η1-Alkynylplatinum(II) complexes with cycloocta-1,5-diene and tri(1-cyclohepta-2,4,6-trienyl)phosphane ligands

Article abstract of DOI:10.1016/S0022-328X(01)01294-3

η¹-Alkynylplatinum(II) complexes of the type (cod)Pt(CCR)₂ (1, cod=η⁴-cycloocta-1,5-diene; R=Me (a), ^tBu (b), Ph (c), Fc (d), SiMe₃ (e)) were prepared in good yields from the reaction of (cod)PtCl

Full text of DOI:10.1016/S0022-328X(01)01294-3

Journal of Organometallic Chemistry 641 (2002) 173–184
www.elsevier.com/locate/jorganchem
h1-Alkynylplatinum(II) complexes with cycloocta-1,5-diene and
tri(1-cyclohepta-2,4,6-trienyl)phosphane ligands
Max Herberhold *, Thomas Schmalz, Wolfgang Milius, Bernd Wrackmeyer *
Laboratorium fu¨r Anorganische Chemie, Uni6ersita¨t Bayreuth, D-95440 Bayreuth, Germany
Received 3 August 2001; accepted 19 September 2001
Dedicated to Professor Rolf Gleiter on the occasion of his 65th birthday
Abstract
h1-Alkynylplatinum(II) complexes of the type (cod)Pt(CꢀCꢁR)2 (1, cod=h4-cycloocta-1,5-diene; R=Me (a), tBu (b), Ph (c), Fc
(d), SiMe3 (e)) were prepared in good yields from the reaction of (cod)PtCl2 with either HCꢀCꢁR and NaOEt (R=tBu, Ph, Fc)
or di(1-alkynyl)dimethyltin, Me2Sn(CꢀCꢁR)2 (R=Me, SiMe3). The analogous reaction of [P]PtCl2 ([P]=tri(1-cyclohepta-2,4,6-
t
trienyl)phosphane, {P(C7H7)2(h2-C7H7)}) with Me2Sn(CꢀCꢁR)2 (R=Me, Bu, Ph, Fc, SiMe3), afforded selectively the complexes
[P]PtCl(CꢀCꢁR) 2a–e in high yield, in which the 1-alkynyl group is in cis position with respect to the phosphorus atom, and one
of the C7H7 rings is h2-coordinated to platinum through the central CꢂC bond. Complexes 3a–e of the type [P]Pt(CꢀCꢁR)2 could
not be prepared by the reaction of 2 with an excess of the 1-alkynyltin reagents. However, the reaction of 1 with the phosphane
P(C7H7)3 gave compounds 3a–e in quantitative yield by substitution of the cod ligand. The molecular structures of 2b and 3d were
determined by X-ray structure analysis, and complexes 1–3 were characterised in solution by multinuclear magnetic resonance
spectroscopy (1H-, 13C-, 29Si-, 31P-, 195Pt-NMR). The structures of 2 and 3 in solution were found to be fluxional with respect to
coordination of the C7H7 rings to platinum. © 2002 Elsevier Science B.V. All rights reserved.
Keywords: Platinum; Tin; Alkynes; Cycloocta-1,5-diene; Phosphanes; NMR; X-ray
[(PR3)2Pt(CꢀCꢁR)2] [1–3]. In the latter cases, the use of
chelating diphosphanes such as dppe [4], dppm [5] or
dmpe and depe helps to increase the stability (dppe=
Ph2PCH2CH2PPh2; dppm=Ph2PCH2PPh2; dmpe=
Me2PCH2CH2PMe2; depe=Et2PCH2CH2PEt2). A few
complexes of the type (cod)Pt(CꢀCꢁR)2 have been de-
scribed which, however, have not been fully character-
ised in solution by NMR spectroscopy [6,7]. With
respect to the reactivity of the PtꢁCꢀ and the CꢀC
bonds, all these complexes are attractive starting mate-
rials for further syntheses, as has been shown in various
research areas (cf. Refs. [2,8–11]). However, little is
known about such platinum(II) complexes, in which
one or both phosphane donor functions are replaced by
h2 bonded alkene ligands. The phosphane [P] [12] offers
unique potential as a chelating ligand since it can use
CꢂC bonds for p complexation in addition to the
metal–phosphorus bond [13]. Considering the already
existing large NMR data set of h1-alkynylplatinum
complexes [3–5,14], the new complexes should also be
1. Introduction
Metal complexes containing different p-systems in
the coordination sphere are of particular interest with
respect to intramolecular ligand–ligand interactions.
We have studied platinum(II) compounds in which the
p-coordinated (h2) olefinic double bond of a cyclic
chelate ligand — such as cycloocta-1,5-diene, C8H12
(cod) in 1 or tri(1-cyclohepta-2,4,6-trienyl)phosphane,
P(C7H7)3 [P] in 2 and 3 — is connected through the
metal with s-coordinated (h1) 1-alkynyl ligands in ei-
ther cis- or trans-position.
Complexes of platinum(II) in which 1-alkynyl groups
are h1-linked to platinum are known mainly as anionic
species, [Pt(CꢀCꢁR)4]2−, or as bis(phosphane) com-
plexes of the type trans-[(PR3)2Pt(CꢀCꢁR)2] and cis-
* Corresponding authors. Fax: +49-921-552-157.
E-mail addresses: max.herberhold@uni-bayreuth.de (M. Herber-
hold), b.wrack@uni-bayreuth.de (B. Wrackmeyer).
0022-328X/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)01294-3

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M. Herberhold et al. / Journal of Organometallic Chemistry 641 (2002) 173–184
of interest from the NMR point of view. So far little
direct structural information is available on h1-
alkynylplatinum complexes [3b,15–17]. In the present
work, we have therefore determined the crystal struc-
tures of 2b and 3d by X-ray analysis.
2. Results and discussion
2.1. Synthesis of the cyclooctadiene complexes
(cod)Pt(CꢀCꢁR)2 (1a–e)
Scheme 1.
In principle, complexes of the type 1 can be prepared
from (cod)PtCl2 and the respective lithium alkynide,
which is formed from the corresponding alkyne and
nBuLi. However, the procedures shown in Scheme 1 are
more convenient and give the desired compounds 1 in
essentially quantitative yield, and the complexes 1 can
be used without further purification. Separation from
dimethyltin dichloride is easily achieved by precipita-
tion of 1 from the reaction mixture; repeated washing
with hexane and drying under high vacuum leads to
pure products 1a and 1e. The complexes 1 are colour-
less (1a, b, e), yellow (1c) or orange solids (1d) which
can be stored indefinitely under an inert atmosphere.
Scheme 2.
2.2. Synthesis of the phosphane complexes
[P]PtCl(CꢀCꢁR) (2a–e) and [P]Pt(CꢀCꢁR)2 (3a–e)
The reaction of the platinum dichloride [P]PtCl2 with
Me2Sn(CꢀCꢁR)2 in a molar ratio of 2:1 provides a
surprisingly clean method to obtain selectively the
monochloro complexes 2 (Scheme 2), after separation
from dimethyltin dichloride in the same way as de-
scribed in Section 2.1. This is remarkable, since the
analogous reactions of, e.g. (dppe)PtCl2 [4] or
(dppm)PtCl2 [5] afford exclusively the di(1-alkynyl)
compounds corresponding to 3, and attempts to pre-
pare the platinum chlorides analogous to 2 have not
been successful. Unexpectedly, the complexes 2 do not
react with an excess of the 1-alkynyltin compound to
give 3. The compounds 2 are yellow (2a–c and e) or
orange (2d) solids, of which 2b could be crystallised to
give single crystals suitable for X-ray structural analysis
(vide infra).
Scheme 3.
ing materials. The reactions of 1 with the phosphane
P(C7H7)3 lead quantitatively to 3 by replacement of the
cod ligand (Scheme 3). Again the complexes 3 are
yellow (3a–c and e) or orange (3d) solids, and single
crystals were obtained in the case of 3d, for which an
X-ray structural analysis was carried out (vide infra).
All compounds 2a–e and 3a–e are stable under an inert
atmosphere and can be stored for extended periods
without decomposition.
The complexes 2 and 3 are fluxional with respect to
the bonding of the cyclohepta-2,4,6-trienyl rings to
platinum [18,19]. The dynamic processes involved can-
not be simply dissociative reducing the coordination
For the preparation of the di(1-alkynyl)platinum(II)
complexes 3, the cod compounds 1 are excellent start-

M. Herberhold et al. / Journal of Organometallic Chemistry 641 (2002) 173–184
175
Scheme 4.
Table 1
195Pt-, 13C- and 29Si-NMR data a of the (cod)platinum(II)di(1-alkynyl) complexes 1a–e
l
195Pt 13C (PtꢁCꢀ) 13C (ꢀCꢁ) 13C (R)
l
l
l
l
13C (cod)
1a
1b
1c
1d
1e
614.6
605.6
592.1
602.3
610.1
82.2 [1413.8]
80.7 [1410.7]
92.7 [1412.0]
90.7 [1352.0]
112.1 [1350.1]
103.0 [371.1]
117.3 [367.0]
103.5 [362.3]
105.0 [374.7]
112.6 [316.0]
6.8 [25.4]
102.7, 30.2 [80.8]
102.5, 30.2 [79.8]
104.2, 30.4 [79.5]
103.5, 29.5 [79.8]
104.2, 30.2 [75.2]
32.1 b
130.9 (i) c [36.6]
69.4 (C-1(Fc)) d [30.9]
0.9 e
a Solutions in CD2Cl2 (saturated; at 23 °C); coupling constants J(195Pt,13C) are given in brackets (91 Hz).
b Overlapping signals.
c Other l13C: 131.8 (o), 127.8 (m), 126.5 (p).
d Other l13C: 67.7, 71.2 (C-3,4(Fc), C-2,5(Fc)), 71.2 (Cp).
e 1J(29Si,13C)=55.5 Hz; l29Si=-21.6; 3J(195Pt,29Si)=30.4 Hz; 1J(29Si,13Cꢀ)=83.9 Hz; 2J(29Si,ꢀ13C)=13.4 Hz; 1D 12/13C(21Si)=−3(Me),
−15(Cꢀ) ppb.
number of platinum, since this would lead to a three-
coordinate intermediate, in which cis/trans scrambling
of the ligands is expected to take place. However, the
coupling constants 2J(31P, ꢀ13C) do not change their
values with temperature in the case of 2, and the
alkynyl groups remain different in 3 when the exchange
of the C7H7 rings in coordination to platinum is fast
with respect to the NMR time scale. This indicates that
the C7H7 exchange probably passes through a transi-
tion state, in which a leaving C7H7 group is immedi-
ately replaced by the incoming next one. Since this
process blocks coordination sites at the platinum cen-
tre, it could explain why the replacement of the remain-
ing chloro ligand in 2 by an alkynyl ligand cannot be
achieved using the alkynyltin compound as a transfer
reagent. It has been proved definitely in the case of
palladium that the PdꢁCl/alkynyltin exchange proceeds
via oxidative addition and reductive elimination [3b,20],
and the same mechanism (see Scheme 4) is likely to
account for PtꢁCl/alkynyltin exchange. Thus, it appears
that the first step leading from [P]PtCl2 to 2 is possible,
whereas the second step, which would lead to 3, is no
longer favourable.
195Pt-NMR spectra can be conveniently recorded at
moderate field strengths B0 (e.g. 5.87 T, corresponding
to the 1H-NMR frequency of 250 MHz). At higher field
strengths B0, the 195Pt-NMR signals broaden signifi-
cantly as a result of increasingly efficient (dependent on
B20) chemical shift anisotropy induced nuclear spin re-
laxation [21]. This becomes evident not only for the
195Pt-NMR signals but also for the 195Pt satellites in the
13C- (Fig. 1), 31P- or 29Si-NMR spectra (Fig. 2). The
l195Pt data for each class of compounds are spread
over a narrow range (1: 23 ppm; 2: 11 ppm; 3: 14 ppm),
and conclusions beyond the identification of the type of
complex cannot be reached, considering the huge range
of l195Pt-NMR data in general [22]. On the other hand,
these narrow ranges of l195Pt data indicate that the
influence of the various groups R in the CꢀCꢁR ligands
is either small (more likely) or that shielding or
deshielding effects on the 195Pt nuclei compensate each
other (less likely in these cases). On going from 2 to 3
the 195Pt nuclear shielding increases by :10595 ppm,
due to the presence of a second alkynyl group instead
of a chloro ligand.
The l31P data of the compounds 2 and 3 also cover
a small range for each type of compound (only :2
ppm) which again points towards rather small effects
exerted by the different groups R on the electronic
structure in the vicinity of the platinum or phosphorus
atom. The 31P nuclear shielding decreases by :1091
ppm on going from 2 to 3. Small changes due to
different groups R in 2 and 3 are also confirmed by the
small range of the respective coupling constants
2.3. NMR spectroscopic results
13C-, 29Si- and 195Pt-NMR data of the complexes 1
are given in Table 1, whereas Tables 2 and 3 contain
13C-, 29Si-, 31P- and 195Pt-NMR data of the complexes 2
and 3, respectively.

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M. Herberhold et al. / Journal of Organometallic Chemistry 641 (2002) 173–184
1J(195Pt,31P) of 2 (3915–3979 Hz) and 3 (2523–2578
Hz). The marked decrease in the magnitude of
1J(195Pt,31P) values on going from 2 to 3 (:1396930
Hz; i.e. 35%) indicates the stronger polarising ability of
the chloro ligand in 2 as compared to the second
alkynyl group in 3.
A typical 13C-NMR spectrum is shown in Fig. 1. The
l13C(alkyne) values of 1 and 2 are similar (slight shift
Table 2
195Pt-, 31P-, and 13C-NMR data a of the [P]Pt(chloro)1-alkynyl complexes 2a–d
No
l
195Pt
l
31P
l
13C(PtꢁCꢀ)
l
13C(ꢀCꢁ)
l
13C(R)
l
13C(Ptꢁ(CꢂC))
l
13C(C-1%)
l
13C (C-1)
2a 70.2 {3966}
2b 59.4 {3979}
2c 67.2 {3915}
2d 64.9 {3945}
2e 69.4 {3943}
92.0 {3966}
91.2 {3979}
93.6 {3915}
92.7 {3945}
91.6 {3943}
77.8 [1525.9]
(17.2)
78.2 [1594.8]
(17.0)
92.2 [1515.1]
(16.9)
88.6 [1524.7]
(17.3)
105.4 [416.6]
(B2)
117.9 [396.9]
(B2)
108.8 [409.3]
(B2)
106.5 [412.3]
(B2)
5.7 [27.0]
95.7 [60.1] (B2) 34.4 b (25.9)
95.9 [58.7] (B2) 33.6 d (26.0)
96.9 [58.4] (B2) 33.7 g (28.6)
34.1 c [55.3]
(43.1)
28.9 (C), 31.3
(Me)
34.0 e [56.3]
(43.4)
125.3 (i) f
34.2 h [56.0]
(42.8)
67.7 i (C-1(Fc)) 95.8 [61.8] (B2) 33.8 j (27.1)
34.1 k [54.4]
(39.2)
109.8 [1419.6]
(15.8)
114.2 [350.6]
(B2)
0.0 l
98.0 [51.5] (B2) 34.1 m (29.3) 34.0 n [58.1]
(42.8)
1
a Solutions in CD2Cl2 (saturated; at −20 °C); coupling constants J(31P,13C) are given in parentheses, J(195Pt,13C) in brackets, and J(195Pt,31P)
in braces.
b Coordinated ring; other l13C: 127.7 [51.4] (C-2%,7%), 130.0 (9.7) (C-3%,6%).
c Non-coordinated rings; other l13C: 112.6, 113.0 (C-2,7), 126.6 (11.5), 126.9 (11.5) (C-3,6), 130.4, 130.5 (C-4,5).
d Coordinated ring; other l13C: 127.6 [53.2] (C-2%,7%), 130.4 (10.4) (C-3%,6%).
e Non-coordinated rings; other l13C: 111.9, 112.8 (C-2,7), 126.5 (12.1), 126.8 (11.3) (C-3,6), 130.5, 130.7 (C-4,5).
f Other l13C: 130.5 (o), 128.0 (m), 126.5 (p).
g Coordinated ring; other l13C: 127.9 [54.1] (C-2%,7%), 130.1 (9.2).
h Non-coordinated rings; other l13C: 113.4, 113.6 (C-2,7), 126.6 (11.8), 126.8 (11.8) (C-3,6), 130.6, 130.8 (C-4,5).
i Other l13C: 67.9, 70.6 (C-2,5(Fc), C-3,4(Fc)), 69.3 (Cp).
j Coordinated ring; other l13C: 127.7 [52.7] (C-2%,7%), 130.0 (9.5) (C-3%,6%).
k Non-coordinated rings; other l13C: 113.8, 113.9 (C-2,7), 126.3 (11.7), 126.5 (11.7) (C-3,6), 130.6, 130.7 (C-4,5).
l 1J(29Si,13C)=55.9 Hz; l29Si=−21.9; 3J(195Pt,29Si)=33.1 Hz; 4J(31P,29Si)=0.6 Hz.
m Coordinated ring; other l13C: 128.0 [50.4] (C-2%,7%), 130.2 (9.4) (C-3%,6%).
n Non-coordinated rings; other l13C: 112.4, 112.7 (C-2,7), 126.6 (11.8), 126.7 (11.2) (C3,6), 130.5, 130.7 (C-4,5).
Fig. 1. 13C-NMR (62.8 MHz) spectrum of 2c (saturated solution in CD2Cl2, measured at −2091 °C to slow down the dynamic process
involving the ligand [P]). The expansion shows the region of the alkynyl 13C resonances, for which the 195Pt satellites (marked by asterisks)
corresponding to the coupling constants nJ(195Pt,13C) are clearly visible.

Table 3
195Pt-, 31P-, and 13C-NMR data a of the [P]Pt(1-alkynyl)2 complexes 3a–d
No
l
195Pt
l
31P
l
13C(PtꢁCꢀ)
l
13C(ꢀCꢁ)
l
13C(R)
l
13C(Ptꢁ(CꢂC))
l
13C(C-1%)
l
13C (C-1)
3a −28.7 {2560}
3b −39.7 {2554}
101.7 {2560}
101.2 {2554}
n.m.
n.m.
n.m.
n.m.
90.1 [59.4]
n.m.
n.m.
78.6 b [1525.7] (15.9); 95.9 c
[1126.7] (163.1)
121.0 b [416.1] (B2); 112.9 c
[284.9] (32.6)
28.5, 28.9 (C), 31.9,
31.2 (Me)
34.0 d (21.6)
(B2)
32.8 e [34.5]
(36.7)
/
3c −38.9 {2578}
3d −40.6 {2576}
3e −26.5 {2523}
103.2 {2578}
102.2 {2576}
101.6 {2523}
90.1 b [1538.1] (15.8); 112.5 c
[1129.0] (159.5)
112.6 b [428.3] (B2); 104.7 c
[293.0] (33.0)
126.0 126.3 (i) f
91.7 [56.9] (B2) 34.5 g (19.5)
90.3 [58.9] (B2) 34.7 j (22.0)
93.1 [53.1] (B2) 34.6 m (21.5)
33.5 h [38.5]
(36.7)
87.6 b [1537.7] (15.9); 108.9 c
[1135.0] (161.7)
110.3 b [434.4] (B2); 100.7 c
[297.7] (33.9)
66.0, 68.9 (C-1(Fc)) i
33.5 k [36.6]
(36.3)
108.3 b [1444.2] (14.7); 133.5 c
[1072.2] (146.7)
117.0 b [365.7] (B2); 108.2 c
[264.4] (26.7)
−0.3, 0.5 l
33.1 n [35.2]
(36.4)
a Solutions in CD2Cl2 (saturated; at −40 °C); coupling constants J(31P,13C) are given in parentheses, J(195Pt,13C) in brackets, and 1J(195Pt,31P) in braces; n.m. means not measured.
b Alkynyl group CꢀCꢁR cis to phosphorus atom.
c Alkynyl group CꢀCꢁR trans to phosphorus atom.
d Coordinated ring; other l13C: 128.4 [45.0] (C-2%,7%), 130.4 (10.1) (C-3%,6%).
e Non-coordinated rings; other l13C: 111.4, 112.0 (C-2,7), 125.8 (11.1), 126.1 (10.2) C(3,6), 130.0, 130.2 (C-4,5).
f Other l13C: 131.1, 131.2 (o), 127.8, 128.0 (m), 126.5, 126.6 (p).
g Coordinated ring; other l13C: 129.1 [45.9] (C-2%,7%), 130.4 (9.0) (C-3%,6%).
641
h Non-coordinated rings; other l13C: 112.9, 113.1 (C-2,7), 125.9 (10.9), 126.2 (10.8) (C-3,6), 130.3, 130.4 (C-4,5).
i Other l13C: 67.4, 67.7, 70.8, 71.0 (C-2,5(Fc), C-3,4(Fc)), 69.6, 70.0 (Cp).
(
j Coordinated ring; other l13C: 128.8 [46.7] (C-2%,7%), 130.5 (9.3) (C-3%,6%).
k Non-coordinated rings; other l13C: 112.9, 113.9 (C-2,7), 126.2 (10.8), 126.6 (10.0) (C-3,6), 130.3, 130.4 (C-4,5).
l In cis position with respect to the phosphorus atom: l29Si=−21.6; 3J(195Pt,29Si)=36.4 Hz; 4J(31P,29Si)=1.4 Hz; in trans position with respect to the phosphorus atom: l29Si=−23.1;
3J(195Pt,29Si)=23.9 Hz; 4J(31P,29Si)=3.5 Hz.
173
184
m Coordinated ring; other l13C: 129.1 [44.2] (C-2%,7%), 130.6 (9.7) (C-3%,6%).
n Non-coordinated rings; other l13C: 112.2, 112.3 (C-2,7), 126.1 (9.2), 126.3 (8.9) (C-3,6), 130.2, 130.3 (C-4,5).

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M. Herberhold et al. / Journal of Organometallic Chemistry 641 (2002) 173–184
from those in cis position, as becomes apparent from
the data in Tables 2 and 3. The 13C(PtꢁCꢀtrans) reso-
nances move to much higher frequencies, and the
13C(ꢀCtrans) resonances are shifted significantly to lower
frequencies. The magnitude of the coupling constants
1J(195Pt,13Cꢀtrans) of 3 is reduced by :25% with respect
to that of 1J(195Pt,13Cꢀcis), which also indicates the
different effects exerted by the phosphane and the CꢂC
bond in trans positions to the alkynyl group. The
influence of the phosphane ligand on the 13C-NMR
parameters observed here corresponds closely to the
effects measured previously for (dppe)Pt(CꢀCꢁR)2,
(dppm)Pt(CꢀCꢁR)2 and (depe)Pt(CꢀCꢁR)2 [4,5,14a]. A
more detailed discussion of the 13C-NMR parameters in
context with other data for organometallic-substituted
alkynes (see Ref. [23] for a collection of data) will be
presented elsewhere [24].
Fig. 2. 29Si-NMR (99.6 MHz) spectrum of 1e (saturated solution in
CD2Cl2, at 2391 °C), recorded by the refocused INEPT pulse
sequence with 1H decoupling [24]. 195Pt (open circles) and 13C satel-
lites (arrows and asterisks) are indicated. The broadening of the 195Pt
satellite signals results from fast 195Pt nuclear spin relaxation owing
to the chemical shift anisotropy mechanism.
29Si-NMR spectra of alkynyl(methyl)silanes can be
recorded most efficiently [25] by applying the refocused
INEPT pulse sequences with 1H decoupling [26], as
shown in Fig. 2 for the determination of all coupling
constants J(29Si,13C) in 1e. Changes in the electronic
structure of the CꢀCꢁSiMe3 group are indicated by the
shift of the 29Si-NMR signals of 1e–3e to lower fre-
quencies (:3.5 ppm for the CꢀCꢁSiMe3 groups in cis
and :5 ppm for CꢀCꢁSiMe3 in trans position with
respect to the phosphorus atom) relative to
alkynyl(trimethyl)silanes without PtꢁCꢀbonds. The
3
trend in the changes of the magnitude of J(195Pt,29Sicis/
trans) follows the 195Pt–13C couplings: in 3e the trans
position of the CꢀCꢁSiMe3 with respect to phosphorus
causes a decrease in the magnitude of 3J(195Pt,29Si)
(23.9 Hz) of 34% when compared with the value 36.4
Hz for the CꢀCꢁSiMe3 group in trans position to the
1
CꢂC bond. The magnitude of J(29Si,13Cꢀ) in 1e (83.9
Hz) has increased slightly with respect to
Me3SiꢁCꢀCꢁMe (80.9 Hz [26]) and markedly with re-
spect to Me3SiꢁCꢀCꢁSiMe3 (76.5 Hz [24]), whereas the
Fig. 3. Molecular structure of [P(C7H7)2(h2-C7H7)]PtCl(CꢀCꢁtBu)
(2b) cf. Table 4.
2
magnitude of J(29Si,ꢀ13C) in 1e (13.4 Hz) is smaller
than that in Me3SiꢁCꢀCꢁMe (15.6 Hz [26]) and similar
to that in Me3SiꢁCꢀCꢁSiMe3 (12.6 Hz [23]). For a
meaningful discussion of these parameters and of iso-
tope-induced chemical shifts D12/13 (29Si) [26,27], there
are still not enough data of this type available.
to lower frequencies of the 13C(PtꢁCꢀ) and to higher
frequencies of the 13C(ꢀC) resonances in 2), in agree-
ment with the expectation that the nature of the ligand
in trans position will determine major changes. In both
1 and 2, an h2 CꢂC bond is coordinated to Pt in trans
position to the alkynyl groups. The magnitude of
2J(31P,ꢀ13C) in 2 is small, which confirms the cis posi-
tion of the alkynyl group with respect to the phospho-
2.4. X-ray structure determinations of 2b and 3d
The molecular structures of two characteristic exam-
ples, [P]PtCl(CꢀCꢁtBu) (2b) and [P]Pt(CꢀCꢁFc)2 (3d),
were determined by X-ray structure analysis (Figs. 3
and 4). Selected bond lengths and angles are collected
in Tables 4 and 5. Both 2b and 3d are square-planar 16e
complexes which contain a chelating P(C7H7)2(h2-
C7H7) ligand, coordinated through both the phospho-
rus atom and the central double bond of one
cyclohepta-2,4,6-trienyl substituent. In the crystal lat-
1
rus atom. In the cases of J(195Pt,13Cꢀ), the magnitude
in general is somewhat smaller in 1 than in 2, although
1
there is no agreement in the trends of J(195Pt,13Cꢀ) as
a function of R, except that the smallest value is always
observed for R=SiMe3 (this also holds for the alkynyl
groups in cis position to phosphorus in the complexes
3). The 13C-NMR parameters of the alkynyl groups in
trans position to phosphorus are significantly different

M. Herberhold et al. / Journal of Organometallic Chemistry 641 (2002) 173–184
179
tice the two pending C7H7 ligands have no connection
with the Pt(II) atom to which the P(C7H7)3 ligand is
attached, in contrast to the situation in solution. The
CꢂC bond axis of the h2-coordinated double bond is
arranged perpendicular to the coordination plane; the
angle of the C(4)ꢁC(5) vector relative to the best (coor-
dination) plane is 88.6° in 2b and 88.4° in 3d. As
expected, the bond length of this CꢂC bond (138.0(10)
in 2b and 140.3(10) in 3d) is found between those of
typical single (154 pm) and typical double (134 pm)
bonds (Tables 4 and 5); it compares well with the bond
distance of the h2-coordinated CꢂC double bonds in
(cod)PtCl2 (137.5(8) and 138.7(8) pm [28]) or
(cod)PtBr(C6H2Me3-2,4,6) (142(3) trans to the bromo
and 134(3) pm trans to the mesityl ligand [29]).
The PtꢁC distance trans to the coordinated double
bond (i.e. cis to the phosphorus atom) in both 2b
(196.2(6) pm) and 3d (195.0(8) pm) is observed in the
normal range of 193–198 pm, expected for such com-
pounds [15–17] (cf. (bipy)Pt(CꢀCꢁPh)2 195.9(5) and
196.2(4) pm [17b]). In the di(ferrocenylethynyl)platinum
complex 3d, the PtꢁC bond length trans to phosphorus
is significantly enlarged to 202.4(7) pm (vs. 195.0(8) pm
cis to P), indicating a stronger trans-influence [30] of
the phosphorus atom which is only slightly compen-
sated by a shorter CꢀC bond length (118.6(9) pm vs.
120.8(10) pm). This may be compared with the struc-
tures
of
the
cis
and
trans
isomers
of
(Ph3P)2Pt(CꢀCꢁtBu)(h1-C(Me)ꢂCH2) [16b], where the
PtꢁC(alkinyl) bond is longer if the h1-alkenyl group
stands trans to the tert-butylethynyl ligand (204(1) pm)
than in the cis arrangement (197(2) pm), indicating the
stronger trans-influence of the h1-alkenyl group. The
strong trans-influence of organyl ligands may also be
deduced from (cod)PtBr(1-mesityl) where the olefinic
bond trans to mesityl is pushed back (PtꢁC 228(2) and
231(2) pm) as compared with that trans to Br (PtꢁC
213(2) pm) [29].
The PtꢁP bond length (220.89(14) pm in 2b and
227.21(18) pm in 3d) is comparatively short (cf. various
1-alkynylplatinum complexes [15–17]), although it still
reflects the higher trans-influence [30] of the 1-alkynyl
as compared to the chloro ligand. In the case of 3d, the
short PtꢁP bond appears to be accompanied by an
elongated PtꢁC(alkinyl) bond (202.4(7) pm) in the trans
position. Different PtꢁP bond lengths have also been
observed in cis-[(Ph3P)2Pt(h1-CꢀCtBu)(h1-C(Me)ꢂCH2)]
(228.6(4) pm trans to tert-butylethynyl, 234.0(4) pm
trans to methylvinyl), whereas the PtꢁP bond distances
are equal (229.3(3) and 229.6(3) pm) in the trans-isomer
[16b]).
Fig. 4. Molecular structure of [P(C7H7)2(h2-C7H7)]Pt(CꢀCꢁFc)2 (3d)
cf. Table 5.
Table 4
Selected bond lengths (pm) and bond angles (°) for [P]PtCl(CꢀCꢁtBu)
(2b)
Bond lengths
PtꢁP
PtꢁC(4)
PtꢁC(5)
220.89(14) PtꢁCl
236.78(15)
196.2(6)
120.3(9)
148.0(9)
185.6(7)
183.2(6)
182.2(6)
225.7(6)
226.2(6)
215.2
148.7(11)
134.2(11)
145.1(10)
138.0(10)
145.0(9)
131.4(11)
149.4(11)
PtꢁC(22)
C(22)ꢁC(23)
C(23)ꢁC(24)
PꢁC(1)
PtꢁZ(C4,5)
C(1)ꢁC(2)
C(2)ꢁC(3)
C(3)ꢁC(4)
C(4)ꢁC(5)
C(5)ꢁC(6)
C(6)ꢁC(7)
C(1)ꢁC(7)
PꢁC(8)
PꢁC(15)
Bond angles
C(4)ꢁPtꢁC(5)
PꢁPtꢁZ(C4,5)
PꢁPtꢁC(22)
35.6(2)
93.1
85.72(18) PtꢁPꢁC(1)
178.91(5) PtꢁPꢁC(8)
93.26(18) PtꢁPꢁC(15)
87.9
PtꢁC(22)ꢁC(23)
C(22)ꢁC(23)ꢁC(24) 178.2(7)
172.6(6)
107.9(2)
114.9(2)
115.3(2)
107.5(3)
102.6(3)
108.3(3)
PꢁPtꢁCl
C(22)ꢁPtꢁCl
ClꢁPtꢁZ(C4,5)
C(22)ꢁPtꢁZ(C4,5)
C(1)ꢁPꢁC(8)
C(8)ꢁPꢁC(15)
C(1)ꢁPꢁC(15)
The CꢀC alkynyl bond vectors deviate slightly from
the coordination plane (C(22)ꢁC(23) in 2b by 5.7°); in
the case of the di(ferrocenylethynyl)platinum complex
3d the angles of the vectors C(22)ꢁC(23) (6.2°) and
C(34)ꢁC(35) (6.8°) are similar, but the ferrocenyl-substi-
tuted CꢀC triple bonds protrude from the coordination
plane into different directions, being arranged either
above or below.
177.9
Dihedral angle
PPt(Z(C4,5)/C(22)
1.8
PtCl
Coordination plane
PtPZ(C4,5)C(22)Cl Z=1.2
Considering the large amount of structural data
which is available for ferrocene derivatives, it is inter-
Z(C4,5) is the centre of the coordinated double bond C(4)ꢁC(5). Z is
the average deviation from the best (coordination) plane (pm).

180
M. Herberhold et al. / Journal of Organometallic Chemistry 641 (2002) 173–184
Table 5
Selected bond lengths (pm) and bond angles (°) for [P]Pt(CꢀCꢁFc)2 (3d)
Bond lengths
PtꢁP
227.21(18)
226.5(8)
227.0(7)
215.6
PtꢁC(22)
195.0(8) (cis to P)
120.8(10)
142.8(10)
202.4(7) (trans to P)
118.6(9)
143.5(10)
PtꢁC(4)
PtꢁC(5)
PtꢁZ(C4,5)
C(22)ꢁC(23)
C(23)ꢁC(24)
PtꢁC(34)
C(34)ꢁC(35)
C(35)ꢁC(36)
C(1)ꢁC(2)
C(2)ꢁC(3)
C(3)ꢁC(4)
C(4)ꢁC(5)
C(5)ꢁC(6)
C(6)ꢁC(7)
C(1)ꢁC(7)
148.8(11)
134.8(11)
144.0(11)
140.3(10)
144.1(10)
132.4(11)
150.0(11)
PꢁC(1)
PꢁC(8)
PꢁC(15)
186.0(7)
184.4(8)
183.4(7)
Bond angles
C(4)ꢁPtꢁC(5)
PꢁPtꢁZ(C4,5)
PꢁPtꢁC(22)
36.0(3)
91.6
92.2(2)
177.4(2)
86.2(3)
175.2
PtꢁC(22)ꢁC(23)
C(22)ꢁC(23)ꢁC(24)
PtꢁC(34)ꢁC(35)
C(34)ꢁC(35)ꢁC(36)
PtꢁPꢁC(1)
PtꢁPꢁC(8)
PtꢁPꢁC(15)
C(1)ꢁPꢁC(8)
C(8)ꢁPꢁC(15)
C(1)ꢁPꢁC(15)
173.8(6) (cis to P)
178.2(7)
174.1(7) (trans to P)
178.9(8)
108.6(3)
118.4(2)
115.2(2)
105.0(4)
101.0(4)
107.8(4)
PꢁPtꢁC(34)
C(22)ꢁPtꢁC(34)
C(22)ꢁPtꢁZ(C4,5)
C(34)ꢁPtꢁZ(C4,5)
90.1
Dihedral angle
PPt(Z(C4,5)/C(22)PtC(34)
Coordination plane
PtPZ(C4,5)C(22)C(34)
3.7
Z=3.8
Z(C4,5) is the centre of the coordinated double bond C(4)ꢁC(5). Z is the average deviation from the best (coordination) plane (pm).
esting to note that the cyclopentadienyl rings of the
ferrocenyl substituents in [P]Pt(CꢀCꢁFc)2 (3d) are al-
most exactly eclipsed — the deviation of the confor-
mational angle ~ from the ideal eclipsed arrangement
(~=0°) is only 1.9° at Fe(1) and 2.9° at Fe(2).
be markedly influenced by the nature of the ligand in
trans-position. This could be demonstrated here for the
first time by NMR parameters for alkynyl groups in the
series of the complexes 1–3, in comparison with data
reported for corresponding bis(phosphane)platinum(II)
complexes [3–5].
3. Conclusions
4. Experimental
Complexes of platinum(II) bearing both p-bonded
h2-alkene ligands and s-bonded h1-alkynyl ligands are
readily available, stable, and easy to characterise by
multinuclear magnetic resonance in solution, and by
X-ray structural analysis in the solid state. The 1-
alkynyltin compounds are attractive alkynyl transfer
reagents, although any prediction about the product
distribution is speculative. In the present cases, the
highly selective transfer of only one alkynyl group is
particularly noteworthy, opening the access to the com-
plexes 2, in which the alkynyl group takes the place
solely in trans-position with respect to the h2-coordi-
nated CꢂC unit of the tri(1-cyclohepta-2,4,6-
4.1. General and starting materials
Preparation and handling of all compounds were
carried out in an atmosphere of dry Ar, and carefully
dried solvents were used throughout. Starting materials
were prepared according to literature procedures, e.g.
(cod)PtCl2 [31], [P]PtCl2 [32], Me2Sn(CꢀCꢁR)2 [33],
CpFe(C5H4ꢁCꢀCH) [34], or were used as commercial
products without further purification, e.g. MeꢁCꢀCH,
tBuꢁCꢀCH, PhꢁCꢀCH, Me3SiꢁCꢀCH and nBuLi (1.6 M
in hexane).
NMR spectroscopy: Bruker ARX 250 or DRX 500
(1H-, 13C-, 29Si-, 31P-, 195Pt-NMR); direct single pulse
measurements, or in the case of some 13C- and 29Si-
NMR spectra by using the refocused INEPT pulse
sequence with 1H decoupling [25], based on
trienyl)phosphane
ligand.
According
to
the
t
solution-state NMR parameters, the group R (Me, Bu,
Ph, Fc, SiMe3) in CꢀCꢁR have very little influence on
the electronic structure of all complexes 1–3, whereas
the electronic structure of the alkynyl groups appears to
2
nJ(13C,1H):3–5 Hz, and J(29Si,1H):7 Hz. Chemical

M. Herberhold et al. / Journal of Organometallic Chemistry 641 (2002) 173–184
181
shifts are given with respect to Me4Si [l1H
(CD(H)Cl2)=5.33; l13C (CD2Cl2)=50.3; l29Si=0 for
](29Si)=19.867184 MHz]; external aqueous H3PO4
(85%) with l31P=0 for ](31P)=40.480747 MHz, and
l195Pt=0 for ](195Pt)=21.400000 MHz. IR spectra:
Perkin–Elmer, Spectrum 2000 FTIR. EIMS: Finnigan
MAT 8500 (ionisation energy 70 eV).
4.2.2.1. (cod)Pt(CꢀCꢁtBu)2 (1b). Reaction time 2 h.
M.p. (dec.) 133 °C. Yield 224 mg (74%), C20H30Pt.
1H-NMR (CD2Cl2, 23 °C): l=1.17 (s, 18H, HtBu), 2.41
(m, 8H, HCH ), 5.40 (s, 4H, 2J(195Pt,1H)=45.4 Hz,
2
HCH). IR (CsI, cm−1): w(CꢀC) 2031. EIMS; m/e (%):
465 (100) [M+], 450 (8) [M+−Me], 408 (10) [M+−
tBu], 357 (12) [M+−cod], 342 (16) [M+−cod−Me],
303 (34) [(cod)Pt+].
4.2. General procedures for the synthesis of complexes
(cod)Pt(CꢀCꢁR)2 (1)
4.2.2.2. (cod)Pt(CꢀCꢁPh)2 (1c). Reaction time 1 h. M.p.
1
(dec.) 180 °C. Yield 299 mg (91%), C24H22Pt. H-NMR
(CD2Cl2, 23 °C): l=2.55 (m, 8H, HCH ), 5.68 (s, 4H,
2
4.2.1. R=Me, SiMe3 (1a and 1e)
2J(195Pt,1H)=43.9 Hz, HCH), 7.10–7.24 (m, 6H, Hp,m),
7.37 (m, 4H, H°). IR (CsI, cm−1): w(CꢀC) 2125. EIMS;
m/e (%): 505 (1) [M+], 397 (1) [M+−cod], 303 (1)
[(cod)Pt+], 204 (88) [PhC4Ph+], 78 (83) [C6H+6 ], 65 (99)
[C5H+5 ], 54 (100) [C4H+6 ].
Di(1-alkynyl)dimethyltin, Me2Sn(CꢀCꢁR)2 (R=Me,
SiMe3), (0.6 mmol) was added to a suspension of
(cod)PtCl2 (0.187 g; 0.5 mmol) in THF (20 ml). The
reaction mixture was stirred for 3 h at room tempera-
ture (r.t.), and became a clear brown solution. This
solution was concentrated under vacuum to 5 ml, be-
fore hexane (40 ml) was added. A pale brown precipi-
tate was formed which was separated and washed
several times with small portions of hexane. Recrystalli-
sation from CH2Cl2–hexane and drying under a high
vacuum gave colourless or pale yellow powders.
4.2.2.3. (cod)Pt(CꢀCꢁFc)2 (1d). Reaction time 1.5 h.
M.p. (dec.) 158 °C. Yield 380 mg (81%), C32H30Fe2Pt.
CH
1H-NMR (CD2Cl2, 23 °C): l=2.52 (m, 8H, H ),
2
4.05 (vt, 4H, H3,4(Fc)), 4.18 (s, 10H, HCp), 4.34 (vt, 4H,
2
H2,5(Fc)), 5.59 (s, 4H, J(195Pt,1H)=45.0 Hz, HCH). IR
(CsI, cm−1): w(CꢀC) 2139. EIMS; m/e (%): 488 (1)
[M+−C2Fc], 418 (22) [FcC4Fc+], 186 (8) [FcH+], 78
(100) [C6H+6 ].
4.2.1.1. (cod)Pt(CꢀCꢁMe)2 (1a). M.p. (dec.) 156 °C.
Yield 166 mg (87%), C14H18Pt. 1H-NMR (CD2Cl2,
4
23 °C): l=1.98 (s, 6H, J(195Pt,1H)=17.6 Hz, HMe),
4.3. General procedure for the synthesis of the
complexes [P]PtCl(CꢀCꢁR) (2)
2.42 (m, 8H, HCH ), 5.43 (s, 4H, J(195Pt,1H)=47.3 Hz,
HCH). IR (CsI, cm−1): w(CꢀC) 2052. EIMS; m/e (%):
381 (100) [M+], 366 (4) [M+−Me], 350 (8) [M+−
2Me], 303 (41) [(cod)Pt+], 272 (59) [M+−cod].
2
2
The complex {P(C7H7)2(h2-C7H7)}PtCl2 (114 mg;
0.20 mmol) was suspended in THF (15 ml), then
t
Me2Sn(CꢀCꢁR)2 (R=Me, Bu, Ph, Fc, SiMe3) (0.12
4.2.1.2. (cod)Pt(CꢀCꢁSiMe3)2 (1e). M.p. (dec.) 142 °C.
mmol) was added, and the mixture was heated under
reflux for 45 min. During this time a clear yellow
solution was formed. The volume of the solution was
reduced under vacuum to 3 ml, and hexane (50 ml) was
added. The precipitate was separated, recrystallised
from CH2Cl2–hexane, and dried in a high vacuum to
give the products as yellow (2a–c and e) or orange (2d)
powders.
1
Yield 206 mg (83%), C18H30PtSi2. H-NMR (CD2Cl2,
2
23 °C): l=0.09 (s, 18H, J(29Si,1H)=119.2 Hz, HMe),
2.46 (m, 8H, HCH ), 5.52 (s, 4H, J(195Pt,1H)=44.9 Hz,
HCH). IR (CsI, cm−1): w(CꢀC) 2061. EIMS; m/e (%):
497 (100) [M+], 482 (66) [M+−Me], 389 (13) [M+−
cod], 375 (30) [M+−cod−Me], 303 (20) [(cod)Pt+].
2
2
4.2.2. R=tBu, Ph, Fc (1b–1d)
The respective terminal alkyne, HCꢀCꢁR (R=tBu,
Ph, Fc) (1.30 mmol) was added to a freshly prepared
NaOEt solution (30 mg (1.30 mmol) Na and 5 ml
EtOH), and this mixture was stirred for 20 min at r.t.
Then it was cooled to 0 °C and slowly transferred to a
suspension of (cod)PtCl2 (243 mg; 0.65 mmol) in EtOH
(20 ml), and the reaction mixture was stirred several
hours at r.t. The solvent was removed in vacuo and the
residue extracted with CH2Cl2. The combined extracts
were reduced in vacuo to 3 ml, then 50 ml of hexane
was added. The precipitate was filtered off and washed
with small portions of hexane. Recrystallisation from
CH2Cl2–hexane and drying under a high vacuum gave
a white (1b), yellow (1c) or orange (1d) powder.
4.3.1. {P(C7H7)2(p2-C7H7)}PtCl(CꢀCꢁMe) (2a)
M.p. (dec.) 176 °C. Yield 97 mg (86%), C24H24ClPPt.
1H-NMR (CD2Cl2, −20 °C): l=1.83 (s, 3H,
4J(195Pt,1H)=18.2 Hz, HMe), 2.45 (dt, 2H,
3
2J(31P,1H)=10.0 Hz, J(1H,1H)=6.5 Hz, H1), 4.59 (dt,
1H, 2J(31P,1H)=11.7 Hz, 3J(1H,1H)=9.1 Hz, H1%),
5.20 (m, 2H, H2,7), 5.26 (m, 2H, H2,7), 5.70 (m, 2H,
2
H2%,7%), 5.92 (m, 2H, J(195Pt,1H)=37.5 Hz, H4%,5%), 6.29
(m, 4H, H3,6), 6.49 (m, 2H, H3%,6%), 6.61 (m, 4H, H4,5).
IR (CsI, cm−1): w(CꢀC) 2149. EIMS; m/e (%): 574 (1)
[M+], 537 (2) [P(C7H7)3Pt(CꢀCMe)+], 481 (1)
[P(C7H7)2Pt(CꢀCMe)Cl+],
446
(2)
[P(C7H7)2Pt-
(CꢀCMe)+], 304 (3) [P(C7H7)3+], 91 (100) [C7H+7 ], 78
(34) [C6H+6 ].

182
M. Herberhold et al. / Journal of Organometallic Chemistry 641 (2002) 173–184
4.3.2. {P(C7H7)2(p2-C7H7)}PtCl(CꢀCꢁtBu) (2b)
M.p. (dec.) 195 °C. Yield 97 mg (79%), C27H30ClPPt.
1H-NMR (CD2Cl2, −20 °C): l=1.01 (s, 9H, HtBu),
4.4. General procedure for the synthesis of the
complexes [P]Pt(CꢀCꢁR)2 (3)
2
3
2.41 (dt, 2H, J(31P,1H)=10.1 Hz, J(1H,1H)=6.5 Hz,
The phosphane P(C7H7)3 (65 mg; 0.21 mmol), dis-
solved in CH2Cl2 (10 ml), was added dropwise to a
solution of (cod)Pt(CꢀCꢁR)2 (1a–e) (0.20 mmol) in
CH2Cl2 (15 ml). The reaction mixture was stirred at r.t.
and then brought to dryness in a high vacuum. The
remaining solid was washed with hexane (50 ml). Re-
crystallisation from CH2Cl2–hexane and drying under
high vacuum gave yellow (3a–c and e) or orange (3d)
powders.
2
3
H1), 4.69 (dt, 1H, J(31P,1H)=12.0 Hz, J(1H,1H)=8.6
Hz, H1%), 5.18 (m, 2H, H2,7), 5.38 (m, 2H, H2,7), 5.73 (m,
2H, H2%,7%), 5.94 (m, 2H, J(195Pt,1H)=36.9 Hz, H4%,5%),
2
6.30 (m, 4H, H3,6), 6.51 (m, 2H, H3%,6%), 6.63 (m, 4H,
H4,5). IR (CsI, cm−1): w(CꢀC) 2127. EIMS; m/e (%):
616 (7) [M+], 579 (8) [P(C7H7)3Pt(CꢀCtBu)+], 534 (5)
[P(C7H7)3PtCl+], 525 (5) [P(C7H7)2Pt(CꢀCtBu)Cl+], 499
(5) [P(C7H7)3Pt+], 488 (10) [P(C7H7)2Pt(CꢀCtBu)+], 443
(3), [P(C7H7)2PtCl+], 408 (5) [P(C7H7)2Pt+], 317 (5)
[P(C7H7)Pt+], 304 (2) [P(C7H7)+3 ], 91 (100) [C7H+7 ].
4.4.1. {P(C7H7)2(p2-C7H7)}Pt(CꢀCꢁMe)2 (3a)
4.3.3. {P(C7H7)2(p2-C7H7)}PtCl(CꢀCꢁPh) (2c)
Reaction time 15 min. M.p. (dec.) 139 °C. Yield 95
mg (82%), C27H27PPt. 1H-NMR (CD2Cl2, −40 °C):
l=1.93 (d, 3H, 4J(195Pt,1H)=10.9 Hz, 5J(31P,1H)=
M.p. (dec.) 181 °C. Yield 114 mg (90%),
C29H26ClPPt. 1H-NMR (CD2Cl2, −20 °C): l=2.49
2
3
4
(dt, 2H, J(31P,1H)=10.1 Hz, J(1H,1H)=6.6 Hz, H1),
2.4 Hz, Htrans-Me), 1.95 (d, 3H, J(195Pt,1H)=12.4 Hz,
4.74 (dt, 1H, J(31P,1H)=11.7 Hz, J(1H,1H)=8.9 Hz,
5J(31P,1H)=2.0 Hz, Hcis-Me), 2.20 (dt, 2H, J(31P,1H)=
2
3
2
H1%), 5.25 (m, 2H, H2,7), 5.35 (m, 2H, H2,7), 5.76 (m,
11.2 Hz, 3J(1H,1H)=6.7 Hz, H1), 4.53 (dt, 1H,
2H, H2%,7%), 6.08 (m, 2H, J(195Pt,1H)=37.4 Hz, H4%,5%),
2J(31P,1H)=13.2 Hz, J(1H,1H)=8.0 Hz, H1%), 5.18 (m,
2
3
6.29 (m, 4H, H3,6), 6.58 (m, 2H, H3%,6%), 6.62 (m, 4H,
H4,5), 7.10–7.20 (m, 5H, Ph). IR (CsI, cm−1): w(CꢀC)
2128. EIMS; m/e (%): 636 (71) [M+], 454 (1)
[P(C7H7)Pt(CꢀCPh)Cl+], 304 (1) [P(C7H7)+3 ], 91 (66)
[C7H+7 ], 78 (100) [C6H+6 ].
2H, H2,7), 5.23 (m, 2H, H2,7), 5.51 (m, 2H, H2%,7%), 5.63
(m, 4H, H3,6), 6.05 (m, 2H, 2J(195Pt,1H)=37.5 Hz,
H4%,5%), 6.24 (m, 4H, H4,5), 6.37 (m, 2H, H3%,6%). IR (CsI,
cm−1): w(CꢀC) 2149.
4.3.4. {P(C7H7)2(p2-C7H7)}PtCl(CꢀCꢁFc) (2d)
4.4.2. {P(C7H7)2(p2-C7H7)}Pt(CꢀCꢁtBu)2 (3b)
M.p. (dec.) 173 °C. Yield 130 mg (92%),
Reaction time 30 min. M.p. (dec.) 149 °C. Yield 122
C33H30FePPt. 1H-NMR (CD2Cl2, −20 °C): l=2.50
mg (92%), C33H39PPt. 1H-NMR (CD2Cl2, −40 °C):
t
2
3
(dt, 2H, J(31P,1H)=10.2 Hz, J(1H,1H)=6.5 Hz, H1),
l=1.01/1.19 (s/s, 9H/9H, Hcis/trans- Bu), 2.17 (dt, 2H,
4.05 (s, 5H, HCp), 4.07 (m, 2H) and 4.14 (m, 2H) (HFc),
2J(31P,1H)=8.3 Hz, J(1H,1H)=6.9 Hz, H1), 4.62 (dt,
3
4.68 (dt, 1H, J(31P,1H)=11.9 Hz, J(1H,1H)=8.8 Hz,
1H, 2J(31P,1H)=12.6 Hz, 3J(1H,1H)=8.8 Hz, H1%),
2
3
H1%), 5.27 (m, 2H, H2,7), 5.42 (m, 2H, H2,7), 5.73 (m,
5.13 (m, 2H, H2,7), 5.33 (m, 2H, H2,7), 5.66 (m, 2H,
2H, H2%,7%), 6.00 (m, 2H, J(195Pt,1H)=36.6 Hz, H4%,5%),
H2%,7%), 6.03 (m, 2H, J(195Pt,1H)=39.8 Hz, H4%,5%), 6.25
2
2
6.29 (m, 4H, H3,6), 6.58 (m, 2H, H3%,6%), 6.67 (m, 4H,
H4,5). IR (CsI, cm−1): w(CꢀC) 2118. EIMS; m/e (%):
418 (38) [FcC4Fc+], 186 (9) [Fc+], 91 (100) [C7H+7 ], 78
(70) [C6H+6 ].
(m, 4H, H3,6), 6.40 (m, 2H, H3%,6%), 6.60 (m, 4H, H4,5).
IR (CsI, cm−1): w(CꢀC) 2114. EIMS; m/e (%): 661 (9)
[M+], 580 (61) [P(C7H7)3Pt(CꢀCtBu)+], 570 (14)
[P(C7H7)2Pt(CꢀCtBu)2+], 499 (68) [P(C7H7)3Pt+], 408 (2)
[P(C7H7)2Pt+], 304 (1) [P(C7H7)+3 ], 91 (100) [C7H+7 ].
4.3.5. {P(C7H7)2(p2-C7H7)}PtCl(CꢀCꢁSiMe3) (2e)
Reaction time 60 min. M.p. (dec.) 202 °C. Yield 91
mg (72%), C26H30ClPPtSi. 1H-NMR (CD2Cl2,
−20 °C): l= −0.03 (s, 9H, 2J(29Si,1H)=119.5 Hz,
4.4.3. {P(C7H7)2(p2-C7H7)}Pt(CꢀCꢁPh)2 (3c)
Reaction time 90 min. M.p. (dec.) 147 °C. Yield 132
2
5J(195Pt,1H)=6.9 Hz, HMe), 2.45 (dt, 2H, J(31P,1H)=
mg (94%), C37H31PPt. 1H-NMR (CD2Cl2, −40 °C):
10.2 Hz, 3J(1H,1H)=6.4 Hz, H1), 4.68 (dt, 1H,
l=2.31 (dt, 2H, J(31P,1H)=9.9 Hz, J(1H,1H)=6.6
Hz, H1), 4.74 (dt, 1H, 2J(31P,1H)=10.2 Hz,
3J(1H,1H)=7.8 Hz, H1%), 5.25 (m, 2H, H2,7), 5.34 (m,
2H, H2,7), 5.73 (m, 2H, H2%,7%), 6.08 (m, 2H,
2J(195Pt,1H)=41.4 Hz, H4%,5%), 6.29 (m, 4H, H3,6), 6.52
(m, 2H, H3%,6%), 6.61 (m, 4H, H4,5), 7.14–7.42 (m, 10H,
Phcis/trans). IR (CsI, cm−1): w(CꢀC) 2117. EIMS; m/e
(%): 601 (2) [P(C7H7)3Pt(CꢀCPh)+], 499 (1)
[P(C7H7)3Pt+], 408 (1) [P(C7H7)2Pt+], 91 (100) [C7H+7 ],
78 (40) [C6H+6 ].
2
3
3
2J(31P,1H)=11.8 Hz, J(1H,1H)=8.6 Hz, H1%), 5.17 (m,
2H, H2,7), 5.39 (m, 2H, H2,7), 5.73 (m, 2H, H2%,7%), 6.06
(m, 2H, 2J(195Pt,1H)=36.3 Hz, H4%,5%), 6.30 (m, 4H,
H3,6), 6.54 (m, 2H, H3%,6%), 6.65 (m, 4H, H4,5). IR (CsI,
cm−1): w(CꢀC) 2062. EIMS; m/e (%): 631 (2) [M+], 616
(2) [P(C7H7)3Pt(CꢀCSiMe2)Cl+], 595 (4) [P(C7H7)3-
Pt(CꢀCSiMe3)+], 504 (5) [P(C7H7)2Pt(CꢀCSiMe3)+],
408 (2) [P(C7H7)2Pt+], 317 (2) [P(C7H7)Pt+], 304 (2)
[P(C7H7)+3 ], 91 (100) [C7H+7 ].

M. Herberhold et al. / Journal of Organometallic Chemistry 641 (2002) 173–184
183
4.4.4. {P(C7H7)2(p2-C7H7)}Pt(CꢀCꢁFc)2 (3d)
Reaction time 90 min. M.p. (dec.) 132 °C. Yield 178
4.5. X-ray structural analyses of complexes 2b and 3d
mg (96%), C46H39Fe2PPt. 1H-NMR (CD2Cl2,
−
Single crystals of 2b and 3b were sealed in Linde-
mann capillaries. Relevant experimental details on the
crystal structure analyses are given in Table 6.
The intensity data were collected on a Siemens P4
diffractometer with Mo–Ka radiation (u=71.073 pm,
graphite monochromator) at r.t. The hydrogen atoms
are in calculated positions. All non-hydrogen atoms
were refined with anisotropic temperature factors. The
hydrogen atoms were refined applying the riding model
with fixed isotropic temperature factors.
40 °C): l=2.30 (dt, 2H, 2J(31P,1H)=9.2 Hz,
3J(1H,1H)=6.8 Hz, H1), 4.05/4.23 (s/s, 5H/5H, HCp),
4.08/4.11 (m/m, 2H/2H) and 4.19/4.38 (m/m, 2H/2H)
2
3
(HFc), 4.63 (dt, 1H, J(31P,1H)=9.0 Hz, J(1H,1H)=
8.1 Hz, H1%), 5.34 (m, 2H, H2,7), 5.43 (m, 2H, H2,7), 5.69
(m, 2H, H2%,7%), 6.19 (m, 2H, 2J(195Pt,1H)=38.5 Hz,
H4%,5%), 6.32 (m, 4H, H3,6), 6.46 (m, 2H, H3%,6%), 6.70 (m,
4H, H4,5). IR (CsI, cm−1): w(CꢀC) 2130.
4.4.5. {P(C7H7)2(p2-C7H7)}Pt(CꢀCꢁSiMe3)2 (3e)
Reaction time 15 min. M.p. (dec.) 158 °C. Yield 125
5. Supplementary material
1
mg (90%), C31H39PPtSi2. H-NMR (CD2Cl2, −40 °C):
l= −0.03/0.05 (s/s, 9H/9H, HMe), 2.21 (dt, 2H,
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC nos. 168419 and 168420 for 2b
and 3d, respectively. Copies 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).
3
2J(31P,1H)=9.3 Hz, J(1H,1H)=6.1 Hz, H1), 4.67 (dt,
1H, 2J(31P,1H)=11.9 Hz, 3J(1H,1H)=9.0 Hz, H1%),
5.12 (m, 2H, H2,7), 5.31 (m, 2H, H2,7), 5.68 (m, 2H,
2
H2%,7%), 6.23 (m, 4H, H3,6), 6.26 (m, 2H, J(195Pt,1H)=
46.8 Hz, H4%,5%), 6.47 (m, 2H, H3%,6%), 6.62 (m, 4H, H4,5).
IR (CsI, cm−1): w(CꢀC) 2058.
Table 6
Crystal data and structure refinement parameters for the complexes
2b and 3d
Acknowledgements
2b
3d
Support of this work by the Deutsche Forschungsge-
meinschaft and the Fonds der Chemischen Industrie is
gratefully acknowledged.
Empirical formula
C27H30ClPPt
C45H39PFe2Pt·
(CH3)2CO
Dark red plate
23
Crystal
Yellow prism
23
Temperature (°C)
Crystal size (mm)
Crystal system
Space group
Unit cell parameters
a (pm)
b (pm)
c (pm)
h (°)
i (°)
0.20×0.16×0.12
Triclinic
0.18×0.14×0.08
Monoclinic
P21/c
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