Synthesis and reactivity of Group 14 substituted amino-functionalised cyclopentadienyl compounds

Article abstract of DOI:10.1016/S0022-328X(02)01470-5

Having isolated and characterised a series of sodium amino-functionalised cyclopentadienide salts, a number of Group 14 derivatives have been synthesised and characterised. These have potential as amino-functionalised cyclopentadienyl transfer reagents and a trimethylsilyl derivative has been used from a new type of 1,3-bisfunctionalised ferrocene compound.

Full text of DOI:10.1016/S0022-328X(02)01470-5

Journal of Organometallic Chemistry 656 (2002) 49ꢁ56
/
www.elsevier.com/locate/jorganchem
Synthesis and reactivity of Group 14 substituted amino-
functionalised cyclopentadienyl compounds
Sam Bradley, Marco M. Corradi, Kenneth D. Camm, Stephen J. Furtado,
Patrick C. McGowan *, Raheela Mumtaz, Mark Thornton-Pett
Department of Chemistry, University of Leeds, Leeds LS2 9JT, UK
Received 8 February 2002; accepted 8 April 2002
Abstract
Having isolated and characterised a series of sodium amino-functionalised cyclopentadienide salts, a number of Group 14
derivatives have been synthesised and characterised. These have potential as amino-functionalised cyclopentadienyl transfer
reagents and a trimethylsilyl derivative has been used from a new type of 1,3-bisfunctionalised ferrocene compound. # 2002
Elsevier Science B.V. All rights reserved.
Keywords: Cyclopentadienyl compounds; Group 14 derivatives; 1,3-Bisfunctionalised ferrocene
1. Introduction
This paper reports general and high yielding routes to
the preparation and isolation of a series of amino-
functionalised sodium cyclopentadienide salts. Part of
this work has been previously communicated [6,9] and
we present here a more detailed account with full
experimental details and characterisation of the amino-
functionalised sodium cyclopentadienide salts. We re-
port new Group 14 amino-functionalised cyclopenta-
We have been interested in transition metal amino-
functionalised cyclopentadienyl compounds due to their
catalytic applications [1] as well as their potential anti-
tumour properties [2,3]. An excellent review of amino-
functionalised cyclopentadienyl compounds has been
written by Jutzi with many relevant references contained
therein [4]. One area of interest is the synthesis of
cyclopentadienyl functionalised Group 5 complexes in
order to evaluate their catalytic potential. These can be
difficult to make by metathesis with alkali metal
cyclopentadienide salts due to reduction problems at
the transition metal centre. Therefore, it was to this end
that we wanted to synthesise Group 14 substituted
amino-functionalised cyclopentadienyl compounds to
act as cyclopentadienyl transfer reagents. Also, one of
our aims was to try to modify the architecture of the
transition metal bound amino-functionalised cyclopen-
tadienyl ligand by addition of a second group to the
cyclopentadienyl ring. We have previously reported a
series of functionalised ferrocenes, [5,6] vanadocenes
[6,7], titanocenes [2,3] and yttrium amino-functionalised
cyclopentadienyl compounds [8].
dienyl compounds as well as
functionalised ferrocene derivative.
a
new bis-1,3-
2. Results and discussion
The ligand precursors were used to synthesise the
corresponding sodium salts NaC5H4(CH2)2NMe2 (1),
NaC5H4(CH2)3NMe2 (2), NaC5H4(CH2)3NH2 (3),
NaC5H4CH(CH2)4NMe (4), NaC5H4(CH2)2N(CH2)5
(5) and NaC5H4(CH2)2N(C5H4N) (6). These com-
pounds are very water and air sensitive white/beige
coloured powders, and after synthesis are stored in a
glove box and used accordingly. They can be synthesised
on a 20 g scale in up to 100% yield. Despite the air and
moisture sensitive nature of these compounds they can
be readily stored under inert atmospheres indefinitely.
Preparation was achieved by addition of the substituted
cyclopentadiene to a THF suspension of sodium hy-
* Corresponding author. Fax: ꢀ
E-mail address: p.c.mcgowan@chem.leeds.ac.uk (P.C. McGowan).
/44-113-2336565
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 1 4 7 0 - 5

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S. Bradley et al. / Journal of Organometallic Chemistry 656 (2002) 49ꢁ56
/
Table 1
1H and 13C-NMR data for compounds 1ꢁ
6
/

S. Bradley et al. / Journal of Organometallic Chemistry 656 (2002) 49ꢁ
/56
51
Table 1 (Continued)
dride. Effervescence was observed as hydrogen is
released. The amino substituted cyclopentadiene was
used in slight excess to minimise the chance of unreacted
sodium hydride contaminating the final product.
Characterisation of these compounds was achieved by
NMR spectroscopy since they are pyrophoric and also
too air and moisture sensitive for microanalysis. The
bis-substituted lithium salt 10. This air and water
sensitive salt has been characterised by 1H and 13C-
NMR spectroscopy. The synthesis and isolation of 10 is
significant because it provides evidence of the possibility
of adding increased steric properties to organometallic
amino-functionalised cyclopentadienyl compounds.
The pertinent crystallographic details for 8 are given
in Table 2. Crystals of 8 were obtained by recrystallisa-
NMR data for the compounds 1ꢁ6 are shown in Table
/
tion from a petroleum ether (40ꢁ60 8C) solution and an
X-ray structure analysis carried out. Selected bond
lengths and angles are shown in Table 3. Compound 8
/
1. Of particular interest is the NMR of 4 and 5, which
shows signals attributable to axial and equatorial
protons of the piperidyl ring. 1Hꢁ1H and 1H{13C}-
/
NMR spectroscopy correlation experiments proved
particularly useful in determining that the axial protons
are furthest downfield in the 1H-NMR spectrum. For 4,
there is a large difference in chemical shift of the axial, d
Table 2
Crystallographic data for compounds 8 and 10
Compound
8
11
3.81ꢁ
/
2.78 ppm, and equatorial protons, d 1.89ꢁ1.79
/
Crystal description
Crystal size (mm)
Chemical formula
Temperature (K)
Yellow prism
0.6ꢂ0.57ꢂ0.5 mm
C29H31NPb
150(2)
Orange plate
0.14ꢂ0.08ꢂ0.08
C28H50FeN2Si2
150(2)
ppm, which are attached to the carbon atoms next to the
nitrogen. The differences in the chemical shifts asso-
ciated with the axial and equatorial protons are the
˚
a (A)
9.0220(3)
9.3607(6)
17.5063(3)
11.5794(3)
16.7952(4)
90
result of the trans diaxial relationship between the CÃ
/
H
˚
b (A)
and the nitrogen lone-pair.
˚
c (A)
14.9421(6)
94.473(2)
98.369(2)
Synthesis of trialkyl Group 14 derivatives was
achieved by the reaction of 4 with either trimethyl silyl
chloride and triphenyl lead bromide to yield the 1,3 bis-
a (8)
b (8)
g (8)
Crystal system
Space group
Z
119.5310(10)
90
99.155(2)
Triclinic
Monoclinic
C2/c
substituted
cyclopentadienyl
derivatives
Me3-
¯
P
/1/
Si(C5H4)CH(CH2)4NMe 7, Ph3Pb(C5H4)(CH2)5NMe 8,
and by the reaction of 5 with triphenyl lead bromide to
yield Ph3Pb(C5H4)(CH2)2N(CH2)5 9 (Scheme 1). Com-
2
14891
4784
4
22456
2891
Reflections collected
Data measured
Unique data
Rint
1
pounds 8 and 9 have been characterised by H and 13C-
4440 [I ꢀ2s(I)]
0.1276
Full
2511 [I ꢀ2s(I)]
0.0577
Full
NMR spectroscopy, microanalysis as well as X-ray
crystallography in the case of 8. The compound
Me3SiC5H4(CH2)2N(CH2)5 has previously been re-
ported in the synthesis of Ti{h-C5H4(CH2)2N-
(CH2)5}2Cl3 [10]. Reaction of 7 with BuLi yields the
Refinement method
Parameters refined
R (all data)
Rw (all data)
282
0.062
0.1547
155
0.0454
0.0943

52
S. Bradley et al. / Journal of Organometallic Chemistry 656 (2002) 49ꢁ56
/
Table 3
˚
Interatomic distances (A) and angles between interatomic vectors (8)
with s.u.s. in parentheses for compound 8
Interatomic distances
Pb(1)ÃC(31)
Pb(1)ÃC(11)
C(1)ÃC(5)
C(2)ÃC(3)
C(4)ÃC(5)
2.191(7)
2.209(7)
Pb(1)ÃC(21)
Pb(1)ÃC(1)
2.191(7)
2.280(9)
1.460(14)
1.472(13)
1.523(13)
1.453(13) C(1)ÃC(2)
1.343(14) C(3)ÃC(4)
1.326(13) C(4)ÃC(51)
Interatomic angles
C(31)ÃPb(1)ÃC(21)
C(21)ÃPb(1)ÃC(11)
C(21)ÃPb(1)ÃC(1)
C(16)ÃC(11)ÃPb(1)
C(22)ÃC(21)ÃPb(1)
C(32)ÃC(31)ÃPb(1)
C(5)ÃC(1)ÃC(2)
C(2)ÃC(1)ÃPb(1)
C(2)ÃC(3)ÃC(4)
C(5)ÃC(4)ÃC(51)
C(4)ÃC(5)ÃC(1)
116.3(2)
109.5(3)
110.2(3)
120.1(5)
119.1(5)
118.3(5)
104.4(8)
104.9(6)
109.3(8)
127.5(9)
110.8(9)
113.1(8)
C(31)ÃPb(1)ÃC(11)
107.5(2)
106.4(3)
106.5(3)
120.6(5)
122.1(6)
123.4(6)
105.8(6)
108.4(9)
106.9(9)
125.5(8)
114.0(8)
C(31)ÃPb(1)ÃC(1)
C(11)ÃPb(1)ÃC(1)
C(12)ÃC(11)ÃPb(1)
C(26)ÃC(21)ÃPb(1)
C(36)ÃC(31)ÃPb(1)
C(5)ÃC(1)ÃPb(1)
C(3)ÃC(2)ÃC(1)
C(5)ÃC(4)ÃC(3)
C(3)ÃC(4)ÃC(51)
C(56)ÃC(51)ÃC(4)
C(52)ÃC(51)ÃC(4)
is the first structurally characterised example of a metal
complex containing a functionalised cyclopentadienyl
triphenylplumbyl substituted compound and the mole-
cular structure shown in Fig. 1: the unsubstituted
cyclopentadiene derivative PbPh3Cp has been previously
synthesised [11]. The structure of 8 shows the expected
sp3 hybridised triphenyl Pb(IV) centre bound in an h1
fashion to the functionalised cyclopentadienyl ring. For
the cyclopentadienyl unit bound to the Pb centre, the
bond lengths and angles are similar to those found for
PbPh3Cp (Table 3) [11].
Fig. 1. The molecular structure of compound 8.
A similar phenomonen was observed for the unfunctio-
nalised derivative PbPh3Cp, where this sample was
cooled to ꢃ40 8C [11].
/
There has been much interest in ferrocene and
ferrocenium complexes for a variety of reasons, includ-
ing their cytotoxic properties [12,13] and anti-malarial
activities [14] We have published in the area of synthesis
and reactivity of mono-functionalised ferrocenes [5,6]. A
1,3 bis-substituted cyclopentadienyl ferrocene derivative
has been synthesised by reaction of 10 and FeCl2 to
produce 11 as shown in Scheme 3. Compound 11 was
characterised by 1H and 13C-NMR spectroscopy, micro-
analysis as well as X-ray crystallography. The pertinent
crystallographic details for 11 are given in Table 2.
Crystals of 11 were obtained by slow evaporation
from an ether solution and an X-ray structure analysis
carried out. For 11, there is half a molecule per
symmetric unit and selected bond lengths and angles
are shown in Table 4. Compound 11 is the first
structurally characterised example of a metal complex
containing a trimethylsilyl substituted amino-functiona-
lised cyclopentadienyl ligand system and the molecular
The NMR spectrum of 8 and 9 consists of an AA?BB?
pattern, which is indicative of a molecular plane of
symmetry. For 8 and 9 there are two sets of coupling
constants for (207PbÃ
/
1H) of Â
/
20 and Â
are indicative of the Pb(IV) centre being attached closer
to one set of CÃH cyclopentadiene peaks than the
/
60 Hz, which
/
others. This is not in accordance with the structure
found in the solid state, therefore, low temperature
NMR experiments were carried out to try to elucidate if
there was a fluxional process within the molecule. It
could be envisaged that the ring can undergo a
molecular flip as shown in Scheme 2. This could be a
way of explaining the symmetrical nature of the
molecule in solution. Collapse of the signals could not
be achieved, even after cooling the sample to ꢃ90 8C.
/
Scheme 1. (i) THF.

S. Bradley et al. / Journal of Organometallic Chemistry 656 (2002) 49ꢁ
/56
53
Scheme 2.
Scheme 3. (i) THF, FeCl2.
structure shown in Fig. 2. The ligands contain N-
methylpiperidinyl ring substituents, which exist in a
chair conformation. The cyclopentadienyl rings are
virtually eclipsed with respect to each other and the
N-methylpiperidinyl side chains are in cis-conformation
to each other. This is different to Fe[h-
C5H4CH(CH2)4NMe]2, [6] where the aminocyclopenta-
dienyl groups lie virtually trans to each other. This is
presumably due to the influence of the trimethylsilyl
group. There are a number of possibilities of diastereoi-
somers which is indicated by NMR spectroscopy, which
are similar to those reported for Fe[C5H3-1-PPh2-
solvents were degassed by three freeze-pump-thaw cycles
˚
and stored over 3 A molecular sieves in a dry box, except
Acetonitrile-d3, which was distilled from CaH2. All
reagents were purchased in reagent grade and used
without further purification.
3.2. Instrumentation
1H and 13C-NMR spectra were recorded on Bruker
250, 300 and 500 MHz spectrometers. *High resolution
mass spectrometry was performed by the University of
Leeds mass spectral service. Elemental analyses were
performed by the University of Leeds microanalytical
services.
3-tBu](C5H5)]2
[15]
Me3](C5H5)]2 [16]. Crystallisation tends to favour the
and
Fe[C5H3-1-PPh2-3-Si-
meso isomer. The iron ring-centroid distance for 11 is
˚
Cp(cent) 1.66 A, which is equal to that of the
Fe(1)Ã
/
monofunctionalised
C5H4CH(CH2)4NMe]2.
ferrocene
analogue,
Fe[h-
3.3. Preparations
In conclusion, this paper reports the preparation and
characterisation of a number of sodium cyclopentadie-
nide salts, as well as some of their Group 14 analogues.
Also presented is the synthesis, isolation and character-
isation of a bis-1, 3 substituted ferrocene. The functio-
nalised ferrocenes open up the possibilities of
synthesising a range of ferrocenium compounds, which
may have potential as anti-tumour reagents.
3.3.1. NaC5H4(CH2)2NMe2 (1)
To a Schlenk tube charged with NaH (2.2 g, 0.092
mol) and THF (100 ml) was added C5H5(CH2)2NMe2
(25.0 g) dropwise with stirring. Evolution of a gas and
formation of a pale brown precipitate was observed. The
reaction mixture was stirred for ca. 6 h. THF was then
removed in vacuo and the product was washed with
petroleum ether (b.p. 40ꢁ
/
60 8C) (3ꢂ30 ml) to give a
/
pale brown powdery solid.
3. Experimental
3.3.2. NaC5H4(CH2)3NMe2 (2)
3.1. General
To a Schlenk tube charged with NaH (3.0 g, 0.125
mol) and THF (100 ml) was added C5H5(CH2)3NMe2
(37.9 g) dropwise with stirring. The reaction mixture was
worked up in the same way as 1 to give a pale brown
powdery solid, (16.5 g, 0.095 mol, 76%, based on NaH).
Standard inert atmosphere techniques were used
throughout. Petroleum ether (40ꢁ
toluene and THF were distilled from Naꢁ
/
608), diethyl ether,
/
Ph2CO. NMR

54
S. Bradley et al. / Journal of Organometallic Chemistry 656 (2002) 49ꢁ56
/
Table 4
˚
Interatomic distances (A) and angles between interatomic vectors (8)
with s.u.s. in parentheses for compound 11
Interatomic distances
Fe(1)ÃC(1)
Fe(1)ÃC(2)
Fe(1)ÃC(3)
Fe(1)ÃC(4)
Fe(1)ÃC(5)
Si(1)ÃC(3)
C(1)ÃC(6)
2.073(2)
2.0499(19)
2.0684(19)
2.045(2)
2.054(2)
1.859(2)
1.508(3)
Interatomic angles
C(4)ÃFe(1)ÃC(4)
C(4)ÃFe(1)ÃC(2)
C(4)ÃFe(1)ÃC(2)
C(4)ÃFe(1)ÃC(5)
C(2)ÃFe(1)ÃC(5)
C(4)ÃFe(1)ÃC(5)
C(2)ÃFe(1)ÃC(5)
C(5)ÃFe(1)ÃC(5)
C(4)ÃFe(1)ÃC(3)
C(2)ÃFe(1)ÃC(3)
C(5)ÃFe(1)ÃC(3)
C(4)ÃFe(1)ÃC(3)
C(2)ÃFe(1)ÃC(3)
C(5)ÃFe(1)ÃC(3)
C(4)ÃFe(1)ÃC(1)
C(2)ÃFe(1)ÃC(1)
C(5)ÃFe(1)ÃC(1)
C(3)ÃFe(1)ÃC(1)
C(4)ÃFe(1)ÃC(1)
C(2)ÃFe(1)ÃC(1)
C(5)ÃFe(1)ÃC(1)
C(3)ÃFe(1)ÃC(1)
C(1)ÃFe(1)ÃC(1)
C(3)ÃSi(1)ÃC(14)
C(3)ÃSi(1)ÃC(12)
C(14)ÃSi(1)ÃC(12)
C(9)ÃN(9)ÃC(8)
C(1)ÃC(2)ÃC(3)
C(3)ÃC(2)ÃFe(1)
C(5)ÃC(4)ÃFe(1)
C(5)ÃC(1)ÃC(2)
C(2)ÃC(1)ÃC(6)
C(2)ÃC(1)ÃFe(1)
C(4)ÃC(5)ÃC(1)
C(1)ÃC(5)ÃFe(1)
C(2)ÃC(3)ÃSi(1)
C(2)ÃC(3)ÃFe(1)
Si(1)ÃC(3)ÃFe(1)
C(8)ÃC(7)ÃC(6)
C(1)ÃC(6)ÃC(7)
N(9)ÃC(10)ÃC(11)
115.32(12) C(4)ÃFe(1)ÃC(2)
133.49(8)
67.87(8)
67.87(8)
133.49(8)
40.51(8)
109.80(8)
146.33(8)
67.80(8)
C(4)ÃFe(1)ÃC(2)
C(2)ÃFe(1)ÃC(2)
C(4)ÃFe(1)ÃC(5)
C(2)ÃFe(1)ÃC(5)
C(4)ÃFe(1)ÃC(5)
C(2)ÃFe(1)ÃC(5)
146.14(11)
146.33(8)
67.80(8)
40.51(8)
109.80(8)
41.06(8)
Fig. 2. The molecular structure of compound 11.
172.29(12) C(4)ÃFe(1)ÃC(3)
3.3.4. NaC5H4CH(CH2)4NMe (4)
108.76(8)
40.86(8)
114.33(8)
41.06(8)
172.59(8)
69.04(8)
172.59(8)
40.57(7)
133.10(8)
145.39(8)
68.25(8)
114.93(8)
40.42(8)
69.27(8)
C(2)ÃFe(1)ÃC(3)
C(5)ÃFe(1)ÃC(3)
C(4)ÃFe(1)ÃC(3)
C(2)ÃFe(1)ÃC(3)
C(5)ÃFe(1)ÃC(3)
C(3)ÃFe(1)ÃC(3)
C(4)ÃFe(1)ÃC(1)
C(2)ÃFe(1)ÃC(1)
C(5)ÃFe(1)ÃC(1)
C(3)ÃFe(1)ÃC(1)
C(4)ÃFe(1)ÃC(1)
C(2)ÃFe(1)ÃC(1)
C(5)ÃFe(1)ÃC(1)
C(3)ÃFe(1)ÃC(1)
172.59(8)
69.04(8)
To a Schlenk tube charged with NaH (2.5 g 0.104
mol) and THF (100 ml) was added C5H5CH(CH2)4NMe
(50.0 g) dropwise with stirring. The reaction mixture was
worked up in the same way as 1 to give a pale brown
powdery solid, (17.7 g, 0.096 mol, 92%, based on NaH).
108.76(8)
40.86(8)
114.33(8)
132.33(11)
68.25(8)
114.93(8)
40.42(8)
69.27(8)
3.3.5. NaC5H4(CH2)2N(CH2)5 (5)
To a Schlenk tube charged with NaH (3.0 g, 0.125
mol)
and
THF
(100
ml)
was
added
172.59(8)
40.57(7)
C5H5CH(CH2)2N(CH2)5 (50.0 g) dropwise with stirring.
The reaction mixture was worked up in the same way as
1 to give a pale brown powdery solid, (15.0 g, 0.075 mol,
60%, based on NaH).
133.10(8)
145.39(8)
108.95(11)
109.79(14)
111.20(14)
111.72(18)
110.80(17)
70.58(11)
109.42(18)
70.32(11)
127.59(18)
69.08(11)
129.91(14)
69.42(11)
105.05(17)
128.33(16)
68.61(11)
111.19(18)
113.61(17)
108.07(16)
110.78(17)
109.04(11) C(3)ÃSi(1)ÃC(13)
111.78(10) C(13)ÃSi(1)ÃC(14)
107.21(10) C(13)ÃSi(1)ÃC(12)
107.89(12) C(9)ÃN(9)ÃC(10)
110.87(18) C(10)ÃN(9)ÃC(8)
110.35(18) C(1)ÃC(2)ÃFe(1)
70.26(11) C(5)ÃC(4)ÃC(3)
70.07(11) C(3)ÃC(4)ÃFe(1)
106.57(17) C(5)ÃC(1)ÃC(6)
125.72(18) C(5)ÃC(1)ÃFe(1)
68.85(11) C(6)ÃC(1)ÃFe(1)
108.61(17) C(4)ÃC(5)ÃFe(1)
70.50(11) C(2)ÃC(3)ÃC(4)
126.47(15) C(4)ÃC(3)ÃSi(1)
68.88(11) C(4)ÃC(3)ÃFe(1)
129.81(11) N(9)ÃC(8)ÃC(7)
110.93(17) C(1)ÃC(6)ÃC(11)
111.39(17) C(11)ÃC(6)ÃC(7)
110.21(18) C(10)ÃC(11)ÃC(6)
3.3.6. NaC5H4CH2(C5H4N) (6)
To a Schlenk tube charged with NaH (3.0 g, 0.125
mol) and THF (100 ml) was added a mixture of
dicyclopentadiene and C5H5CH(CH2)2N(CH2)5 (24.7
g) dropwise with stirring. The reaction mixture was
worked up in the same way as 1 to give a pale brown
powdery solid, (22.4 g, 0.125 mol, 100%, based on
NaH).
3.3.7. Me3Si(C5H4)CH(CH2)4NMe (7)
Under an atmosphere of nitrogen, 4 (2.28 g, 0.01 mol)
was dissolved in dry THF (25 ml) with stirring. ClSiMe3
(1.23g, 0.01 mol) was added producing a yellow solution
with a white precipitate. The THF was removed under
reduced pressure and the compound extracted in
petroleum ether (b.p. 40ꢁ
product was isolated as a clear oil. H-NMR (CDCl3,
250 MHz, 300 K) 6.35 [m, 3H, C5H3H(Si-
/
60 8C) (2ꢂ
/
30 ml). The
1
3.3.3. NaC5H4(CH2)3NH2 (3)
d
¯
To a Schlenk tube charged with NaH (2.4 g, 0.100
mol) and THF (100 ml) was added C5H5(CH2)3NH2
(35.0 g) dropwise with stirring. The reaction mixture
was worked up in the same way as 1 to give a pale
brown powdery solid, (8.7 g, 0.060 mol, 60%, based on
NaH).
Me3)CH(CH2CH2)2NMe], 3.1 [s, 1H, C5H3H(Si-
¯
Me3)CH(CH2CH2)2NMe], 2.75 [m, 2H, C5H4(SiMe3)-
CH(CH2CH2)2NMe], 2.20 [m, 1H, C5H4(SiMe3)CH-
¯
¯
(CH2CH2)2NMe], 2.15 [m, 3H, C5H4(SiMe3)CH(CH2-
CH2)2NMe], 1.83 [m, 4H, C5H4(SiMe3)CH(CH2CH2)2-
¯
¯
NMe], 1.70 [m, 2H, C5H4(SiMe3)CH(CH2CH2)2NMe],
¯

S. Bradley et al. / Journal of Organometallic Chemistry 656 (2002) 49ꢁ
/56
55
ꢃ
/
0.2 [s, 9H, SiMe3]. 13C{1H}-NMR (CDCl3, 250 MHz,
300 K) 138.0, 130.0, 138.1, [3ꢂs, C5H4(Si-
Me3)CH(CH2CH2)2NMe], 109.3 [s, CCH(CH2CH2)2-
K) d 155.0 [s, CPb)], 142.8 [s, C5H4, Pb(CH)2(CH)2-
¯
¯
2
d
/
CCH2)], 137.0 [CH (meta)] J (107PbÃ
/
13C) 67.74 Hz,
¯
¯
¯
1
130.2 [CH (ortho)] J (107PbÃ
/
13C) 79.56 Hz, 129.3 [CH
¯
¯
¯
NMe], 57.0 [s, C5H4(SiMe3)CH(CH2CH2)2NMe], 51.0
[s, CHSiMe3], 47.1 [s, C5H4(SiMe3)CH(CH2-
(para)] 3J
Pb(CH)2(CH)2C)], 102.6 [s, C5H4, (Pb(CH)2(CH)2C],
(
107PbÃ
/
13C) 16.85 Hz, 128.2 [s, C5H4,
¯
¯
¯
¯
¯
¯
CH2)2NMe], 34.0 [s, C5H4(SiMe3)CH(CH2CH2)2NMe],
¯
60.7 [s, PbC5H4(CH2CH2)N(CH2)5], 55.2 [s, PbC5H4-
¯
32.0 [s, C5H4(SiMe3)CH(CH2CH2)2NMe], ꢃ
/2.0 [s,
(CH2)2N(CH2CH2)2CH2)], 28.7 [s PbC5H4(CH2-
¯
CH2)N(CH2)5], 27.0 [s PbC5H4(CH2)2N(CH2CH2)2-
¯
¯
¯
C5H4(SiMe3)CH(CH2CH2)2NMe].
¯
CH2)], 25.5 [s, PbC5H4(CH2)2N(CH2CH2)2CH2)].
¯
3.3.8. Ph3Pb(C5H4)CH(CH2)4NMe (8)
Ph3PbBr (0.72 g, 0.0014 mol) was dissolved in toluene
(30 ml) to give a clear solution to which 4 (0.25 g, 0.0014
mol) in toluene (30 ml), was added. The solution turned
yellow immediately with a white precipitate and was left
to stir for 24 h. The solution was filtered and the toluene
removed under reduced pressure. The resulting yellow
3.3.10. Li{C5H3-1-SiMe3-3-CH(CH2)4NMe} (10)
Under an atmosphere of nitrogen, C5H5CH(CH2)4-
NMe (3.54 g, 0.022 mol) was dissolved in dry THF (25
ml) with stirring. After addition of nBuLi in hexanes
(1.41 g, 0.022 mol), the solution turned from red to
yellow. To this solution, ClSiMe3 (2.4 g, 0.022 mol) was
added producing a yellow solution with a white pre-
cipitate. The THF was removed under reduced pressure
oily solid was extracted in petroleum ether (b.p. 40ꢁ
/
60 8C) (50 ml) and recrystallised yielding large yellow
crystals of Ph3Pb((C5H4)(CH2)5NMe) (0.41 g, 0.000683
mol, 49% yield). Found: C, 57.8; H, 5.3; N, 2.3. Calc.: C,
and the compound extracted in petroleum ether (b.p.
n
30 ml). BuLi in hexanes (1.16 g, 0.018
40ꢁ
/
60 8C) (2ꢂ
/
1
58.0; H, 5.2; N, 2.3%. H-NMR (C6D6, 500 MHz, 300
K) d 7.22 [m 15H, (C6H5)3Pb)], 6.41 [m, 2H, C5H4,
mol) was added to the resultant mixture yielding a
white/yellow precipitate. The petroleum ether (b.p. 40ꢁ
60 8C) was filtered off and the solid washed with the
petroleum ether (b.p. 40ꢁ60 8C) (25 mlꢂ3). The
/
3
¯
¯
Pb(CH)2(CH)2C] J (207PbÃ
/
1H) 19.0 Hz, 5.81 [m, 2H,
¯
C5H4, Pb(CH)2(CH)2C] 2J (207PbÃ
/
1H) 60.0 Hz, 2.75 [m,
2H, PbC5H4CH(CH2CH2)2NMe], 2.32 [m, 1H,
/
/
¯
¯
resulting solid was dried under reduced pressure to yield
Li(C5H3)(SiMe3)(CH2)5NMe (3.7 g, 0.015 mol, 70%).
1H-NMR (C6D6, 250 MHz, 300 K) d 5.56 [m, 3H,
C5H3(SiMe3)CH(CH2CH2)2NMe], 2.84 [m, 2H, C5H3-
¯
PbC5H4CH(CH2CH2)2NMe], 2.18 [m, 3H, PbC5H4CH-
¯
(CH2CH2)2NMe], 1.82 [m, 2H, PbC5H4CH(CH2-
CH2)2NMe], 1.66 [m, 4H, PbC5H4CH(CH2CH2)2NMe].
¯
¯
¯
13C{1H}-NMR (C6D6, 500 MHz, 300 K) d 153.3 [s,
CPb)], 148.6 [s, C5H4, Pb(CH)(CH)2CCH(CH2)4NMe)],
(SiMe3)CH(CH2CH2)2NMe], 2.29 [m, 1H, C5H3(Si-
¯
Me3)CH(CH2CH2)2NMe], 2.19 [m, 3H, C5H3(SiMe3)-
¯
¯
¯
¯
137.7 [s, CH (meta)] J (107PbÃ
/
13C), 67.51 Hz, 130.0 [s,
CH(CH2CH2)2NMe], 1.95 [m, 4H, C5H3(SiMe3)CH-
¯
2
¯
CH (ortho)] 1J (107PbÃ
/
13C) 79.91 Hz, 129.1 [s, CH
¯
(CH2CH2)2NMe], 1.51 [m, 2H, C5H3(SiMe3)CH(CH2-
¯
¯
(para)] 3J
Pb(CH)2(CH)2C], 99.3 [s, C5H4, Pb(CH)2(CH)2C], 56.8
(
107PbÃ
/
13C) 18.53 Hz, 121.4 [s, C5H4,
¯
CH2)2NMe], 0.08 [s, 9H, SiMe3]. 13C{1H}-NMR (C6D6,
¯
250 MHz, 300 K) d 128.9 [s, CSiMe3], 111.0, 108.7,
¯
¯
¯
¯
[s, PbC5H4CH(CH2CH2)2NMe], 47.0 [s, PbC5H4CH-
¯
105.6, [3ꢂ
/
s, C5H3(SiMe3)CH(CH2CH2)2NMe], 109.3
¯
(CH2CH2)2NMe], 36.9 [s, PbC5H4CH(CH2CH2)2NMe],
¯
[s, CCH(CH2CH2)2NMe], 57.7 [s, C5H3(SiMe3)CH-
¯
33.5 [s, PbC5H4CH(CH2CH2)2NMe],
¯
(CH2CH2)2NMe], 47.1 [s, C5H3(SiMe3)CH(CH2CH2)2-
¯
NMe], 37.1 [s, C5H3(SiMe3)CH(CH2CH2)2NMe], 35.7
¯
3.3.9. Ph3Pb(C5H4)(CH2)2N(CH2)5 (9)
[s, C5H3(SiMe3)CH(CH2CH2)2NMe], 1.3 [s, C5H3(Si-
¯
Ph3PbBr (0.64 g, 0.0012 mol) was dissolved in toluene
(30 ml) to give a clear solution to which 5 (0.25 g, 0.0012
mol) in toluene (30 ml), was added. The solution turned
immediately yellow with a white precipitate and was left
to stir for 24 h. The solution was filtered and the toluene
removed under reduced pressure resulting in yellow oil
Ph3Pb(C5H4)(CH2)2N(CH2)5 (0.44 g, 0.000716 mol, 53%
yield). Found: C, 58.5; H, 5.7; N, 2.1. Calc.: C, 58.6; H,
Me3)CH(CH2CH2)2NMe].
3.3.11. [Fe{C5H3-1-SiMe3-3-CH(CH2)4NMe}2] (11)
To a stirred solution of iron(II)chloride (0.095 g,
0.00075 mol) in THF at 08 was added a solution of the
10 (0.36, 0.0015 mol) in THF. The THF was removed
under reduced pressure to leave a brown solid. The
product was extracted with petroleum ether (b.p. 40ꢁ
60 8C). Recrystallisation from petroleum ether (b.p.
40ꢁ60 8C) afforded an orange crystalline solid. Yield:
/
1
5.4; N, 2.3% H-NMR (C6D6, 500 MHz, 300 K) d 7.27
[m 15H, (C6H5)3Pb], 6.40 [m, 2H, C5H4,
/
¯
3
¯
Pb(CH)2(CH)2C)] J (207PbÃ
/
1H) 22.8 Hz, 5.97 [m, 2H,
0.255 g, 65%. Found: C, 63.7; H, 9.9; N, 5.6. Calc.: C,
1
64.1; H, 9.2; N, 5.3%. H-NMR (C6D6, 250 MHz, 300
¯
C5H4, Pb(CH)2(CH)2C] 2J (207PbÃ
/
1H) 51.5 Hz, 2.81 [m,
2H, PbC5H4(CH2CH2)N(CH2)5], 2.44 [m, 2H,
¯
¯
K) d 5.56 [m, 3H, C5H3(SiMe3)CH(CH2CH2)2NMe],
¯
¯
PbC5H4(CH2CH2)N(CH2)5)], 2.41 [m, 4H, PbC5H4-
¯
2.84 [m, 2H, C5H3(SiMe3)CH(CH2CH2)2NMe], 2.29 [m,
¯
(CH2)2N(CH2CH2)2CH2)], 1.64 [m, 4H, PbC5H4(CH2)2-
¯
1H, C5H3(SiMe3)CH(CH2CH2)2NMe], 2.19 [m, 3H,
¯
N(CH2CH2)2CH2)], 1.44 [m, 2H, PbC5H4(CH2)2-
¯
C5H3(SiMe3)CH(CH2CH2)2NMe], 1.95 [m, 4H, C5H3-
¯
N(CH2)4CH2)]. 13C{1H}-NMR (C6D6, 500 MHz, 300
(SiMe3)CH(CH2CH2)2NMe], 1.51 [m, 2H, C5H3(Si-
¯
¯

56
S. Bradley et al. / Journal of Organometallic Chemistry 656 (2002) 49ꢁ56
/
Me3)CH(CH2CH2)2NMe]. 13C{1H}-NMR (C6D6, 250
[6] S. Bradley, P.C. McGowan, K.A. Oughton, M. Thornton-Pett,
M.E. Walsh, Chem. Commun. (1999) 77.
¯
MHz, 300 K) d 97.0, 96.7 [s, CSiMe3], 72.7, 72.0, 69.5,
¯
[7] S. Bradley, K.D. Camm, S.J. Furtado, A.L. Gott, P.C. McGo-
wan, T.J. Podesta, M. Thornton-Pett, accepted for publication.
[8] M.M. Corradi, M.A.D. McGowan, P.C. McGowan, M. Thorn-
ton-Pett, in press.
69.0, 67.7, 66.6 [6ꢂ
/
s, C5H3(SiMe3)CH(CH2-
¯
CH2)2NMe], 71.3, 71.2 [s, CCH(CH2CH2)2NMe], 56.3
¯
[2ꢂ
C5H3(SiMe3)CH(CH2CH2)2NMe], 35.6, 35.3 [2ꢂ
C5H3(SiMe3)CH(CH2CH2)2NMe], 35.2, 35.0, 32.9,
/s, C5H3(SiMe3)CH(CH2CH2)2NMe], 46.4 [s,
¯
[9] P.C. McGowan, C.E. Hart, B. Donnadieu, R. Poilblanc, J.
Organomet. Chem. 528 (1997) 191.
/s,
¯
[10] W.A. Herrmann, M.J.A. Morawietz, T. Priermeier, K. Mashima,
J. Organomet. Chem. 486 (1995) 291.
32.5 [4ꢂ
/
s, C5H3(SiMe3)CH(CH2CH2)2NMe], 1.3 [3ꢂ
/
¯
¯
s, C5H3(SiMe3)CH(CH2CH2)2NMe].
[11] C. Caffney, P.G. Harrison, J. Chem. Soc.-Dalton Trans. (1982)
1055.
[12] A.S. Georgopoulou, D.M.P. Mingos, A.J.P. White, D.J. Wil-
liams, B.R. Horrocks, A. Houlton, J. Chem. Soc.-Dalton Trans.
(2000) 2969.
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