Macrocyclic gold(I) complexes and [2]catenanes containing carbonyl functionalized diacetylide ligands

Article abstract of DOI:10.1016/S0022-328X(02)02070-3

The carbonyl derivatized bis(alkyne) O=C(4-C₆H₄OCH₂C≡CH)₂ was converted into the imine derivatives RN=C(4-C₆H₄OCH₂C≡CH)₂ [R = OH, NHC(O)NH₂, NHC₆

Full text of DOI:10.1016/S0022-328X(02)02070-3

Journal of Organometallic Chemistry 670 (2003) 27Á36
/
www.elsevier.com/locate/jorganchem
Macrocyclic gold(I) complexes and [2]catenanes containing carbonyl
functionalized diacetylide ligands
Fabian Mohr, Dana J. Eisler, Christopher P. McArdle, Khaled Atieh,
Michael C. Jennings, Richard J. Puddephatt *
Department of Chemistry, The University of Western Ontario, London, Ont., Canada N6A 5B7
Received 1 October 2002; accepted 24 October 2002
Abstract
The carbonyl derivatized bis(alkyne) OÄ
C6H4OCH2CÅCH)2 [RꢀOH, NHC(O)NH2, NHC6H3-2,4-(NO2)2] and into the 4-bromomethyl-1,3-dioxolane derivative
BrCH2C2H3O2C(4-C6H4OCH2CÅCH)2. The alkyne units in these compounds react with [AuCl(SMe2)] in the presence of base to
form the corresponding digold(I) diacetylide complexes, that exist as insoluble oligomers or polymers. They reacted with the
diphosphines Ph2PZPPh2 [ZꢀCC, trans-HCÄCH and (CH2)n, nꢀ3Á5] to give macrocyclic gold(I) complexes of the type [Au2(m-
/
C(4-C6H4OCH2CÅ
/
CH)2 was converted into the imine derivatives RNÄ
/C(4-
/
/
/
/
/
/
/
LL)(m-PP)], where LL is the diacetylide and PP the diphosphine ligand. The ability of these macrocyclic complexes to self-assemble
to [2]catenanes has been studied. The ketone and imine derivatives do not form [2]catenanes because the orientation of the aryl
groups is unfavorable, but the 1,3-dioxolane derivatives may catenate if the ring size is optimum.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Gold; Acetylide; Macrocycle; [2]Catenane; Self-assembly
1. Introduction
Linear gold(I) units are versatile building-blocks for
constructing organometallic network polymers and
rings because of favorable geometry, low steric effects
and the potential to bind to other gold(I) units through
The vast majority of known catenanes, which are of
current interest as supramolecular compounds with
potential applications in nanoscale devices, are based
aurophilic attractions [9,10]. These secondary goldÁ
bonds typically have energies of 7Á
11 kcal molꢁ1 with
goldÁgold distances ranging from 2.75 to 3.40 A [11],
/
gold
/
on organic or inorganic molecules [1Á7]. The first
/
˚
/
organometallic [2]catenane was reported in 1993 [8].
Several elegant strategies for synthesis of [2]catenanes
have been developed and, if the [2]catenane is to be
thermodynamically favored with respect to the separate
ring complexes, it is recognized that inter-ring secondary
and they can be very useful in self-assembly of complex
structures. For example, aurophilic attractions play a
part in favoring [2]catenane formation from gold(I)
macrocycles, and the effect has been exploited in the
synthesis of several organometallic [2]catenanes contain-
bonding forces, such as pÁ
/
p interactions, dipoleÁ
/
dipole
ing gold(I) centers and diacetylide bridging ligands [12Á
/
attractions or hydrogen bonding, should operate in such
a way as to counteract the usual entropy effects that
favor dissociation [6,7].
15]. It has been shown that both the ‘hinge group’ in the
diacetylide ligand (X, Scheme 1) and the ‘spacer group’
between the phosphorus atoms (Z, Scheme 1) are
important in determining whether macrocyclic com-
plexes or [2]catenanes are formed as major components
in the equilibrium of Scheme 1. Short and sterically
* Corresponding author. Tel.: ꢂ
3022
E-mail address: pudd@uwo.ca (R.J. Puddephatt).
/
1-519-661-2111; fax: ꢂ1-519-661-
/
demanding spacer groups such as (CH2)2, HCÄ
/
CH, CÅ
/
C and [Fe(C5H4)2] favor macrocycles, while longer
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 2 0 7 0 - 3

28
F. Mohr et al. / Journal of Organometallic Chemistry 670 (2003) 27Á36
/
might be developed by converting an unsaturated to a
saturated hinge group X.
2. Results and discussion
The starting bis(alkyne) OÄ
was prepared in almost quantitative yield by the
C(4-C6H4OH)2 with propargyl bromide
/C(4-C6H4OCH2CCH)2, 1,
reaction of OÄ
/
and potassium carbonate [19]. Compound 1 could then
be converted into the corresponding imine derivatives
RNÄ
/
C(4-C6H4OCH2CCH)2 [RꢀOH, 2; NHC(O)NH2,
/
3; NH{C6H3-2,4-(NO2)2}, 4]. Compounds 2 and 3 were
formed by reaction of 1 with hydroxylamine hydrochlo-
ride or semicarbazide hydrochloride respectively in the
presence of base, while 4 was prepared by reaction of 1
with 2,4-dinitrophenylhydrazine (DNP) under acidic
conditions. The 4-bromomethyl-1,3-dioxolane (5) was
prepared by the tin(IV)chloride catalysed reaction of (1)
with epibromohydrin (Scheme 2) [20]. The bis(alkynes)
were readily characterized by their using H and 13C
1
Scheme 1. X, hinge group; Z, spacer group.
NMR spectra, IR and mass spectra (Section 3).
Attempts to prepare dioxolanes by reaction of 1 with
diols (ethylene glycol, propylene glycol) were unsuccess-
ful, since complete conversion was difficult to achieve
and the products hydrolysed partly during chromato-
graphy.
spacer groups such as (CH2)4 and (CH2)5 may favor the
[2]catenanes, depending on the nature of the hinge
group. The case where the spacer group is (CH2)3 often
leads to an equilibrium containing both the macrocycle
and [2]catenane, and sometimes more complex products
Reaction of the bis(alkyne) 1 with [AuCl(SMe2)] in
the presence of Et3N gave the corresponding yellow,
[12Á15]. The hinge group effect controls the twist of the
/
aryl rings of the diacetylide units with respect to the XC2
plane (Scheme 1). Twist angles of both aryl groups in the
insoluble oligomeric digold(I) diacetylide complex [{OÄ
/
range 45Á908 are good for [2]catenane formation, but
/
one or more such angles that are close to zero are not
because the macrocycle cavity is blocked by the in-plane
aryl group [12Á16]. The unfavorable twist arises when
/
the group X can form p-bonds and so conjugate with
one of the adjacent aryl groups. This p-bonding often
leads to twist angles close to 0 and 908 for the two aryl
groups, and the result is that no catenanes are formed
with p-donor hinge groups Xꢀ
/
O or S [12Á16].
/
The aim of the present work was to prepare a series of
digold(I) macrocycles derived from the diacetylene
precursor OÄ/C(4-C6H4OCH2CCH)2, in which the hinge
group X is a carbonyl group. Since the carbonyl group is
unsaturated it was considered unlikely that it would
form [2]catenanes, but the carbonyl group can be
transformed into a variety of other functional groups
[17]. Some of these, including imine derivatives such as
oximes, semicarbazones, and 2,4-dinitrophenylhydra-
zones, would retain the unsaturation of the hinge group
but others, such as cyclic ketal derivatives formed by
reaction with diols or epoxides [18], would not and so
might favor self-assembly to [2]catenanes. Hence, the
Scheme 2. Reagents: (i) BrCH2CCH, K2CO3; (ii) HONH2×
H2NC(ÄO)NHNH2×HCL; (iv) H2NNHC6H3(NO2)2;
BrCH2CHCH2O.
/
HCL; (iii)
current hypotheses about [2]catenane formation [12Á
/16]
/
/
(v)
can be tested and perhaps a catenation switch or trigger

F. Mohr et al. / Journal of Organometallic Chemistry 670 (2003) 27Á
/36
29
Scheme 3.
Scheme 5.
C(4-C6H4OCH2CCAu)2}n], 6, that could be converted
derivative 6 gave n(CÅ
/
C)ꢀ ,
2121 and 2008 cmꢁ1
respectively. The organic functional groups gave IR
/
to the soluble diphosphine derivatives 7aÁ
to Scheme 3. Similarly the imine derivatives 2Á
be converted to the insoluble digold(I) oligomers [{RNÄ
C(4-C6H4OCH2CCAu)2}n] [RꢀOH, 8; Rꢀ
NHC(O)NH2, 9; RꢀNH{C6H3-2,4-(NO2)2}, 10, and
then to the corresponding soluble diphosphine deriva-
tives 11Á13 (Scheme 4). Finally, the ketal derivative 5
was converted to the digold(I) derivative 14 and then to
the diphosphine derivatives 15aÁ15d according to
/
7e according
/
4 could
bands in the expected regions. For example, the
O)ꢀ
1647 cmꢁ1 for
/
oligomeric complex 6 gave n(CÄ
/
/
/
/
the ketone group. None of these oligomeric complexes
was sufficiently soluble to allow characterization by
NMR.
/
The soluble ketone complexes 7aÁ7e each give a
/
/
singlet in the 31P NMR spectra and a single resonance
for the OCH2 protons of the propargyl groups in the 1H
NMR spectra, assigned to the simple macrocyclic
compounds. The macrocycles evidently have effective
/
Scheme 5. These reactions all occurred in high yields.
The IR spectrum of each of the oligomeric digold(I)
complexes 6, 8Á
ca. 2000 cmꢁ1, considerably lower (ca. 100 cmꢁ1) than
those of the precursor bis(alkyne) compounds 2Á5. This
lowering of the CÅC stretch is characteristic for the
alkynyl group acting as a p-donor to the gold(I) centers
[21]. For example, bis(alkyne) 1 and its digold(I)
/
10, 14 shows a weak n(CÅ
/
C) stretch at
C2v symmetry in solution, as expected [12Á16]. The
/
structure of complex 7e, containing the diphosphine
ligand Ph2P(CH2)5PPh2, was confirmed crystallographi-
cally (Fig. 1Table 1) and shown to contain a 26-
membered macrocyclic ring.
/
/
Fig. 1. A view of the structure of complex 7e, showing two adjacent
macrocyclic rings. The closest approach of two gold atoms is the
˚
Auꢀ6.99 A; the transannular distance
intermolecular distance AuÁ
/
/
˚
Auꢀ8.61 A.
Scheme 4.
AuÁ
/
/

30
F. Mohr et al. / Journal of Organometallic Chemistry 670 (2003) 27Á36
/
Table 1
similar to those for the ketone derivatives and in the
range that does not favor catenation.
˚
Selected bond distances (A) and angles (8) in complex 7e
The cyclic ketal complexes 15 have the lowest
symmetry of the macrocycles prepared. The presence
of the chiral C*H(CH2Br)(O)(CH2) center causes the
complexes to have C1 symmetry, with all atoms inequi-
valent except for equivalent protons and carbon atoms
of the individual aryl groups. A [2]catenane could then
give four geometrical isomers since all four possible
positions of the CH2Br group on the second ring are
inequivalent (Scheme 6). The complex with the ligand
Au(1)Á
Au(1)Á
C(1)Á
C(11)Á
/
C(1)
2.028(9) Au(2)Á
/
C(22)
2.010(10)
2.269(3)
1.19(1)
/P(1)
2.280(2) Au(2)Á
/
P(2)
/
C(2)
1.18(1)
1.22(2)
C(21)ÁC(22)
/
/
O(12)
C(1)ÁAu(1)Á
C(2)Á
C(1)Á
O(12)Á
C(10)Á
/
/
P(1)
176.7(3) C(22)Á
/
Au(2)Á
C(22)Á
C(21)Á
C(11)Á
/
P(2)
174.5(3)
175(1)
173(2)
119(2)
/C(1)Á
/
Au(1)
C(3)
177(1)
179(1)
122(2)
120(1)
C(21)Á
C(22)Á
O(12)Á
/
/
Au(2)
C(20)
/C(2)Á
/
/
/
/
C(11)Á
/C(10)
/
/C(13)
/
C(11)Á
/C(13)
1
Ph2PCCPPh2 gave the macrocycle 15a whose H NMR
Fig. 1 shows two neighboring rings of complex 7e that
clearly do not catenate. The intramolecular goldÁgold
spectrum reflected the expected low symmetry but
whose 31P NMR spectrum gave only a singlet, pre-
sumably as a result of accidental degeneracy of the
chemical shifts. The structure of complex 15a was
determined and is shown in Fig. 2A, with selected
bond distances and angles in Table 2. The complex
exists in the form of a 23-membered macrocycle. There
was disorder of the atoms of the cyclic ketal unit and the
associated bromomethyl group, and these atoms are less
well defined than the rest of the structure.
/
˚
distance is 8.61 A and the closest intermolecular goldÁ
/
˚
gold distance is 6.99 A, indicating the absence of
aurophilic attractions. The neighboring rings pack so
that the phenyl group of one ring partially penetrates the
cavity of the other (Fig. 1). The twist angles of the two
aryl rings with respect to the plane of the hinge atom
C(11) are 40 and 248, and so are in the range that does
not favor catenane formation [12Á
certainly large enough to allow catenation, the minimum
ring size being established as 24-membered [12Á16], so
/16]. The ring size is
Individual rings are twisted to allow bridging by the
short-bite and rigid diphosphine ligand Ph2PCCPPh2, as
is most clearly seen in the side view of Fig. 2B. The
individual macrocycles are ordered into chains through
/
the unfavorable orientation of the aryl groups arising
from conjugation with the carbonyl group is presumed
to disfavor the threading needed for catenation.
strong inter-ring aurophilic attractions with Au
/
Á Á Á
/
Auꢀ
/
˚
3.0414(8) A as shown in Fig. 2B and C. Within each
chain, the molecules are related by a screw axis and so
have the same chirality (isotactic), but neighboring
chains have opposite chirality. It should be noted,
however, that the ketal units are disordered and so the
symmetry of these chains is almost certainly less than
the crystallographic ideal. The twist angle for each of the
aryl groups with respect to the hinge unit in 15a is 748,
and this conformation is one that should favor catena-
tion. The 23-membered ring with the rigid, short-bite
The imine complexes 11Á
sequence of the presence of the angular Ä
/
13 (Scheme 4), as a con-
NR groups,
/
have lower symmetry (Cs) compared to the ketone
derivatives 7 (C2v). Hence they are expected to give
two resonances in the 31P NMR spectra and two OCH2
1
resonances in the H NMR spectra and, in favorable
cases, this pattern was observed. For example, complex
13a gave two singlet resonances in the 31P NMR at dꢀ
/
38.28 and 38.45, and two singlet OCH2 resonances in the
1H NMR spectrum at dꢀ
4.88 and 4.96. In many cases,
only one 31P resonance was observed. For example,
/
complex 11a gave a singlet resonance at dꢀ37.22 in the
/
31P NMR, though the overall Cs symmetry is shown by
the presence of two OCH2 resonances in the 1H NMR at
dꢀ
4.79 and 4.85. Low temperature 31P NMR spectra
/
of complex 11a also gave only one 31P resonance, so it is
likely that the chemical shifts are accidentally degenerate
rather than that the phosphine groups are fluxional at
room temperature. The NMR data for the imine
complexes do not indicate formation of [2]catenanes,
and MALDI-TOF MS give parent ions for the macro-
cyclic complexes 11Á13 but no evidence for the [2]cate-
/
nanes. The [2]catenanes would be expected to be
topologically chiral and so should give more complex
NMR spectra than those observed. No crystals suitable
for structure determination were obtained for these
complexes, but it is likely that the aryl twist angles are
Scheme 6. Four isomers of 16 can have CH2Br group in positions aÁd.
/

F. Mohr et al. / Journal of Organometallic Chemistry 670 (2003) 27Á
/36
31
Fig. 2. The structure of complex 15a. (A) The 23-membered macrocycle, with one component of the disordered cyclic ketal unit. (B) A side view of
˚
four adjacent macrocycles, showing the ring twist and the aurophilic bonds that link the macrocycles [Au(1)Á
/
Au(2)ꢀ3.0414(8) A]. (C) A top view
/
along the chain direction. In (B) and (C) the phenyl groups are omitted for clarity.
diphosphine does not form a large enough cavity
however, so no catenation can occur.
Table 2
Selected bond distances (A) and angles (8) in complex 15a
The corresponding complex with the ligand
Ph2P(CH2)3PPh2 was formed as a mixture of isomers,
but crystallization gave the pure [2]catenane 16b. This
complex is sparingly soluble in CD2Cl2 but a freshly
prepared solution gave the spectrum of the [2]catenane
only. The 31P NMR spectrum contained only a singlet at
˚
Au(1)Á
Au(1)Á
C(1)Á
Au(1)Á
/
C(11)
2.01(2)
2.273(5)
1.20(2)
Au(2)Á
Au(2)Á
C(11)Á
/
C(21)
2.01(3)
2.269(5)
1.17(2)
/P(1)
/P(2)
/
C(2)
/C(12)
/Au(2A)
3.0414(8)
C(11)ÁAu(1)Á
C(2)ÁC(1)ÁP(1)
C(12)ÁC(11)ÁAu(1)
C(11)ÁC(12)ÁC(13)
/
/
P(1)
172.3(4)
177(2)
175(1)
176(2)
C(21)Á
C(1)ÁC(2)Á
C(22)ÁC(21)Á
C(21)ÁC(22)Á
/
Au(2)Á
/
P(2)
171.8(5)
174(2)
176(2)
178(2)
dꢀ31.91, while the same number of ring resonances as
/
/
/
/
/
P(2)
for the simple macrocycle 15a was observed. More
complex spectra were expected for 16b since a mixture
of several isomers is expected (Scheme 6). The presence
/
/
/
/Au(2)
/
/
/
/C(23)

32
F. Mohr et al. / Journal of Organometallic Chemistry 670 (2003) 27Á36
/
of the [2]catenane is signalled by the presence of much
more shielded aromatic resonances compared to 15a,
arising because of the tight contact with phenylpho-
Table 3
Selected bond distances (A) and angles (8) in complex 15b
˚
Au(1)Á
Au(2)Á
Au(3)Á
Au(4)Á
Au(1)Á
C(4A)Á
C(4B)ÁC(5B)
/
C(4A)
C(13A)
C(4B)
C(13B)
Au(3)
1.992(6) Au(1)Á
1.998(7) Au(2)Á
2.002(7) Au(3)Á
1.998(7) Au(4)Á
3.2672(4) Au(2)Á
1.192(9) C(12A)Á
1.187(10) C(12B)ÁC(13B)
/
P(1)
P(2)
P(3)
P(4)
Au(4)
2.272(2)
2.275(2)
2.274(2)
2.277(2)
3.2981(4)
1.198(10)
1.183(9)
sphorus groups of the interlocked ring [12Á
16b has aromatic resonances ortho to oxygen at dꢀ
6.08, 6.10, whereas 15a has these resonances at dꢀ
/
16]. Thus,
/
/
/
/
/
/
/
/
/
/
7.02, 7.05. Complex 16b slowly equilibrated with a
second isomer, identified as the simple macrocycle 15b,
over a period of days (Scheme 6). Complex 15b had a
/
C(5A)
/C(13A)
/
/
C(4A)ÁAu(1)Á
C(4B)ÁAu(3)Á
C(5A)ÁC(4A)Á
C(5B)ÁC(4B)ÁAu(3) 172.9(6) C(12B)Á
C(5A)Á 175.9(9) C(13A)Á
C(11A)
C(6B) 176.0(8) C(13B)Á
Au(3) 85.2(2) C(13A)Á
Au(1) 86.0(2) C(13B)ÁAu(4)Á
102.73(5) P(2)ÁAu(2)ÁAu(4)
101.96(5) P(4)ÁAu(4)ÁAu(2)
/
/
P(1)
170.9(2) C(13A)ÁAu(2)Á
171.9(2) C(13B)ÁAu(4)ÁP(4)
C(13A)Á
C(13B)ÁAu(4) 173.2(7)
C(12A)Á 176.1(7)
/
/
P(2)
171.9(2)
31P NMR resonance at dꢀ
resonances ortho to oxygen were at dꢀ
/
35.90, and its aromatic
/
/P(3)
/
/
173.5(2)
/7.00, 7.02. The
/
/Au(1) 169.9(7) C(12A)Á
/
/Au(2) 172.7(7)
/
/
/
/
structure of complex 16b was determined and is shown
in Fig. 3, with selected bond distances and angles in
Table 3.
The structure is clearly a [2]catenane in which two 24-
membered macrocycles are interlocked across the dipho-
sphine ligand backbones. The catenane is stabilized by
C(4A)Á
/
/
/
/
C(6A)
C(4B)Á
C(4A)Á
C(4B)ÁAu(3)Á
P(1)ÁAu(1)Á
P(3)ÁAu(3)Á
/
C(5B)Á
/
/
C(12B)Á
Au(2)ÁAu(4)
Au(2)
/
C(11B) 176.8(8)
/
Au(1)Á
/
/
/
84.3(2)
81.1(2)
/
/
/
/
/
/
Au(3)
Au(1)
/
/
102.97(5)
104.99(5)
/
/
/
/
the presence of two close goldÁ
/
gold contacts [Au(1)
/
Á Á Á
/
˚
˚
Au(3)ꢀ
as well as by several secondary phenyl-C6H4 and
phenylÁphenyl interactions. There is considerable bow-
ing of the CCAuP units, with angles CCAu and CAuP
distorted from linearity and in the range 170Á1748, in
/
3.2672(4) A and Au(2)
/
Á Á Á
/
Au(4)ꢀ/3.2981(4) A]
in a disordered manner. Only one component of the
disorder of each ketal unit is shown in Fig. 3. It seems
that the bromomethyl groups are far enough removed
from the interlocking diphosphine groups that they can
position themselves independently of one another, and
that their position also has only local influence on the
NMR parameters. The isomers will therefore have very
similar energies and essentially identical NMR spectral
properties.
/
/
order to allow closer mutual approach of pairs of gold
atoms.
The twist angles of the aryl groups with respect to the
hinge atom plane in 16b are 84, 868 for ring A and 77,
818 for ring B, in the range that favors [2]catenane
formation [12Á16]. These angles are not very different
/
Can the concept of a catenation switch be realized in
this system? The principle is established since converting
the ketone unit in 7c to the ketal unit in 15b should lead
to partial [2]catenane formation, as shown by study of
the separate systems. Unfortunately, the reaction con-
ditions needed to effect the change in functional group
(high temperature, acid catalyst) leads to decomposition
of the gold acetylide units, so a direct demonstration
was not possible. However, the ketal is susceptible to
hydrolysis and a solution of 15b in moist acetone/
dichloromethane underwent slow hydrolysis with for-
mation of 7c. This then confirms that such transforma-
tions are possible, in this case involving decatenation.
Success requires a labile metal center to allow easy
threading/dethreading, and easy transformation be-
tween functional groups that favor or disfavor the
catenation. It is likely that more successful catenation
switches will be developed based on these principles.
from the twist angles for 15a of 74, 748, but very
different from those of the ketone derivative 7e of 24,
408. Hence, in these compounds, the aryl twist angles are
primarily determined by the nature of the bonding to the
hinge group and the angles do not change markedly on
[2]catenane formation.
The interesting problem of isomerism in 16b, which
contains two chiral carbon atoms and is also topologi-
cally chiral [16], is not fully resolved by the structure
determination. The structure was modelled by a 50:50
disorder of the bromomethyl group between two posi-
tions on each ring, but there was also evidence for
further unresolved disorder. It is likely therefore that all
possible isomers are present and that they co-crystallize
3. Experimental
NMR spectra were recorded using Varian Mercury
400 and Inova 600 MHz spectrometers. 1H and 13C
NMR chemical shifts are reported relative to tetra-
methylsilane, while 31P chemical shifts are reported
relative to 85% H3PO4 as an external standard. IR
Fig. 3. The [2]catenane structure of complex 15b, showing the inter-
ring aurophilic attractions [Au(1)Á
/
Au(3)ꢀ
/
3.2672(4); Au(2)Á
/
Au(4)ꢀ
/
˚
3.2981(4) A].

F. Mohr et al. / Journal of Organometallic Chemistry 670 (2003) 27Á
/36
33
spectra were recorded using a Perkin Elmer 2000 FT-IR
as KBr disks. MALDI-TOF mass spectra were recorded
using a Micromass MALDI-LR instrument in positive
ion mode. The samples were dissolved in CH2Cl2 and
spotted onto a dried layer of matrix (1 ml a-cyano-4-
hydroxycinnamic acid 10 mg/ml in CAN/EtOH 50:50).
The samples were analysed in reflection mode and MS
spectra were externally calibrated using a tryptic digest
of alcohol dehydrogenase. All reactions involving gold
complexes were carried out in reactions vessels shielded
from light. The complex [AuCl(SMe2)] was prepared by
a literature procedure [22].
3.3. HONÄ
/
C(4-C6H4OCH2CCH)2, 3
A mixture of 1 (0.50 g, 1.72 mmol) and hydroxyla-
mine hydrochloride (0.50 g, 7.30 mmol) in EtOH (10 ml)
and pyridine (2.5 ml) was heated under reflux for 24 h.
The solvents were removed under vacuum and water (30
ml) was added to the residue. The resulting oil was
extracted into ether and the organic phase was washed
with 5% HCl and water. Evaporation of the solvent gave
1
a white solid (0.42 g, 80%). H NMR (DMSO-d6) d
3.50, 3.53 (t, Jꢀ
2.4 Hz, 2H, OCH2), 6.87, 6.94, 7.16, 7.21 (d, Jꢀ
2H, C6H4), 11.00 (s, 1H, OH); 13C NMR (DMSO-d6) d
55.27, 55.31 (OCH2), 78.21 (ÅCH), 78.92, 79.03
(OCH2C Å), 114.00, 114.34, 125.96, 128.19, 129.97,
130.27, 156.69, 157.31 (C6H4), 153.89 (C ÄN); EI-MS
m/z 305 [M]ꢂ, 288 [MÁOH]ꢂ; IR (KBr disk, cmꢁ1
3287 (s, ÅCH), 3070 (br, OH), 2125 (w, CÅC); Anal.
/
2.4 Hz, 1H, Å
/
CH), 4.71, 4.75 (d, Jꢀ
/
/
8.6 Hz,
/
/
3.1. OÄ
/
C(4-C6H4OCH2CCH)2, 1
CH (2.2 g, 18.6 mmol) and K2CO3 (1.6 g,
/
/
)
BrCH2CÅ
/
/
/
13.7 mmol) was added to a solution of OC(4-C6H4OH)2
(2.0 g, 9.3 mmol) in acetone (60 ml). The mixture was
heated under reflux for about 24 h. The cooled solution
was filtered to give a pale yellow filtrate. The solvent
was removed under reduced pressure and the resultant
Found: C, 74.77; H, 5.14; N, 4.88. Calc. for C19H15NO3:
C, 74.74; H, 4.95; N, 4.50.
3.4. H2NC(O)NHNÄ
/
C(4-C6H4OCH2CCH)2, 4
1
off-white solid dried in vacuum. Yield: 2.6 g, 95%. H
This was prepared similarly from 1 (0.50 g, 1.72
mmol) and semicarbazide hydrochloride (0.50 g, 4.48
1
mmol). Yield: 0.40 g (67%). H NMR (DMSO-d6) d
NMR (CDCl3) d 2.58 (t, Jꢀ
Jꢀ2.4 Hz, 4H, OCH2), 7.03, 7.78 (d, Jꢀ
C6H4); 13C NMR (CDCl3) d 55.8 (OCH2), 76.1 (Å
77.8 (OCH2C), 114.1, 131.1 131.9, 160.4 (C6H4), 193.9
(C Ä
O); EI-MS m/z 291 [M]ꢂ; IR (KBr disk, cmꢁ1
3300, 3271 (s, ÅCH), 2121 (w, CÅC), 1646 (s, CÄO).
/
2.4 Hz, 2H, Å
/
CH), 4.77 (d,
8.6 Hz, 4H,
CH),
/
/
/
3.58, 3.65 (t, Jꢀ
2.4 Hz, 2H, OCH2), 6.63 (br. s, 2H, NH2), 6.94, 7.17,
7.22, 7.48 (d, Jꢀ8.6 Hz, 4H, C6H4), 7.79 (br. s, 1H,
NH); 13C NMR (DMSO-d6) d 56.27, 56.35 (OCH2),
79.16, 79.36 (ÅCH), 79.81, 79.83 (OCH2C Å), 115.19,
116.43, 125.32, 128.94, 130.48, 131.42, 158.34 (C6H4),
146.75 (CÄN), 156.50 (C ÄO); HR-MS found m/z
347.12639, calculated for C20H17N3O3 m/z 347.12699;
IR (KBr disk, cmꢁ1) 3476, 3454 (s, Å
CH), 3286, 3206
(br. s NH, NH2), 2124 (w, CÅC), 1696 (s, CÄO).
/
2.4 Hz, 1H, CÅ
/
CH), 4.81, 4.89 (d, Jꢀ
/
/
)
/
/
/
/
/
/
3.2. 2,4-(NO2)2C6H3NÄ
/
C(4-C6H4OCH2CCH)2, 2
/
/
2,4-Dinitrophenyl hydrazine (0.25 g, 1.26 mmol) was
suspended in MeOH (5 ml) and concentrated sulfuric
acid (0.5 ml) was added with cooling to give a yellow
solution. To this was added suspension of 1 (0.35 g, 1.21
mmol) in MeOH (5 ml) and the mixture heated under
reflux for 30 min. The resulting brick red precipitate was
isolated by filtration and washed with water (200 ml).
The dried solid was recrystallized from 1-BuOH to give
0.52 g (91%) brick red feathery needles. 1H NMR
/
/
/
3.5. OCH2CH(CH2Br)OC(4-C6H4OCH2CCH)2, 5
Stannic chloride (344 ml 1.0 M solution in CH2Cl2,
3.44 mmol) was added slowly to a solution of epibro-
mohydrin (0.548 g, 4.00 mmol) and 1 (1.00 g, 3.44
mmol) in dichloromethane (20 ml). The reaction mixture
was stirred at room temperature for 2.5 h, then
neutralised by addition of potassium carbonate and
concentrated in vacuum. Ether (30 ml) was added to the
residue and the etheral extract was washed with water,
dried and concentrated in vacuum to give a pale yellow
(CD2Cl2) d 3.15, 3.25 (t, Jꢀ
4.78 (d, Jꢀ2.4 Hz, 2H, OCH2), 7.10, 7.30, 7.45, 7.68 (d,
Jꢀ8.6 Hz, 4H, C6H4), 8.32 (d, Jꢀ9.4 Hz, 1H, DNP),
8.44 (dd, Jꢀ9.8/2.7 Hz, 1H, DNP), 8.95 (d, Jꢀ2.3 Hz,
1H, DNP), 11.20 (s, 1H, NH); 13C NMR (CD2Cl2) d
56.41, 56.58 (OCH2), 76.19, 76.42 (ÅCH), 78.54, 78.65
(OCH2C Å), 115.25, 116.68, 117.07, 123.94, 125.20,
129.94, 130.10, 130.41, 130.52, 130.89, 138.31, 145.10,
159.44, 159.84 (C6H4), 155.56 (C ÄN); EI-MS m/z 470
[M]ꢂ; IR (KBr disk, cmꢁ1) 3310 (w, NH), 3290, 3271 (s,
C); Anal. Found: C, 63.83; H, 3.86;
/
2.4 Hz, 1H, Å/CH), 4.78,
/
/
/
/
/
1
/
oil (0.892 g, 61%). H NMR (CD2Cl2) d 2.57, 2.58 (m,
/
1H, Å
1H, CHOCH2), 4.43 (m, 1H, HC), 4.69, 4.70 (m, 2H,
OCH2CÅ
), 6.91, 6.94, 7.39, 7.41 (m, 2H, C6H4); 13C
NMR (CD2Cl2) d 34.90 (CH2Br), 55.84 (OCH2CÅ),
CH), 77.74 (C Å
/CH), 3.36, 3.52 (m, 1H, CH2Br), 3.94, 4.01 (m,
/
/
/
Å
/
CH), 2127 (w, CÅ
/
69.16 (CHOCH2), 75.85 (HC), 76.27 (Å
/
/
N, 11.75. Calc. for C25H18N4O6: C, 63.83; H, 3.86; N,
11.91.
CH), 113.90, 114.22, 130.98, 132.01, 135.26, 135.58,
160.48 (C6H4); HR-MS found m/z 426.0467, calc. for

34
F. Mohr et al. / Journal of Organometallic Chemistry 670 (2003) 27Á36
/
C22H19BrO4 m/z 426.0467; IR (neat on NaCl plates,
cmꢁ1) 3302 (s, Å
CH), 2123 (w, CÅC).
4H, C6H4); 31P NMR (CD2Cl2) d 38.69. 7e: Anal.
Found: C, 50.95; H, 3.73. Calc. for C48H42Au2O3P2: C,
/
/
1
51.35; H, 3.77. H NMR (CD2Cl2) d 1.50 (br. s, 6H,
CH2), 2.29 (br. s, 4H, CH2), 4.80 (s, 4H, OCH2), 7.10 (d,
3.6. [OÄ
/
C(4-C6H4OCH2CCAu)2]n, 6
Jꢀ
(d, Jꢀ
/
8.6 Hz, 4H, C6H4), 7.33Á
/
7.60 (m, 20H, PPh2), 7.73
8.6 Hz, 4H, C6H4); 31P NMR (CD2Cl2) d 37.44.
11a: Anal. Found: C, 50.01; H, 3.53; N, 1.02. Calc. for
To a solution of [(Me2S)AuCl] (1.31 mmol) in THF
(40 ml) and MeOH (20 ml) was added a solution of
compound 1 (0.655 mmol) in THF (20 ml) and Et3N
(2.16 mmol, 0.3 ml). Instantly a yellow precipitate
formed. The mixture was stirred for 2 h and then the
precipitate isolated by filtration. The solid was washed
with THF, MeOH, Et2O and pentane and then dried in
/
1
C47H41Au2NO3P2: C, 49.77; H, 3.54; N, 1.26. H NMR
(CD2Cl2) d 1.86 (br. s, 2H, CH2), 2.77 (br. s, 4H, CH2),
4.79, 4.85 (s, 2H, OCH2), 6.84Á
PPh2); 31P NMR (CD2Cl2) d 34.54; MALDI-TOF MS
(m/z) 1110 [Mꢂ
H]ꢂ. 11b: Anal. Found: C, 44.76; H,
3.77; N, 1.03. Calc. for C47H41Au2NO3P2×6H2O: C,
45.15; H, 4.44; N, 1.12. H NMR (CD2Cl2) d 1.74, 2.41
(br. s, 4H, CH2), 4.80, 4.85 (s, 2H, OCH2), 6.87Á7.74
(m, 28H, C6H4, PPh2); 31P NMR (CD2Cl2) d 37.22;
MALDI-TOF MS (m/z) 1124 [Mꢂ
H]ꢂ. 12a: Anal.
Found: C, 48.47; H, 3.68; N, 3.53. Calc. for
C47H41Au2N3O3P2×1/4CH2Cl2: C, 48.37; H, 3.58; N,
3.58. H NMR (CDCl3) d 1.56 (br. s, 2H, CH2), 2.64
(br. s 4H, CH2), 4.82, 4.87 (s, 2H, OCH2), 6.64 (d, Jꢀ
9.4 Hz, 2H, C6H4), 7.42Á7.76 (m, 29H, C6H4, PPh2,
NH2, NH); 31P NMR (CDCl3) d 35.45; MALDI-TOF
MS (m/z) 1152 [Mꢂ
H]ꢂ. 12b: Anal. Found: C, 49.03;
/7.77 (m, 28H, C6H4,
/
air. Yield: 80%. IR (KBr disk, cmꢁ1) 2008 (w, CÅ
1647 (s, CÄO); Anal. Found: C, 33.52; H, 1.72. Calc. for
C19H12Au2O3: C, 33.45; H, 1.77.
Similarly were prepared: [2,4-(NO2)2C6H3NÄ
C(4-6H4OCH2CCAu)2]n, 8, IR (KBr disk, cmꢁ1) 3284
(m, NH), 2007 (w, CÅC), 1624 (s, CÄN); Anal. Found:
C, 34.38; H, 1.89; N, 6.33. Calc. for C25H16Au2N4O6: C,
34.82; H, 1.87; N, 6.50. [HONÄC(4-C6H4OCH2C-
CAu)2]n, 9, IR (KBr disk, cmꢁ1) 3382 (bs, OH), 2002
(w, CÅC). [H2NC(O)NHNÄC(4-C6H4OCH2CCAu)2]n,
10, IR (KBr disk, cmꢁ1) 3479, 3348 (s, NH, NH2), 2010
(w, CÅC), 1680 (s, CÄO). [OCH2CH(CH2Br)OC(4-
C6H4OCH2CCAu)2]n, 14, IR (KBr disk, cmꢁ1) 2013
(w, CÅC); Anal. Found: C, 32.77; H, 2.03. Calc. for
C19H12Au2O3: C, 32.26; H, 2.09.
/
C),
/
1
/
/
/
/
/
/
/
1
/
/
/
/
/
/
/
/
H, 3.78; N, 3.55. Calc. for C48H43Au2N3O3P2: C, 49.43;
1
H, 3.72; N, 3.61. H NMR (CDCl3) d 1.58, 2.68 (br. s,
/
4H, CH2), 4.75, 4.86 (s, 2H, OCH2), 6.97 (d, Jꢀ
C6H4), 7.44Á
7.74 (m, 29H, C6H4, PPh2, NH, NH2); 31P
NMR (CDCl3) d 38.55; MALDI-TOF MS (m/z) 1166
/9.4 Hz,
/
3.7. [OÄ
/
C(4-C6H4OCH2CC)2Au2(Ph2PCCPPh2)], 7a
[Mꢂ
H]ꢂ. 13a: Anal. Found: C, 48.73; H, 3.30. Calc. for
/
A mixture of digold(I) diacetylide oligomer [OÄ
/
C52H42Au2N4O6P2: C, 48.97; H, 3.32. 1H NMR
(CDCl3) d 1.82, 2.76 (br. s, 4H, CH2), 4.88, 4.96 (s,
C(4-6H4OCH2CCAu)2]n, 6 (0.108 mmol) and dipho-
sphine Ph2PCCPPh2 (0.091 mmol) was stirred in CH2Cl2
(20 ml) for 3 h. After this time the resulting solution was
filtered through Celite and concentrated in vacuum.
Addition of pentane precipitated the product, which was
isolated by filtration, washed with Et2O and pentane,
and dried under vacuum. Yield: 70%. Anal. Found: C,
49.95; H, 2.89. Calc. for C45H32Au2O3P2: C, 50.20; H,
2H, OCH2), 7.18 (d, Jꢀ
(m, 24H, PPh2, C6H4), 7.71 (d, Jꢀ
8.20 (d, Jꢀ9.6 Hz, 1H, DNP), 8.34 (dd, Jꢀ
1H, DNP), 9.03 (d, Jꢀ2.7 Hz, 1H, DNP), 11.19 (s, 1H,
NH); 31P NMR (CD2Cl2) d 38.28, 38.45; MALDI-TOF
MS (m/z) 1275 [Mꢂ
H]ꢂ. 13b: Anal. Found: C, 45.25;
H, 3.38; N, 3.48. Calc. for C53H44Au2N4O6P2×2CH2Cl2:
/
8.6 Hz, 2H, C6H4), 7.41Á
8.6 Hz, 2H, C6H4),
9.6, 2.7 Hz,
/
7.68
/
/
/
/
/
/
1
1
3.00. H NMR (CD2Cl2) d 4.88 (s, 4H, OCH2), 7.21 (d,
C, 45.32; H, 3.32; N, 3.85. H NMR (CD2Cl2) d 1.77,
2.39 (br. s, 4H, CH2), 4.85, 4.96 (s, 2H, OCH2), 7.16 (d,
Jꢀ
7.75 (m, 8H, PPh2), 7.77 (d, Jꢀ
NMR (CD2Cl2) d 18.25.
/
7.8 Hz, 4H, C6H4), 7.46Á
/
7.60 (m, 12H, PPh2), 7.68Á
/
/
7.8 Hz, 4H, C6H4); 31P
Jꢀ
/
8.6 Hz, 2H, C6H4), 7.41Á/7.68 (m, 24H, PPh2, C6H4),
7.71 (d, Jꢀ
/
8.6 Hz, 2H, C6H4), 8.20 (d, Jꢀ/9.6 Hz, 1H,
Similarly were prepared from the appropriate di-
gold(I) diacetylide and diphosphine ligand: 7b: Anal.
Found: C, 50.02; H, 3.19. Calc. for C45H34Au2O3P2: C,
50.11; H, 3.18. 1H NMR (CD2Cl2) d 4.87 (s, 4H,
DNP), 8.34 (dd, Jꢀ
/
9.6, 2.7 Hz, 1H, DNP), 9.03 (d, Jꢀ
/
2.7 Hz, 1H, DNP), 11.19 (s, 1H, NH); 31P NMR
(CD2Cl2) d 38.28, 38.45; MALDI-TOF MS (m/z) 1289
[Mꢂ
H]ꢂ. 13c: Anal. Found: C, 49.85; H, 3.57; N, 4.50.
Calc. for C54H46Au2N4O6P2: C, 49.78; H, 3.56; N, 4.30.
/
OCH2), 6.97 (t, Jꢀ
8.7 Hz, 4H, C6H4), 7.48Á
Jꢀ
8.7 Hz, 4H, C6H4); 31P NMR (CD2Cl2) d 39.35. 7c:
/
20.6 Hz, 2H, HCÄ
/
), 7.25 (d, Jꢀ
/
/
7.62 (m, 20H, PPh2), 7.70 (d,
1H NMR (CD2Cl2) d 1.57 (br. s, 6H, CH2), 2.37 (br. s,
/
4H, CH2), 4.84, 4.93 (s, 2H, OCH2), 7.15Á
PPh2, C6H4), 7.64 (d, Jꢀ8.6 Hz, 2H, C6H4), 8.19 (d,
Jꢀ9.4 Hz, 1H, DNP), 8.33 (dd, Jꢀ9.4, 2.3 Hz, 1H,
DNP), 9.02 (d, Jꢀ2.3 Hz, 1H, DNP), 11.28 (s, 1H,
/7.57 (m, 26H,
Anal. Found: C, 49.99; H, 3.21. Calc. for
C46H38Au2O3P2: C, 50.47; H, 3.50. 7d: Anal. Found:
C, 50.44; H, 3.36. Calc. for C47H40Au2O3P2: C, 50.91;
/
/
/
/
1
H, 3.64. H NMR (CD2Cl2) d 1.78, 2.41 (br. s, 2H,
8.8 Hz, 4H,
8.8 Hz,
NH); 31P NMR (CD2Cl2) d 37.20; MALDI-TOF MS
CH2), 4.89 (s, 4H, OCH2), 7.20 (d, Jꢀ
/
(m/z) 1303 [Mꢂ
/
H]ꢂ. 15a: Anal. Found: C, 47.52; H,
1
3.12. Calc. for C48H37Au2BrO4P2: C, 47.50; H, 3.07. H
C6H4), 7.43Á7.68 (m, 20H, PPh2), 7.79 (d, Jꢀ
/
/

F. Mohr et al. / Journal of Organometallic Chemistry 670 (2003) 27Á
/36
35
NMR (CD2Cl2) d 3.31, 3.50 (m, 1H, BrCH2), 3.91, 4.07
(m, 1H, CHOCH2), 4.39 (m, 1H, CH), 4.79, 4.80 (s, 2H,
4. Structure determinations
Data for 6d, 10a and 10b were collected at ꢁ
using a Nonius Kappa CCD diffractometer operating
/
73 8C by
OCH2), 7.02, 7.05 (d, Jꢀ
/
8.6 Hz, 4H, C6H4), 7.31Á7.77
/
(m, 24H, C6H4, PPh2); 31P NMR (CD2Cl2) d 18.76. 15b/
16b: Anal. Found: C, 48.04; H, 3.68. Calc. for
C49H43Au2BrO4P2: C, 47.78; H, 3.52. 15b (ring): 1H
NMR (CD2Cl2) d 1.80 (m, 2H, CH2), 2.46 (m, 4H,
CH2), 3.34, 3.52 (m, 1H, BrCH2), 3.92, 4.11 (m, 1H,
CHOCH2), 4.48 (m, 1H, CH), 4.80, 4.81 (br. m, 4H,
with MoÁKa radiation using COLLECT software [23].
/
The unit cell parameters were calculated and refined
from the full data set. Crystal cell refinement and data
reduction was carried out using DENZO and absorption
correction was carried out using SCALEPACK [23].
Hydrogen atoms were included at geometrically deter-
mined positions riding on their respective carbon atoms.
All calculations were performed using the SHELXTL 5.1
crystallographic software package [24]. The crystallo-
graphic details for the complexes are listed in Table 4.
7e. CH3CN: A colorless plate was mounted on a glass
fibre. All of the non-hydrogen atoms were refined with
anisotropic thermal parameters.
15a. 1.3CH2Cl2: A colorless needle was mounted on a
glass fibre. The five-membered ring connected at C31
was disordered and was modelled as three parts with
50:30:20 occupancy, while two solvent molecules with
0.8 and 0.5 occupancy were refined anisotropically and
isotropically, respectively. The bond lengths of the
disordered ring were fixed with reasonable values and
were refined isotropically. The bond distances of the
dichloromethane molecules were also fixed. All other
non-hydrogen atoms were refined anisotropically.
15b. 3.5CHCl3: A colorless square prism was mounted
on a glass fibre. There was disorder in the five
membered ring hinge groups with a bromomethyl
OCH2), 7.00, 7.02 (m, 4H, C6H4), 7.3Á7.8 (m, 24H,
/
C6H4, PPh2); 31P NMR (CD2Cl2) d 35.90. 16b (cate-
nane): 1H NMR (CD2Cl2) d 1.53 (m, 2H, CH2), 2.16 (m,
4H, CH2), 3.02, 3.29 (m, 1H, BrCH2), 3.72, 3.88 (m, 1H,
CHOCH2), 4.21 (m, 1H, CH), 4.65 (br. m, 4H, OCH2),
6.08, 6.10 (d, Jꢀ
Hz, 2H, C6H4), 7.30Á
/
8 Hz, 2H, C6H4), 6.93, 6.95 (d, Jꢀ
/
8
/
7.42 (m, 20H, PPh2); 31P NMR
(CD2Cl2) d 31.91. 15c: Anal. Found: C, 47.77; H, 3.59.
Calc. for C50H45Au2BrO4P2: C, 48.21; H, 3.64. 1H
NMR (CD2Cl2) d 1.71 (br. s, 4H, CH2), 2.33 (br. s,
4H, CH2), 3.33, 3.52 (m, 1H, BrCH2), 3.93, 4.09 (m, 1H,
CHOCH2), 4.42 (m, 1H, CH), 4.79, 4.80 (s, 4H, OCH2),
7.03, 7.05 (d, Jꢀ
/
9 Hz, 4H, C6H4), 7.41Á7.63 (m, 24H,
/
C6H4, PPh2); 31P NMR (CD2Cl2) d 38.89. 15d: Anal.
Found: C, 49.03; H, 3.88. Calc. for C51H47Au2BrO4P2:
1
C, 48.63; H, 3.76. H NMR (CD2Cl2) d 1.55 (br. s, 6H,
CH2), 2.34 (br. s, 4H, CH2), 3.36, 3.54 (m, 1H, BrCH2),
3.95, 4.10 (m, 1H, CHOCH2), 4.43 (m, 1H, CH), 4.79,
4.80 (s, 4H, OCH2), 7.03, 7.05 (d, Jꢀ
7.39Á
7.67 (m, 24H, C6H4, PPh2); 31P NMR (CD2Cl2) d
37.55.
/8.6 Hz, 4H, C6H4),
/
Table 4
Crystallographic data for compounds 7e, 15a and 15b
7e. MeCN
15a. 1.3CH2Cl2
15b. 3.5CHCl3
Formula
C50H45Au2NO3P2
1163.74
Triclinic
C49.5H40Au2BrCl3O4P2
1323.96
Monoclinic
P21/n
C101.5H89.5Au4Br2Cl10.5O8P4
2881.02
Triclinic
Formula weight
Crystal system
Space group
¯
¯
P/
1
/
P/
1
/
˚
a (A)
13.0195(4)
14.0979(5)
14.2496(6)
62.937(2)
70.657(2)
80.313(2)
2197.15(14)
2
19.1699(8)
14.0774(10)
20.2440(12)
90
17.9062(2)
18.3527(2)
19.2385(3)
100.076(1)
110.919(1)
108.954(1)
5273.81(12)
2
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
112.671(3)
90
3
˚
V (A )
Z
5041.0(5)
4
1.744
rcalc (g cmꢁ3
)
1.759
6.785
1128
1.814
6.684
2774
m (mmꢁ1
F(0 0 0)
)
6.848
2538
Absorption correction
u limits (8)
Measured reflections
Unique reflections
Parameters
GOF on F2
Integration
2.68/27.57
23 584
Integration
2.58/25.16
25 035
Integration
2.61/30.06
68 348
10 010
475
1.102
7728
506
30 686
1075
1.039
1.044
R1, wR2 [I ꢀ/2s(I)]
0.0602, 0.1614
0.0747, 0.1870
0.0535, 0.1227

36
F. Mohr et al. / Journal of Organometallic Chemistry 670 (2003) 27Á36
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substituent. This disorder was modelled as a mixture of
two half occupancy groups. The atoms of these rings
were modelled isotropically, except for the bromine
atoms of one set of bromethyl groups which were
anisotropic. There were indications of a third disorder
component of one ring, but no suitable model could be
refined. The half occupancy chloroform molecule was
modelled isotropically. All other non-hydrogen atoms
were refined with anisotropic thermal parameters.
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Crystallographic data for the structural analyses have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC No’s 193955, 193956, 193957.
Copies of this information may be obtained free of
charge from The Director, CCDC, 12 Union Road,
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