The role of secondary interactions in group 11 metal complexes containing the ferrocene ligand FcCH2NHpyMe in supramolecular structures

Article abstract of DOI:10.1002/ejic.200400479

The ferrocene ligand 6-[(ferrocenylmethyl)amino]-2-picoline, FcCH ₂NHpyMe [Fc = (η⁵-C₅H₅) Fe(η⁵-C₅H₄)], has been prepared by treatment of FcCH₂NMe₂ with 6-amino-2-picoline, NH ₂pyMe. The coordination chemistry with group 11 metals has been studied and several complexes with coordination of the metal atom to the pyridine nitrogen atom, such as [M(PPh₃)(FcCH₂NHpyMe)]OTf, [Au(C₆F₅)(FcCH₂NHpyMe)] and [AuR ₃(FcCH₂NHPyMe)] (M = Au, Ag; R₃ = (C ₆F₅)₃, (C₆F₅) ₂Cl; OTf = trifluoromethanesulfonate), have been obtained. The complex [Cu(FcCH₂NHpyMe)₂]PF₆ has also been synthesised with a probable coordination of the copper centre to the pyridine and amine nitrogen atoms. Deprotonation of the NH group allows the synthesis of dinuclear complexes of the type [M₂(PPh₃) ₂(FcCH₂NpyMe)]X or [Au₂(C₆F ₅)(PPh₃)(FcCH₂NPyMe)] with a mixed pyridine-amide ligand. Some of the complexes have been characterised by X-ray diffraction and show the presence of intramolecular aurophilic interactions in the dinuclear complex and intermolecular interactions leading to chains in the mononuclear complex. Other types of secondary bonds are present in these structures, such as hydrogen bonding and weak η² interactions between the gold centre and the cyclopentadienyl ring. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200400479

FULL PAPER
The Role of Secondary Interactions in Group 11 Metal Complexes Containing
the Ferrocene Ligand FcCH2NHpyMe in Supramolecular Structures
[a]
[a]
[a]
[b]
´
Eva M. Barranco, Olga Crespo, M. Concepcion Gimeno,* Peter G. Jones, and
Antonio Laguna[a]
Keywords: Ferrocenyl derivatives / Group 11 compounds / Supramolecular chemistry / Aurophilic attractions / N ligands
The ferrocene ligand 6-[(ferrocenylmethyl)amino]-2-picoline,
complexes of the type [M2(PPh3)2(FcCH2NpyMe)]X or
FcCH2NHpyMe [Fc = (η5-C5H5)Fe(η5-C5H4)], has been pre- [Au2(C6F5)(PPh3)(FcCH2NpyMe)] with a mixed pyridine−
pared by treatment of FcCH2NMe2 with 6-amino-2-picoline,
NH2pyMe. The coordination chemistry with group 11 metals
has been studied and several complexes with coordination of
the metal atom to the pyridine nitrogen atom, such as
[M(PPh3)(FcCH2NHpyMe)]OTf, [Au(C6F5)(FcCH2NHpyMe)]
amide ligand. Some of the complexes have been charac-
terised by X-ray diffraction and show the presence of intra-
molecular aurophilic interactions in the dinuclear complex
and intermolecular interactions leading to chains in the
mononuclear complex. Other types of secondary bonds are
and [AuR3(FcCH2NHpyMe)] (M = Au, Ag; R3 = (C6F5)3, present in these structures, such as hydrogen bonding and
(C6F5)2Cl; OTf = trifluoromethanesulfonate), have been ob-
tained. The complex [Cu(FcCH2NHpyMe)2]PF6 has also
been synthesised with a probable coordination of the copper
weak η2 interactions between the gold centre and the cyclo-
pentadienyl ring.
centre to the pyridine and amine nitrogen atoms. Depro- ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
tonation of the NH group allows the synthesis of dinuclear
Germany, 2004)
Introduction
dine groups. In our work with ferrocene derivatives[6] we
have observed that the ferrocenyl group confers a great deal
of stability on these types of ligands. Consequently, in this
case, it is possible to coordinate the pyridine nitrogen atom
to the metal fragments and also to substitute the proton
Gold complexes with nitrogen ligands, especially with
amine ligands, have not been extensively studied until re-
cently perhaps because of their limited stability.[1] This can
be rationalised in terms of incompatibility between the soft
metal centre and the hard nitrogen donor. Additional stabil-
isation of these compounds may be provided by aurophilic
interactions or by formation of NϪH···X hydrogen bonds.
In this manner, several complexes of stoichiometry [AuClL]
have been recently reported.[2] Stabilisation of these com-
plexes with a phosphane ligand is also possible and several
examples of the type [AuL(PR3)]ϩ are known.[3] However,
complexes in which there are more than one type of nitro-
gen donor atoms in the same ligand are not frequent. As far
as we are aware there is only one gold() derivative, namely
[(AuPPh3)4NQuin]BF4 (NQuin ϭ 8-quinolinaminato),[4]
with a pyridineϪimido ligand as well as some gold() com-
pounds with amineϪamide ligands.[5] Here we report the
synthesis of several gold, silver and copper complexes con-
taining the ligand FcCH2NHpyMe which has two types of
nitrogen donor atoms belonging to the amine and the pyri-
ϩ
in the NH group with the isolobal fragments AgPPh3 or
AuPPh3ϩ, leading to the formation of the mixed gold or
silver complexes with the pyridineϪamide ligands. The
crystal structure determinations provide experimental evi-
dence for the importance of secondary bonds in the molec-
ular architectures. Here, aurophilic interactions and hydro-
gen bonding are present in some of the complexes as illus-
trated by X-ray diffraction.
Results and Discussion
Synthesis of the Complexes
The reaction of FcCH2NMe2 with 6-amino-2-picoline
(NH2pyMe) in acetic acid gives the ferrocene ligand
FcCH2NHpyMe (1) [Equation (1)]. A closely related ferro-
cene derivative, FcCONHpyMe, has previously been re-
ported and the effect of protonation on the spectroscopic
and redox properties was studied.[7] Compound 1 has been
characterised by NMR spectroscopy and its 1H NMR spec-
trum shows the three resonances for the three types of pyri-
dine protons as two doublets and a doublet of doublets
[a]
´
´
Departamento de Quımica Inorganica, Instituto de Ciencia de
´
Materiales de Aragon, Universidad de Zaragoza-C.S.I.C.,
50009 Zaragoza, Spain
[b]
Institut für Anorganische und Analytische Chemie der
Technischen Universität Braunschweig,
Postfach 3329, 38023 Braunschweig, Germany
4820
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejic.200400479
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Role of Secondary Interactions in Group 11 Metal Complexes Containing a Ferrocene Ligand
FULL PAPER
with the NH signal at δ ϭ 4.73 ppm, the signal of the meth- or broad (in 3) resonance appears. At Ϫ55 °C the broad
ylene protons at δ ϭ 4.12 ppm and the cyclopentadienyl singlet from 3 splits into two doublets because of the coup-
proton signals at δ ϭ 4.10, 4.19 and 4.22 ppm in a ratio of ling with the 109,107Ag nuclei. The positive liquid secondary-
2:5:2, respectively. The positive liquid secondary-ion mass ion mass spectra (LSIMSϩ) exhibit the molecular peaks at
spectrum (LSIMS) exhibits the molecular peak at m/z ϭ m/z (%) ϭ 917 (5) [2] or 825 (12) [3] or the cationic peaks
306 as the most intense.
[M Ϫ OTf] at m/z (%) ϭ 765 (95) [2] or 676 (30) [3].
The reaction of ligand 1 with the oxonium compound
[O(AuPPh3)3]ClO4 proceeds with the deprotonation of the
ϩ
NH group and coordination of two AuPPh3 fragments to
the amine nitrogen atom and to the pyridine group, giving
the complex [Au2(PPh3)2(FcCH2NpyMe)]ClO4 (4). This de-
rivative, with triflate as counter anion, is also accessible by
treatment of complex 2 with [Au(acac)(PPh3)]. The anal-
ogous silver derivative [Ag2(PPh3)2(FcCH2NpyMe)]OTf (5)
(1)
The reactivity of ligand 1 towards several gold, silver and can be obtained by treatment of 3 with [Ag(OTf)(PPh3)] in
copper compounds has been studied. Thus, treatment of 1 the presence of triethylamine. The IR spectra show absorp-
with [M(OTf)PPh3] in a 1:1 molar ratio affords complexes tions from the perchlorate anion at ν˜ ϭ 1096 (vs, br.) and
of stoichiometry [M(PPh3)(FcCH2NHpyMe)]OTf [M ϭ Au 623 (m) cmϪ1 for 4 and for 5 the typical absorptions for the
(2), Ag (3)] (see Scheme 1).
trifluoromethanesulfonate anion can be observed. In the 1H
Complexes 2Ϫ3 are air- and moisture-stable yellow NMR spectra the resonances for the ferrocenyl protons ap-
solids. Their IR spectra show bands for the trifluorome- pear as two singlets for the methyl and unsubstituted Cp
thanesulfonate group at ν˜ ഠ 1265 [vs, br., νas(SO3)], 1223 groups, three multiplets for the α and β protons of the sub-
[s, νs(CF3)], 1150 [s, νas(CF3)] and 1023 [s, νs(SO3)] cmϪ1
.
stituted Cp group and for the methylene protons. The res-
1
The H NMR spectra for both complexes show broad sig- onance of the NH group disappears. For the pyridine pro-
nals at δ ഠ 4.3 ppm where the resonances for the ferrocenyl, tons, only two resonances can be observed because the third
methylene and NH protons are overlapping. The signals of overlaps with the signals from the phenyl protons. The
only two of the pyridine protons can be observed because 31P(1H) NMR spectrum of complex 4 shows two reson-
that of the other is also overlapping with those of the phe- ances for the two inequivalent phosphorus atoms. For com-
nyl protons. In the 31P(1H) NMR spectra one sharp (in 2) pound 5 the spectrum at room temperature consists of two
Scheme 1. i) [M(OTf)(PPh3)], ii) [O(AuPPh3)3]ClO4 or 2 [Ag(OTf)(PPh3)] ϩ NEt3, iii) [Au(C6F5)(tht)], iv) [Au(acac)(PPh3)], v) [Au-
(C6F5)3(OEt2)] or 1/2 [Au(C6F5)2Cl]2, vi) 1/2 [Cu(NCMe)4]PF6
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E. M. Barranco, O. Crespo, M. C. Gimeno, P. G. Jones, A. Laguna
FULL PAPER
broad signals that split at Ϫ55 °C into four doublets as a LSIMSϩ spectra the molecular peaks appear at m/z (%) ϭ
consequence of the coupling of two inequivalent phos- 1004 (5) and 872 (100), respectively.
phorus atoms with the two silver nuclei. In the LSIMSϩ
A copper derivative [Cu{(FcCH2NHpyMe)}2]PF6 (10)
mass spectra the cationic molecular peaks appear at m/z has been obtained by treatment of 1 with [Cu(NCMe)4]PF6
(%) ϭ 1223 (20) [4] and 1044 (40) [5].
in a molar ratio of 2:1. Because of the tendency of CuI to
adopt higher coordination numbers than gold, we propose
a tetrahedral derivative with the copper atom bonded to
Treatment of with an equimolar amount of
1
[Au(C6F5)(tht)] (tht ϭ tetrahydrothiophene) affords the
compound [Au(C6F5)(FcCH2NHpyMe)] (6). Complex 6 is
an air- and moisture-stable yellow solid which is a noncon-
ductor in acetone solution. The IR spectrum shows bands
arising from the pentafluorophenyl group at ν˜ ϭ 1500 (vs),
1
both pyridine and amine nitrogen atoms. In the H NMR
spectrum both ferrocene units are equivalent and the pro-
tons appear as a broad resonance. A singlet for the methyl
protons and a multiplet for the methylene protons also ap-
pear. The pyridine units show two multiplets for the two
different types of protons.
1
954 (s) and 793 (m) cmϪ1. In the H NMR spectrum of 6
the typical resonances for the ferrocenyl, methyl and meth-
ylene (as a doublet) protons are apparent. The three pyri-
dine protons appear as two doublets and a doublet of dou-
blets and the resonance for the NH proton has shifted
downfield to δ ϭ 6.73 ppm. The 19F NMR spectrum shows
the three resonances for a pentafluorophenyl group as two
multiplets for the ortho- and meta-fluorine atoms and a
triplet for the para-fluorine atom. The LSIMSϩ mass spec-
trum shows the molecular peak at m/z (%) ϭ 670 (85) and
a peak arising from loss of the pentafluorophenyl group at
m/z (%) ϭ 503 (7) can also be observed. The reaction of
complex 6 with 1 equiv. of [Au(acac)(PPh3)] leads to depro-
tonation of the amine group and coordination of the nitro-
Crystal Structure Determinations
The crystal structure of the cyclohexane solvate of
[Au2(PPh3)2(FcCH2NpyMe)]ClO4 (4) has been determined
by a single-crystal X-ray diffraction study (Figure 1). A
selection of bond lengths and angles are shown in Table 1.
The gold atoms have a distorted linear geometry with
angles
N(1)ϪAu(1)ϪP(1)
of
172.8(2)°
and
N(2)ϪAu(2)ϪP(2) of 170.26(14)°. This distortion may be a
consequence of a short intramolecular gold()Ϫgold() in-
˚
teraction of 2.9732(5) A. The AuϪN distances are 2.091(5)
˚
˚
A to the pyridine nitrogen atom and 2.052(5) A to the am-
ine nitrogen atom which are among the longest found in
ϩ
gen atom to the AuPPh3 fragment. The compound
[Au2(C6F5)(PPh3)(FcCH2NpyMe)] (7) is an air- and moist-
ure-stable yellow solid which is a nonconductor in acetone
1
solution. The H NMR spectrum shows the resonances for
the ferrocenyl unit, a singlet for the unsubstituted cyclopen-
tadienyl Cp ligand and a broad multiplet for the substituted
cyclopentadienyl Cp unit. The methylene and the methyl
protons appear as a multiplet and a singlet, respectively,
and the resonances for the phenyl and pyridine groups are
overlapping. The signal for the NH proton disappears. The
31P NMR spectrum shows one singlet for the phosphorus
atom and the 19F NMR spectrum has a typical pattern for
the pentafluorophenyl group. In the LSIMSϩ spectrum the
molecular peak at m/z (%) ϭ 1128 (5) and the [M ϩ
AuPPh3]ϩ fragment at m/z (%) ϭ 1587 (10) may be ob-
served.
Figure 1. Structure of the cation of complex 4 showing the atom
Ligand 1 also reacts with gold() complexes of the
type [Au(C6F5)3(OEt2)] or [Au(C6F5)2Cl]2 to afford
the compounds [Au(C6F5)3(FcCH2NHpyMe)] (8) or
[Au(C6F5)2Cl(FcCH2NHpyMe)] (9), respectively. Com-
plexes 8 and 9 are air- and moisture-stable yellow solids
which are nonconductors in acetone solution. Their IR
labelling scheme; radii are arbitrary, H atoms are omitted for clarity
˚
Table 1. Selected bond lengths [A] and angles [°] for 4
Au(1)ϪN(1)
Au(1)ϪP(1)
2.054(5)
Au(2)ϪP(2)
2.2341(18)
1.469(8)
1.352(8)
2.2412(16) C(11)ϪN(1)
2.9733(5) N(1)ϪC(51)
2.093(5)
spectra show typical bands for the pentafluorophenyl frag- Au(1)ϪAu(2)
Au(2)ϪN(2)
ments bonded to gold() at ν˜ ഠ 1507 (s), 972 (s), 800 (s)
N(1)ϪAu(1)ϪP(1) 172.85(16)
C(61)ϪP(2)ϪAu(2) 116.3(2)
and 795 (m) cmϪ1. The 19F NMR spectrum of 8 shows the
typical pattern of an Au(C6F5)3 group in which the trans-
pentafluorophenyl groups are equivalent. Six resonances in
a 2:1 ratio are observed corresponding to the ortho-, meta-
and para-fluorines of the inequivalent C6F5 moieties. For
compound 9, two inequivalent pentafluorophenyl units may
N(1)ϪAu(1)ϪAu(2) 71.67(15)
P(1)ϪAu(1)ϪAu(2) 114.49(5)
N(2)ϪAu(2)ϪP(2) 170.25(14)
N(2)ϪAu(2)ϪAu(1) 75.80(13)
P(2)ϪAu(2)ϪAu(1) 113.94(5)
C(31)ϪP(1)ϪAu(1) 112.6(2)
C(41)ϪP(1)ϪAu(1) 112.2(2)
C(21)ϪP(1)ϪAu(1) 110.9(2)
C(71)ϪP(2)ϪAu(2) 111.9(2)
C(81)ϪP(2)ϪAu(2) 110.1(2)
N(1)ϪC(11)ϪC(1) 109.6(5)
C(51)ϪN(1)ϪAu(1) 119.0(4)
C(11)ϪN(1)ϪAu(1) 115.9(4)
C(51)ϪN(2)ϪAu(2) 117.1(4)
C(55)ϪN(2)ϪAu(2) 119.8(4)
1
be observed corresponding to a cis configuration. The H
NMR spectrum is in agreement with the formula. In the
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Role of Secondary Interactions in Group 11 Metal Complexes Containing a Ferrocene Ligand
FULL PAPER
˚
complexes with the unit NpyridinicϪAuϪPPh3. The latter
Table 2. Selected bond lengths [A] and angles [°] for 6
generally range from 1.986(3)[8] to 2.108[9] A. The longer
˚
AuϪC(21)
AuϪN(1)
N(1)ϪC(12)
N(1)ϪC(16)
C(12)ϪN(2)
1.988(4) C(21)ϪC(22)
2.073(4) C(21)ϪC(26)
1.345(5) C(22)ϪF(1)
1.370(5) C(22)ϪC(23)
1.358(5) C(23)ϪF(2)
1.392(6) C(23)ϪC(24)
1.375(6) C(24)ϪF(3)
1.395(7) C(24)ϪC(25)
1.355(7) C(25)ϪF(4)
1.507(6) C(25)ϪC(26)
1.460(5) C(26)ϪF(5)
1.382(6)
1.397(6)
1.362(5)
1.365(6)
1.343(5)
1.378(7)
1.338(6)
1.368(7)
1.345(5)
1.375(7)
1.352(5)
AuϪP bond in 4 is opposite to the shorter AuϪN bond.
The values are similar to those observed in other complexes
with the NϪAuϪP unit.[8,9] The two PϪAuϪN units are
skewed with respect to each other as shown by the torsion
angle P(1)ϪAu(1)ϪAu(2)ϪP(2) of Ϫ45.8(1)°. The cyclo- C(12)ϪC(13)
C(13)ϪC(14)
pentadienyl rings display an essentially eclipsed geometry
C(14)ϪC(15)
[torsion angle C(1)ϪCpϪCpϪC(6) 0.3°]. The gold atom
C(15)ϪC(16)
Au(1) is located close to and with short contacts to the
C(16)ϪC(17)
N(2)ϪC(36)
C(1)ϪC(2) bond of the cyclopentadienyl group [distances
2
˚
C(21)ϪAuϪN(1)
C(12)ϪN(1)ϪC(16)
C(12)ϪN(1)ϪAu
C(16)ϪN(1)ϪAu
N(1)ϪC(12)ϪN(2)
177.65(13) C(16)ϪC(15)ϪC(14) 119.0(4)
to C(1) and C(2): 3.150 and 3.357 A] indicating a weak η
interaction with the Cp ring in a similar manner as has
already been observed in other gold and silver complexes
with ferrocene derivatives.[10,11] In the lattice there are sev-
119.1(4)
120.6(3)
120.3(3)
116.5(4)
121.9(4)
121.6(4)
C(15)ϪC(16)ϪN(1)
C(15)ϪC(16)ϪC(17) 121.7(4)
N(1)ϪC(16)ϪC(17)
C(12)ϪN(2)ϪC(36)
C(22)ϪC(21)ϪC(26) 113.2(4)
121.7(4)
116.6(4)
124.2(4)
eral O···H interactions involving the oxygen atoms of the N(1)ϪC(12)ϪC(13)
N(2)ϪC(12)ϪC(13)
C(14)ϪC(13)ϪC(12) 118.0(4)
C(13)ϪC(14)ϪC(15) 120.4(4)
C(22)ϪC(21)ϪAu
C(26)ϪC(21)ϪAu
121.3(3)
125.5(3)
perchlorate anion and the protons of the phenyl and cyclo-
˚
pentadienyl moieties. These contacts are around 2.6 A and
are mostly of such a linearity as to be considered hydro-
gen bonds.
The structure of complex 6 has been confirmed by X-ray
diffraction and is shown in Figure 2. Selected bond lengths
and angles are shown in Table 2. The gold centre has a lin-
ear geometry with an angle CϪAuϪN of 177.65(13)°. The
˚
AuϪN distance is 2.073(4) A. Few examples of compounds
with the NpyridinicϪAuϪC6F5 moiety have been character-
ised by X-ray analysis and this value is shorter than the
˚
AuϪN bond length of 2.124(15) A in [Au(C6F5)(3-Fcpy)]
(3-Fcpy ϭ 3-ferrocenylpyridine).[12] It is similar, however, to
[2a]
that in [Au(C6F5)(3-Mepy)] (2.066 A) or the AuϪN(sp2)
˚
[13]
˚
value of 2.069(5) A found in [Au(C6F5)(N2C2Ph4)].
The
˚
AuϪC distance is 1.988(5) A and resembles the values
found in the complexes cited above. The cyclopentadienyl
ring deviates slightly from an eclipsed geometry [torsion
angle C(31)ϪCpϪCpϪC(41) 7.7°]. The NH group does not
participate in hydrogen bonding but has a short intramo-
lecular contact of 2.55 A to the gold atom (NϪH···Au 117°).
The molecules are associated through intermolecular auro-
philic interactions of 3.429 A giving a chain of gold atoms
˚
˚
Figure 3. Association of molecules in complex 6 through aurophilic
interactions; H atoms (expect NH) are omitted for clarity
parallel to the short axis (Figure 3). The chain structure is
reinforced by offset ring stacking, with a perpendicular dis-
˚
tance of ca. 3.33 A and a centroidϪplane distance of 3.48
˚
A. The molecules are further linked to form a 3D structure
through CϪH···F hydrogen bonds.
The structures of complexes 8 and 9 have also been estab-
lished by X-ray diffraction studies and the molecules are
shown in Figures 4 and 5, respectively. Selected bond
lengths and angles are collected in Tables 3 and 4. In both
complexes the gold() centres are in a square-planar ge-
ometry with the mean deviations from the ideal angles be-
ing 3.6° (8) and 3.8° (9). In 8 the AuϪC bond lengths are
˚
2.026(6), 2.064(5) and 2.071(5) A, the shortest is to the
pentafluorophenyl group trans to the pyridine ligand. In 9
˚
the distances are 2.012(2) and 2.028(3) A which are similar
to the shortest distance in compound 8. This shows the
higher trans influence of the pentafluorophenyl group com-
pared with amine or chloro ligands. The AuϪN distances
Figure 2. Molecular structure of complex 6 with the atom labelling
scheme; H atoms (expect NH) are omitted for clarity
˚
are 2.104(4) and 2.101(2) A and are very similar because
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E. M. Barranco, O. Crespo, M. C. Gimeno, P. G. Jones, A. Laguna
FULL PAPER
˚
both have a pentafluorophenyl group trans to them. Few
examples with the units NϪAu(C6F5)3 or NϪAuϪtrans-
(C6F5)2Cl have been structurally characterised but the val-
ues are similar to those reported, as for example in
[{Au(C6F5)3}2{Fc(Spy)2}].[6f] The cyclopentadienyl rings in
these complexes are eclipsed with torsion angles
Table 3. Selected bond lengths [A] and angles [°] for 8
AuϪC(31)
AuϪC(21)
AuϪC(41)
AuϪN(2)
2.026(6)
2.064(5)
2.071(5)
2.104(4)
88.9(2)
N(1)ϪC(12)
N(1)ϪC(11)
N(2)ϪC(12)
N(2)ϪC(16)
C(16)ϪN(2)ϪAu
C(22)ϪC(21)ϪAu
C(26)ϪC(21)ϪAu
C(32)ϪC(31)ϪAu
C(36)ϪC(31)ϪAu
C(42)ϪC(41)ϪAu
C(46)ϪC(41)ϪAu
1.340(6)
1.455(6)
1.352(6)
1.379(7)
C(31)ϪAuϪC(21)
119.8(4)
C(1)ϪCpϪCpϪC(6) of 0.9° in 8 and 8.8° in 9. Both com- C(31)ϪAuϪC(41)
89.1(2)
124.7(4)
120.4(4)
122.5(4)
120.1(4)
122.4(4)
122.1(4)
C(21)ϪAuϪC(41)
C(31)ϪAuϪN(2)
C(21)ϪAuϪN(2)
C(41)ϪAuϪN(2)
177.9(2)
176.60(19)
93.64(18)
88.38(18)
119.4(4)
plexes show intramolecular NϪH···Au hydrogen contacts
˚
of 2.62(8) and 2.67(9) A, respectively, but these are better
considered as the weaker parts of three-centred interactions
involving F5 or Cl, respectively, as the main hydrogen bond
acceptor. Additional CϪH···F (and CϪH···Cl for 9) hydro-
gen bonds between various molecules create a 3D extended
structure in 8 or the disposition of the molecules into planes
in 9 (Figure 6). Table 5 lists the hydrogen bonds found in
these complexes.
C(12)ϪN(2)ϪAu
˚
Table 4. Selected bond lengths [A] and angles [°] for 9
AuϪC(31)
AuϪC(21)
2.012(2)
2.028(3)
86.25(10)
177.22(9)
91.52(9)
AuϪN(2)
AuϪCl
2.101(2)
2.3303(7)
91.03(6)
120.96(17)
118.51(17)
122.8(2)
C(31)ϪAuϪC(21)
C(31)ϪAuϪN(2)
C(21)ϪAuϪN(2)
C(31)ϪAuϪCl
C(21)ϪAuϪCl
N(2)ϪAuϪCl
C(12)ϪN(2)ϪAu
C(16)ϪN(2)ϪAu
C(22)ϪC(21)ϪAu
C(36)ϪC(31)ϪAu
91.28(7)
176.22(7)
122.39(19)
Figure 4. Perspective view of complex 8 with the atom labelling
scheme; H atoms (except NH) are omitted for clarity
Figure 6. Supramolecular structure through hydrogen bonding in
complex 9
Figure 5. Molecular structure of complex 9 with the atom labelling
deprotonating agents causing substitution of the proton for
scheme; H atoms (except NH) are omitted for clarity
ϩ
ϩ
the isolobal AgPPh3 or AuPPh3 fragments. In the struc-
tures of these derivatives it is worth mentioning the pres-
ence of intra- and intermolecular goldϪgold interactions.
In some cases the aurophilic interactions provide a supra-
Conclusions
The ligand FcCH2NHpyMe can form several complexes molecular chain-like structure. The presence of other sec-
with copper, silver or gold with different geometries and ondary interactions is also noteworthy, for example the
coordination modes. Coordination through the pyridine ni- weak η2 interaction between the gold centre and the cyclo-
trogen atom is ususally preferred by the three metals but pendienyl ring and the intra- and intermolecular hydrogen
bonding to the amine nitrogen atom can be achieved using bonds.
4824
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 4820Ϫ4827

Role of Secondary Interactions in Group 11 Metal Complexes Containing a Ferrocene Ligand
FULL PAPER
with a VG Autospec instrument with the liquid secondary-ion mass
spectroscopy (LSIMS) technique using nitrobenzyl alcohol as a
matrix. NMR spectra were recorded with a Varian Unity 300 spec-
trometer or a Bruker ARX 300 spectrometer in CDCl3. Chemical
shifts are given relative to SiMe4 (1H, external), CFCl3 (19F, exter-
nal) or 85% H3PO4 (31P, external).
Table 5. Hydrogen bonds for compounds 4, 6, 8 and 9
Compound 4
DϪH···A
d(DϪH) d(H···A) d(D···A) Є(DHA)
C(32)ϪH(32)···O(1)
0.95
2.53
2.57
2.57
2.58
2.55
2.47
2.64
3.256(8) 133.5
3.500(9) 165.1
3.465(11) 158.2
3.258(9) 128.6
3.232(10) 128.6
3.376(9) 160.4
3.492(8) 149.6
C(83)ϪH(83)···O(2)#1 0.95
C(53)ϪH(53)···O(3)#2 0.95
C(73)ϪH(73)···O(3)#3 0.95
Starting Materials: The starting materials [Au(acac)(PPh3)],[14]
[O(AuPPh3)3]ClO4,[15] [Au(C6F5)(tht)],[16] [Au(C6F5)3(OEt2)],[17]
[18]
and [Ag(OTf)(PPh3)][19] were prepared accord-
C(23)ϪH(23)···O(4)
0.95
[Au(C6F5)2Cl]2
C(64)ϪH(64)···O(4)#4 0.95
ing to published procedures. All other reagents were commercially
available.
C(10)ϪH(10)···N(1)#5 0.95
Symmetry transformations used to generate equivalent atoms: #1:
x ϩ 1, Ϫy ϩ 3/2, z Ϫ 1/2; #2: Ϫ x ϩ 1, y Ϫ 1/2, Ϫz ϩ 1/2; #3: x
ϩ 1, y, z; #4: x, Ϫy ϩ 3/2, z Ϫ 1/2; #5: Ϫ x ϩ 1, Ϫy ϩ 1, Ϫz.
Synthesis of FcCH2NHpyMe (1): To a solution of 6-amino-2-pico-
line (0.756 g, 7 mmol) in acetic acid (30 mL) was added
FcCH2NMe2 (1.7 g, 14 mmol) and the mixture was heated at 80
°C for 3 h. The solution was then cooled and an aqueous solution
of NaHCO3 was added in order to raise the pH to 7. The organic
phase was extracted with CH2Cl2 (3 ϫ 1 mL) and dried with
MgSO4. The solution was then concentrated to ca. 2 mL and chro-
matographed on alumina with diethyl ether/hexane (4:1) as eluent.
Evaporation of the solvent to ca. 5 mL and addition of hexane
Compound 6
DϪH···A
d(DϪH) d(H···A) d(D···A) Є(DHA)
C(32)ϪH(32)···F(1)#1 0.95
C(35)ϪH(35)···F(1)#2 0.95
C(42)ϪH(42)···F(2)#3 0.95
C(34)ϪH(34)···F(3)#4 0.95
C(17)ϪH(17C)···F(4)#5 0.98
2.49
2.55
2.43
2.60
2.52
3.130(6) 125.0
3.316(6) 137.7
3.335(7) 159.9
3.520(6) 164.3
3.299(6) 136.2
gave the ligand 1 as an orange solid. Yield 40%, 856.9 mg. ΛM
ϭ
0.4 ΩϪ1·cm2·molϪ1. C17H18FeN2 (306.2): calcd. C 66.69, H 5.92, N
Symmetry transformations used to generate equivalent atoms: #1:
Ϫ x ϩ 1, Ϫy ϩ 1, Ϫz ϩ 1; #2: Ϫx, Ϫy ϩ 1, Ϫz ϩ 1; #3: x ϩ 1,
y, z Ϫ 1; #4: Ϫx, Ϫy ϩ 2, Ϫz ϩ 1; #5: x, y Ϫ 1, z.
1
9.15; found C 66.57, H 5.90, N 9.10. H NMR: δ ϭ 2.39 (s, 3 H,
Me), 4.10 (m, 2 H, C5H4), 4.12 (m, 2 H, CH2), 4.19 (s, 5 H, C5H5),
4.22 (m, 2 H, C5H4), 4.73 (br. m, 1 H, NH), 6.23 [d, J(H,H) ϭ 8.3
Hz, 1 H, py], 6.46 [d, J(H,H) ϭ 7.7 Hz, 1 H, py], 7.35 [dd,
J(H,H) ϭ 8.3, 7.7 Hz, 1 H, py] ppm.
Compound 8
DϪH···A
d(DϪH) d(H···A) d(D···A) Є(DHA)
C(11)ϪH(11B)···F(3)#1 0.99
C(10)ϪH(10)···F(4)#1 0.95
2.35
2.57
2.26
2.47
2.38
2.59
2.62
2.59
3.328(7) 169.4
3.459(8) 155.6
3.105(6) 161.8
3.404(7) 169.5
3.112(7) 134.0
3.435(8) 147.7
3.128(5) 117.6
3.435(8) 147.7
Synthesis of [M(PPh3)(FcCH2NHpyMe)]OTf, M ؍ Au (2), Ag (3):
To a solution of 1 (0.031 g, 0.1 mmol) in dichloromethane (20 mL)
was added [Au(OTf)(PPh3)] (0.061 g, 0.1 mmol) or [Ag(OTf)(PPh3)]
(0.052 g, 0.1 mmol) and the mixture was stirred for 30 min. Evapor-
ation of the solvent to ca. 5 mL and addition of hexane (10 mL)
gave complexes 2 or 3 as orange solids.
N(1)ϪH(1)···F(5)
0.88
C(13)ϪH(13)···F(9)#2 0.95
C(14)ϪH(14)···F(5)#2 0.95
C(9)ϪH(9)···F(15)#3
N(1)ϪH(1)···Au
C(4)ϪH(4)···F(14)#3
0.95
0.88
0.95
Complex 2: Yield 72%, 65.8 mg. ΛM ϭ 120 ΩϪ1·cm2·molϪ1
.
Symmetry transformations used to generate equivalent atoms: #1:
x Ϫ 1, y, z; #2: x Ϫ 1/2, Ϫy ϩ 1/2, z Ϫ 1/2; #3: Ϫx ϩ 3/2, y Ϫ 1/
2, Ϫz ϩ 1/2.
C36H33AuF3FeN2O3PS (914.27): calcd. C 47.30, H 3.63, N 3.06, S
3.50; found C 46.86, H 3.29, N 2.90, S 3.64. 1H NMR: δ ϭ 2.58
(s, 3 H, Me), 4.3 (br. m, 10 H, C5H4, C5H5, NH, CH2), 6.46 [d,
J(H,H) ϭ 6.6 Hz, 1 H, py], 6.63 [d, py, J(H,H) ϭ 7.4, 1 H], 7.2Ϫ7.8
(m, 16 H, Ph, py) ppm. 31P(1H) NMR: δ ϭ 30.6 (s, 1 P, PPh3) ppm.
Compound 9
DϪH···A
d(DϪH) d(H···A) d(D···A) Є(DHA)
Complex 3: Yield 85%, 70.31 mg. ΛM ϭ 110 ΩϪ1·cm2·molϪ1
.
N(1)ϪH(01)···Au
N(1)ϪH(01)···Cl
0.88
0.88
0.95
2.67
2.93
2.60
2.51
2.56
2.86
2.91
3.143(2) 115.2
3.580(2) 132.1
3.298(4) 130.8
2.967(3) 108.3
2.967(3) 108.3
3.759(3) 157.4
3.882(3) 167.9
C36H33AgF3FeN2O3PS (827.171): calcd. C 52.38, H 4.03, N 3.41,
C(8)ϪH(8)···F(1)#1[a]
1
S 3.88; found C 52.24, H 4.22, N 3.33, S 3.87. H NMR: δ ϭ 2.44
C(17)ϪH(17A)···F(6)#2 0.98
C(17)ϪH(17B)···F(6)#2 0.98
C(4)ϪH(4)···Cl#3
C(11)ϪH(11A)···Cl#4
Symmetry transformations used to generate equivalent atoms: #1:
x ϩ 1/2, Ϫy ϩ 1/2, z Ϫ 1/2, #2: x Ϫ 1, y, z; #3: x ϩ 1, y, z; #4:
0.5 ϩ x, 0.5 ϩ y, 0.5 Ϫ z.
(s, 3 H, Me), 4Ϫ5 (br. m, 10 H, C5H4, C5H5, CH2), 6.47 (m, 1 H,
py), 6.52 (m, 1 H, py), 6.76 (s, 1 H, NH), 7.2Ϫ7.8 (m, 16 H, py,
Ph) ppm. 31P(1H) NMR (Ϫ55 °C): δ ϭ 11.3 [2 d, J(107AgP) ϭ
475.1, J(109AgP) ϭ 547.4 Hz, 1 P, PPh3] ppm.
0.95
0.99
Synthesis of [M2(PPh3)2(FcCH2NpyMe)]X, M ؍ Au, X ؍ ClO4 (4),
M ؍ Ag, X ؍ OTf (5)
Complex 4: To a solution of 1 (0.031 g, 0.1 mmol) in dichloro-
methane (20 mL) was added [O(AuPPh3)3]ClO4 (0.149 g, 0.1 mmol)
and the mixture was stirred for 2 h. Evaporation of the solvent to
ca. 5 mL and addition of diethyl ether (10 mL) gave complex
Experimental Section
4
as a yellow solid. Yield 95%, 124.33 mg. ΛM ϭ 110
Instrumentation: Infrared spectra were recorded in the range
4000Ϫ200 cmϪ1 with a PerkinϪElmer 883 spectrometer using Nu-
jol mulls between polyethylene sheets. Conductivities were meas-
ured in ca. 5 ϫ 10Ϫ4 mol·dmϪ3 solutions with a Philips 9509 con-
ductimeter. C, H, N and S analyses were carried out with a
Ω
Ϫ1·cm2·molϪ1. C52H45Au2ClFeN2O4P2 (1308.806): calcd. C 48.11,
H 3.58, N 2.12; found C 47.98, H 3.39, N 1.99. 1H NMR: δ ϭ 2.56
(s, 3 H, Me), 4.04 (m, 2 H, C5H4), 4.16 (s, 5 H, C5H5), 4.18 (m, 2
H, CH2), 4.23 (m, 2 H, C5H4), 6.44 [d, J(H,H) ϭ 7.0 Hz, 2 H, py],
6.68 [d, J(H,H) ϭ 8.4 Hz, 2 H, py], 7.1Ϫ7.8 (m, 31 H, py, Ph) ppm.
PerkinϪElmer 2400 microanalyser. Mass spectra were recorded 31P(1 H) NMR: δ ϭ 30.5 (s, 1 P, PPh3), 24.3 (s, 1 P, PPh3) ppm.
Eur. J. Inorg. Chem. 2004, 4820Ϫ4827
www.eurjic.org  2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 4825

E. M. Barranco, O. Crespo, M. C. Gimeno, P. G. Jones, A. Laguna
FULL PAPER
The triflate salt [Au2(PPh3)2(FcCH2NpyMe)]OTf is also accessible
by treatment of complex 2, [Au(PPh3)(FcCH2NHpyMe)]OTf, with
[Au(acac)(PPh3)] in dichloromethane. Yield, 89%.
19F NMR: δ ϭ Ϫ117.3 (m, 2 F, m-F), 160.5 [t, J(F,F) ϭ 20.6 Hz,
1 F, p-F], Ϫ164.1 (m, 2 F, o-F) ppm.
Synthesis of [Au2(C6F5)(PPh3)(FcCH2NpyMe)] (7): To a solution of
complex 6 (0.067 g, 0.1 mmol) in dichloromethane (20 mL) was
added [Au(acac)(PPh3)] (0.056 g, 0.1 mmol) and the mixture was
stirred for 2 h. Evaporation of the solvent to ca. 5 mL and addition
of diethyl ether (10 mL) gave complex 7 as a yellow solid. Yield
66%, 72.74 mg. ΛM ϭ 8 ΩϪ1·cm2·molϪ1. C39H30Au2F5FeN2P
(1102.21): calcd. C 43.64, H 2.86, N 2.48; found C 43.42, H 2.80,
Complex 5: To a solution of 1 (0.031 g, 0.1 mmol) in dichlorometh-
ane (20 mL) was added [Ag(OTf)(PPh3)] (0.104 g, 0.2 mmol) and
NEt3 (0.021 mL, 0.15 mmol) and the mixture was stirred for 1 h.
Evaporation of the solvent to ca. 5 mL and addition of hexane (10
mL) gave complex 5 as a red solid. Yield 70%, 82.61 mg. ΛM
ϭ
100 ΩϪ1·cm2·molϪ1. C53H45Ag2F3FeN2O3P2S (1180.226): calcd. C
1
54.30, H 3.96, N 1.17, S 2.68; found C 54.13, H 4.05, N 1.31, S
N 2.33. H NMR: δ ϭ 2.67 (s, 3 H, Me), 3.80 (m, 2 H, CH2), 4.12
1
2.34. H NMR: δ ϭ 2.50 (s, 3 H, Me), 4.04 (m, 2 H, C5H4), 4.10
(s, 5 H, C5H5), 4.31 (m, 4 H, C5H4), 6.26 [d, J(H,H) ϭ 6.0 Hz, 1
H, py], 6.53 [d, J(H,H) ϭ 8.7 Hz, 1 H, py], 7.1Ϫ7.8 (m, py, Ph)
ppm. 19F NMR: δ ϭ Ϫ116.0 (m, 2 F, m-F), 163.3 [t, 1 F, p-F,
J(F,F) ϭ 20.6 Hz], Ϫ164.5 (m, 2 F, o-F) ppm. 31P(1H) NMR: δ ϭ
30.7 (s, 1 P, PPh3) ppm.
(m, 2 H, CH2), 4.14 (s, 5 H, C5H5), 4.23 (m, 2 H, C5H4), 6.49 (m,
1 H, py), 6.56 (m, 1 H, py), 7.1Ϫ7.8 (m, 31 H, py, Ph) ppm. 31P(1H)
NMR (Ϫ55 °C): δ ϭ 10.4 [2 d, J(107AgP) ϭ 402.9, J(109AgP) ϭ
465.9 Hz, 1 P, PPh3], 11.2 [2 d, J(107AgP) ϭ 430.1, J(109AgP) ϭ
492.5 Hz, 1 P, PPh3] ppm.
Synthesis of [Au(C6F5)2X(FcCH2NHpyMe)], X ؍ C6F5 (8), Cl (9):
To a solution of 1 (0.031 g, 0.1 mmol) in dichloromethane (20 mL)
Synthesis of [Au(C6F5)(FcCH2NHpyMe)] (6): To a solution of 1
(0.031 g, 0.1 mmol) in dichloromethane (20 mL) was added
[Au(C6F5)(tht)] (0.045 g, 0.1 mmol) and the mixture was stirred for
30 min. Evaporation of the solvent to ca. 5 mL and addition of
hexane (10 mL) gave complex 6 as a yellow solid. Yield 76%,
49.86 mg. ΛM ϭ 4 ΩϪ1·cm2·molϪ1. C22H16AuF5FeN2 (656.056):
was
added
[Au(C6F5)3(OEt2)]
(0.077 g,
0.1 mmol)
or
[Au(C6F5)2Cl]2 (0.056 g, 0.05 mmol) and the mixture was stirred
for 1 h. Evaporation of the solvent to ca. 5 mL and addition of
hexane (10 mL) gave complexes 8 or 9 as yellow solids.
1
calcd. C 41.22, H 2.71, N 4.18; found C 41.09, H 2.50, N 3.99. H
Complex 8: Yield 75%, 75.25 mg, ΛM ϭ 4 Ω .
Ϫ1·cm2·molϪ1
NMR: δ ϭ 2.80 (s, 3 H, Me), 4.07 [d, J(H,H) ϭ 5.1 Hz, 2 H, CH2], C35H18AuF15FeN2 (1004.35): calcd. C 41.86, H 1.81, N 2.79; found
4.20 (s, 5 H, C5H5), 4.20 (m, 2 H, C5H4), 4.27 (m, 2 H, C5H4), 6.55
C 41.79, H 1.56, N 2.34. 1H NMR: δ ϭ 2.71 (s, 3 H, Me), 4.11 (m,
[d, J(H,H) ϭ 7.2 Hz, 1 H, py], 6.64 [d, J(H,H) ϭ 8.7 Hz, 1 H, py], 2 H, CH2), 4.20 (m, 9 H, C5H5, C5H4, NH), 5.89 (m, 1 H, py),
6.73 (m, 1 H, NH), 7.58 [dd, J(H,H) ϭ 8.7, 7.2 Hz, 1 H, py] ppm. 6.57 (m, 2 H, py), 7.53 (m, 1 H, py) ppm. 19F NMR: δ ϭ Ϫ121.6
Table 6. X-ray data for complexes 4, 6, 8 and 9
Compound
4·C6H12
6
8·C5H12
9
Formula
Mr
C59H59Au2ClFeN2O4P2
1407.26
C23H18AuF5FeN2
670.21
C40H30AuF15FeN2
1076.48
C29H18AuClF10FeN2
872.72
Habit
orange tablet
0.45 ϫ 0.25 ϫ 0.15
monoclinic
orange prism
0.55 ϫ 0.45 ϫ 0.3
triclinic
orange pyramid
0.50 ϫ 0.45 ϫ 0.25
monoclinic
orange tablet
0.18 ϫ 0.15 ϫ 0.09
monoclinic
Crystal size [mm]
Crystal system
Space group
Cell constants:
P21/c
P(Ϫ1)
P21/n
P21/n
˚
a [A]
10.879(2)
21.245(3)
23.773(3)
90
97.687(10)
90
5445.3
4
1.717
5.8
6.641(3)
11.151(4)
14.737(5)
84.66(2)
77.56(2)
85.54(2)
1059.2
2
10.3534(16)
22.911(3)
16.993(2)
90
100.170(12)
90
3967.6
4
1.802
4.2
8.1587(8)
14.5039(14)
23.688(2)
90
94.312(3)
90
2795.1
4
2.074
5.9
˚
b [A]
˚
c [A]
α [°]
β [°]
γ [°]
3
˚
V [A ]
Z
Dx [Mg·mϪ3
]
2.101
7.7
640
µ [mmϪ1
F(000)
]
2760
2096
1672
T [°C]
Ϫ100
50
Ϫ130
50
Ϫ100
50
Ϫ130
60
2θmax. [°]
No. of reflections
Measured
Independent
Transmissions
Rint
10394
9552
0.45Ϫ0.96
0.036
641
4425
3723
0.46Ϫ0.81
0.024
295
7479
6936
0.50Ϫ0.99
0.025
498
59912
8194
0.69Ϫ0.86
0.059
398
Parameters
Restraints
632
274
149
138
wR(F2, all refl.)
R [F, Ͼ 4σ(F)]
S
0.073
0.034
0.88
0.062
0.024
1.07
0.069
0.033
0.89
0.052
0.023
0.99
Ϫ3
˚
max. ∆ρ [e·A
]
1.9
1.7
0.8
1.8
4826
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 4820Ϫ4827

Role of Secondary Interactions in Group 11 Metal Complexes Containing a Ferrocene Ligand
FULL PAPER
[3b]
Parish, L. S. Moore, Inorg. Chim. Acta 1986, 112, 205.
J.
(m, 4 F, m-F), Ϫ123.0 (m, 2 F, m-F), Ϫ156.2 [t, J(F F) ϭ 19.5 Hz,
2 F, p-F], Ϫ156.7 (t, J(F,F) ϭ 19.6 Hz, 1 F, p-F], Ϫ160.8 (m, 4 F,
o-F), Ϫ161.4 (m, 2 F, o-F) ppm.
Vicente, M. T. Chicote, R. Guerrero, P. G. Jones, J. Chem. Soc.,
[3c]
Dalton Trans. 1995, 1251.
M. Munakata, S. G. Yam, M.
Maekawa, M. Akiyama, S. Kitagawa, J. Chem. Soc., Dalton
Trans. 1997, 4257. [3d] A. Grohmann, J. Riede, H. Schmidbaur,
Complex 9: Yield 74%, 64.39 mg, ΛM ϭ 18 ΩϪ1·cm2·molϪ1
.
[3e]
Z. Naturforsch., Teil B 1992, 47, 1255.
U. M. Tripathi, G.
C29H18AuClF10FeN2 (872.61): calcd. C 39.91, H 2.08, N 3.22;
L. Wegner, A. Schier, A. Jockisch, H. Schmidbaur, Z. Natur-
forsch., Teil B 1998, 53, 939. [3f] J. Zou, P. Taylor, J. Dornan, S.
P. Robinson, M. D. Walkinshaw, P. J. Sadler, Angew. Chem. Int.
Ed. 2000, 39, 2931. [3g] J. F. Vollano, D. H. Picker, J. A. Statler,
Inorg. Chim. Acta 1989, 155, 31.
1
found C 39.89, H 1.65, N 2.93. H NMR: δ ϭ 2.85 (s, 3 H, Me),
4.12 (m, 2 H, CH2), 4.20 (m, 9 H, C5H5, C5H4), 4.41 (m, 1 H, NH),
6.04 (m, 1 H, py), 6.60 [2 d, J(H,H) ϭ 7.3, 8.5 Hz, 2 H, py], 7.58
[dd, J(H,H) ϭ 7.3, 8.5 Hz, 1 H, py] ppm. 19F NMR: δ ϭ Ϫ122.0
(m, 2 F, m-F), Ϫ123.0 (m, 2 F, m-F), Ϫ154.7 [t, J(F,F) ϭ 19.6 Hz,
1 F, p-F], Ϫ156.0 [t, J(F,F) ϭ 19.6 Hz, 1 F, p-F], Ϫ160.0 (m, 2 F,
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solved for 4 and 8) or using a riding model. Refinement special
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The structure of 8 contains one poorly resolved pentane solvate
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and related parameters correspond to the idealised compositions
including solvent. Further crystallographic data are collected in
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tallographic data for this paper. These data can be obtained free
of charge at www.ccdc.cam.uk/conts/retrieving.html [or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ; Fax: (internat.) ϩ 44-1223-336-033; E-mail:
deposit@ccdc.cam.ac.uk].
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We thank the Direccion General de Investigacion Cientıfica y Tec-
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Early View Article
Published Online November 5, 2004
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Eur. J. Inorg. Chem. 2004, 4820Ϫ4827
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 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4827