were
determined by a least-squares fit on 25 reflections.
Intensity data were corrected for absorption on the
basis of an experimental „ rotation curve. The refine-
ment procedure was by a full-matrix least-squares
method, including all the non-hydrogen atoms an-
isotropically. Hydrogen atoms were fixed at the ideal
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6432; ibid. 103 (1981) 5972; ibid. 105 (1983) 2315. (b) B.M.
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Pure Appl. Chem. 60 (1988) 1615. (d) B.M. Trost, S.A. King, J.
Schmidt, J. Am. Chem. Soc. 111 (1989) 5902. (e) B.M. Trost,
S.A. King, J. Am. Chem. Soc. 112 (1990) 408. (f) B.M. Trost,
C.H. Marrs, J. Am. Chem. Soc. 115 (1993) 6636.
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Chem. Soc., Chem. Commun. (1986) 427. (b) B.M. Trost, S.
Schneider, J. Am. Chem. Soc. 111 (1989) 4430. (c) B.M. Trost,
C.H. Marrs, J. Am. Chem. Soc. 115 (1993) 6636. (d) A. Ohsuka,
T. Fujimori, T. Hirao, H. Kurosawa, I. Ikeda, J. Chem. Soc.,
Chem. Commun. (1993) 1039. (e) M.W. Baize, P.W. Blosser, V.
Plantevin, D.G. Schimpff, J.C. Gallucci, A. Wojcicki,
Organometallics 15 (1996) 164. (f) I. Ikeda, A. Ohsuka, K. Tani,
T. Hirao, H. Kurosawa, J. Org. Chem. 61 (1996) 4971.
[7] (a) J.-T. Chen, T.-M. Huang, M.-C. Cheng, Y.-C. Lin, Y. Wang,
Organometallics 11 (1992) 1761. (b) F.-Y. Tsai, H.-W. Chen,
J.-T. Chen, G.-H. Lee, Y. Wang, Organometallics 16 (1997) 822.
[8] R.-H. Hsu, J.-T. Chen, G.-H. Lee, Y. Wang, Organometallics 16
(1997) 3667.
˚
geometry and the C–H distance of 1.0 A; their isotopic
thermal parameters were fixed to the values of the
attached carbon atoms at the convergence of the
isotropic refinement. Atomic scattering factors were
taken from Ref. [15]. Computing programs are from
the NRCC SDP VAX package [16]. Crystallographic
data of 3a%, 3d, 3g%, 3h, 3i, 3j, 4m, 7d, 7g, 7i, 8i, 15, and
16 are listed in Table 4. The selected bond parameters
of 3a, 4m, and 15 are listed in Table 5. Other detailed
data are supplied in Section 5.
5. Supplementary material
Fully labeled ORTEP drawing and tables giving
complete crystal data, complete bond lengths and an-
gles, atomic coordinates, and thermal parameters for
3a%, 3d, 3g%, 3h, 3i%, 3j, 4m, 7d, 7g, 7i, 8i, 15, and 16 (115
pages). Ordering information is given on any current
masthead page.
[9] (a) M.W. Baize, V. Plantevin, J.C. Gallucci, A. Wojcicki, Inorg.
Chim. Acta 235 (1995) 1. (b) K. Ohe, H. Matsuda, T. Morimoto,
S. Ogoshi, N. Chatani, S. Murai, J. Am. Chem. Soc. 116 (1994)
4125.
[10] J.-T. Chen, Y.-K. Chen, J.-B. Chu, G.-H. Lee, Y. Wang,
Organometallics 16 (1997) 1476.
[11] (a) A.L. Casalnuovo, J.C. Calabrese, D. Milstein, J. Am. Chem.
Soc. 110 (1988) 6738. (b) L.A. Villanueva, K.A. Abbound, J.M.
Boncella, Organometallics 11 (1992) 2963. (c) R.L. Cowan, W.C.
Trogler, Organometallics 6 (1987) 2451.
Acknowledgements
[12] F.-Y. Tsai, T.-M. Huang, J.-T. Chen, G.-H. Lee, Y. Wang, J.
Organomet. Chem. 520 (1996) 85.
[13] (a) P.W. Jolly, R. Mynott, Adv. Organomet. Chem., 19 (1981)
257. (b) R. Benn, A. Rufinska, Organometallics 4 (1985) 209.
[14] J. Sieler, J. Kaiser, D. Walther, L. Golic, J. Siftar, J. Organomet.
Chem. 224 (1982) 313.
We gratefully thank the National Science Council,
Taipei, Taiwan, Republic of China, for financial
support.
References
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Press, Birmingham, UK, 1974.
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White, J. Appl. Cryst. 22 (1989) 384.
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