The coordination behaviour of ferrocene-based pyridylphosphine ligands towards AgI and AuI

Article abstract of DOI:10.1002/zaac.201100209

Abstract. The reaction of the P,N-ligands [Fe(C₅H ₄-PPh₂)(C₅H₄-2-py)] (1) (2-py = pyrid-2-yl), [Fe(C₅H₄-PPh₂)(C₅H ₄-CH₂-2-py)] (2) and [Fe(C₅H ₄-PPh₂)(C₅H₄-3-py)] (3) (3-py = pyrid-3-yl) with Ag[BF₄] in a 1:1 stoichiometric ratio afforded complexes of the type [Ag(L)][BF₄] (L = 1-3), which were structurally characterised by X-ray diffraction. Two structure types were observed in the solid state, viz. coordination polymer (L = 1, 2) and cyclic dimer (L = 2, 3). The reaction of1-3 with one equivalent of [AuCl(tht)] (tht = tetrahydrothiophene) afforded complexes of the type [AuCl(L-κP)] (L = 1-3), whose crystal structures were determined by X-ray diffraction. Their reactions with one equivalent of Ag[BF₄] gave products of the general composition [Au(L)][BF₄]; of these the cyclic dimer {[Au(μ-1)][BF₄]}₂ wasstructurally characterised by X-ray diffraction. The P,N,P-ligandC₅H₃N-2,6-(fcPPh ₂)₂ (4, fc = 1,1′-ferrocenediyl) was synthesised by Negishi cross-coupling of Ph₂PfcZnCl with 2,6-dibromopyridine. Its crystal structure was determined by X-ray diffraction. The reaction of 4 with two equivalents of [AuCl(tht)] afforded the dinuclear gold(I) complex [(AuCl)₂(μ-4-κ²P,P)]. The mononuclear gold(I) complex [Au(4-κ²P,P)][SbF₆] was obtained in a one-pot reaction of 4 with one equivalent of [AuCl(tht)] and subsequently with one equivalent of Ag[SbF₆]; it contains 4 in a trans-chelating binding mode, as revealed by a crystal structure determination. Copyright

Full text of DOI:10.1002/zaac.201100209

ARTICLE
DOI: 10.1002/zaac.201100209
The Coordination Behaviour of Ferrocene-based Pyridylphosphine Ligands
towards AgI and AuI
Ulrich Siemeling,*[a] Thorsten Klemann,[a] Clemens Bruhn,[a] Jirˇí Schulz,[b] and
[b]
ˇ
Petr Steˇpnicˇka
In Memory of Professor Kurt Dehnicke
Keywords: Bridging ligands; Coordination modes; Gold; N,P ligands; Silver
Abstract. The reaction of the P,N-ligands [Fe(C5H4-PPh2)(C5H4-2-py)]
[Au(L)][BF4]; of these the cyclic dimer {[Au(μ-1)][BF4]}2 was
(1) (2-py = pyrid-2-yl), [Fe(C5H4-PPh2)(C5H4-CH2-2-py)] (2) and structurally characterised by X-ray diffraction. The P,N,P-ligand
[Fe(C5H4-PPh2)(C5H4-3-py)] (3) (3-py = pyrid-3-yl) with Ag[BF4] in a
C5H3N-2,6-(fcPPh2)2 (4, fc = 1,1Ј-ferrocenediyl) was synthesised by
1:1 stoichiometric ratio afforded complexes of the type [Ag(L)][BF4] Negishi cross-coupling of Ph2PfcZnCl with 2,6-dibromopyridine. Its
(L = 1–3), which were structurally characterised by X-ray diffraction. crystal structure was determined by X-ray diffraction. The reaction of
Two structure types were observed in the solid state, viz. coordination 4 with two equivalents of [AuCl(tht)] afforded the dinuclear gold(I)
polymer (L = 1, 2) and cyclic dimer (L = 2, 3). The reaction of complex [(AuCl)2(μ-4-κ2P,P)]. The mononuclear gold(I) complex
1–3 with one equivalent of [AuCl(tht)] (tht = tetrahydrothiophene) af- [Au(4-κ2P,P)][SbF6] was obtained in a one-pot reaction of 4 with one
forded complexes of the type [AuCl(L-κP)] (L = 1–3), whose crystal
equivalent of [AuCl(tht)] and subsequently with one equivalent of
structures were determined by X-ray diffraction. Their reactions with Ag[SbF6]; it contains 4 in a trans-chelating binding mode, as revealed
one equivalent of Ag[BF4] gave products of the general composition by a crystal structure determination.
(3, 3-py = pyrid-3-yl) (Scheme 1) in this context and recently
reported results of a study focusing on their coordination be-
Introduction
haviour toward a range of tetracoordinate metal atoms.[4c,d]
The pseudotetrahedral, d10 configured Group 12 metal atoms
ZnII, CdII, and HgII were investigated particularly comprehen-
sively.[4d] Saliently, we found three structure types in the solid
state for the Group 12 metal dihalogenido complexes [MX2(L)]
(L = 1–3), viz. chelate, cyclic dimer and chain-like coordina-
tion polymer. Ligand 1 prefers the formation of chelates
[MX2(1-κ2N,P)]. 3 forms coordination polymers [MX2(μ-3)]n.
With the more flexible 2 all three structure types can occur.
The P–M–N angle is much larger in the chelates (up to 125°)
than in the ligand-bridged structures ( Յ 109°).
Pyridylphosphines are highly versatile P,N-ligands which
are widely used in coordination chemistry. The combination of
a soft P-donor site with a borderline to hard N-donor site has
been utilised for applications in catalysis and supramolecular
chemistry.[1] We have a long-standing interest in ferrocene-
based bidentate ligands with a focus on symmetric N,N-ligands
which contain a 1,1Ј-ferrocenediyl (fc) backbone.[2] We re-
cently expanded our work to related heteroditopic P,N-systems,
since to date the majority of ferrocene-based P,N-ligands does
not contain the 1,1Ј-ferrocenediyl backbone but rather have the
P- and N-donor groups attached to the same cyclopentadienyl
ring.[3] Following our recent studies on phosphinoferrocene
carboxamides with pyridine pendants,[4a,b] we have been ad-
dressing, inter alia, the pyridylphosphine ligands [Fe(C5H4-
PPh2)(C5H4-2-py)] (1, 2-py = pyrid-2-yl), [Fe(C5H4-PPh2)-
(C5H4-CH2-2-py)] (2) and [Fe(C5H4-PPh2)(C5H4-3-py)]
* Prof. Dr. U. Siemeling
Fax: +49-561-804-4777
E-Mail: siemeling@uni-kassel.de
[a] Institut für Chemie
Scheme 1. P,N-ligands investigated in this work.
We have now extended our study systematically to AgI and
AuI. Like the previously investigated ZnII, CdII, and HgII, these
monovalent Group 11 metal atoms are d10 configured. However,
in contrast to the divalent Group 12 metals they frequently exhi-
bit coordination numbers lower than four and hence particularly
large coordination angles. Whereas the coordination chemistry
Universität Kassel
Heinrich-Plett-Str. 40
34132 Kassel, Germany
[b] Department of Inorganic Chemistry
Faculty of Science
Charles University in Prague
Hlavova 2030
12840 Prague 2, Czech Republic
1824
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Z. Anorg. Allg. Chem. 2011, 637, 1824–1833

Coordination of Ferrocene-based Pyridylphosphine Ligands towards AgI and AuI
of AuI is clearly dominated by linear two-coordinate complexes, recrystallisation from chloroform. The results of the X-ray dif-
AgI is more flexible, typically giving rise to coordination num- fraction studies are shown in Figure 1, Figure 2 and Figure 3.
bers from two to four.[5] A moderate number of structurally char- The crystalline compounds obtained with ligands 1 and 2 are
acterised AgI pyridylphosphine complexes have been reported,[6] coordination polymers, whereas a cyclic dimer was obtained
with PPh2(2-py) being the most popular such ligand.[7] It is in- with ligand 3. Recrystallisation of [Ag(2)][BF4] from dichloro-
structive to inspect representative silver(I) and gold(I) complexes methane gave single-crystals of the cyclic dimer
of this iconic pyridylphosphine to illustrate pertinent differences {[Ag(μ-2)][BF4]}2 (Figure 4). This result underlines the struc-
between AgI and AuI. The theoretically calculated strength of tural flexibility of ligand 2, which had already shown similar
the M+–L interaction (gas phase; M = Ag, Au; L = pyridine, “ambiguous” coordination behaviour with zinc bromide, af-
PH3) increases in the order Ag Ͻ Au, this increase being notably fording both the chelate [ZnBr2(2-κ2N,P)] and the cyclic dimer
steeper for L = PH3.[8] It is evident that pyridyl N-coordination [ZnBr2(μ-2)]2.[4d] The silver atoms are P,N-coordinated in each
is rather unattractive for these soft metal centres and occurs only case. Pertinent bond parameters are collected in Table 1.
if their coordination requirements cannot be satisfied other-
wise.[9] For example, no N-coordination is observed for the
chlorido complexes [MCl{PPh2(2-py)}] (M = Ag,[10] Au[11]).
Whereas the gold complex is monomeric (coordination number
2), the silver complex is tetrameric with a heterocubanoid
Ag4Cl4 core (coordination number 4). Replacement of Cl– by
less strongly coordinating anions may result in pyridyl N-coor-
dination, as is observed, for example, for the silver nitrito and
nitrato analogues. These complexes crystallise as cyclic “head-
[12]
to-tail” dimers, viz. [Ag(NO2–κ2O){μ-PPh2(2-py)}]2
and
[Ag(NO3–κ1O){μ-PPh2(2-py)}]2,[13] exhibiting coordination
numbers of 4 and 3, respectively. With the essentially non-
coordinating tetrafluoroborate anion, NMR spectroscopic data
(CDCl3 solution) are in accord with the cyclic “head-to-tail”
[14]
dimer [Ag{μ-PPh2(2-py)}]2[BF4]2
containing dicoordinate
Figure 1. Section of the polymeric chain of {[Ag(μ-1)][BF4]}n in the
crystal.
AgI. The gold analogue is known to exhibit such a struc-
ture in the solid state.[15] The “head-to-tail” dimer
[Ag2{μ-PPh2(2-py)}2{PPh2(2-py)-κP}](ClO4)2, where an ad-
ditional PPh2(2-py) ligand is P-coordinated to one of the two
silver atoms, has also been structurally characterised.[16] The
structure of the heterobimetallic complex [Ag(ClO4–κ1O)2-
[14]
{μ-PPh2(2-py)}2Au]2
demonstrates that the preference
of AuI for P-coordination is even stronger than that of AgI.
The silver atom is in a distorted pseudotetrahedral environ-
ment, being coordinated by two nitrogen atoms and one
oxygen atom each of the weakly coordinating perchlorate
anions. The gold atom, on the other hand, is in an essentially
linear P,P-dicoordinate environment. Finally, the P-philicty of
AuI isalsoreflectedbythefactthat[AuCl(SMe2)]cleanlyaffords
the tricoordinate complex [AuCl{PPh2(2-py)}2] with two
equivalents of PPh2(2-py).[17] In contrast, the analogous
reaction of AgCl with two equivalents of the ligand results
Figure 2. Section of the polymeric chain of {[Ag(μ-2)][BF4]}n in the
crystal.
in
the
formation
of
the
dinuclear
complex
[Ag2(μ-Cl)2{μ-PPh2(2-py)}{PPh2(2-py)-κP}2], which contains
two tetracoordinate, chlorido-bridged AgI atoms, one being
P,P- and the other one P,N-coordinated.[10]
The Ag–N and Ag–P bond lengths are each almost identical
for these complexes, their average values being ca. 2.17 Å and
2.36 Å, respectively. These values compare well to those of
closely related compounds. For example, Ag–N and Ag–P
bond lengths of 2.181(5) Å and 2.376(2) Å, respectively, were
reported for [{Ag(PPh3)}2(μ-4,4Ј-bipy)](ClO4)2, which exhib-
its a P–Ag–N angle of 158.4(1)°.[18] A very similar situation
has also been found for the P,N-coordinated AgI atom in the
Results and Discussion
Silver Complexes
The reaction of ligands 1–3 with one equivalent of silver dinuclear [Ag2{μ-PPh2(2-py)}2{PPh2(2-py)-κP}](ClO4)2 al-
tetrafluoroborate in methanol afforded products of the ex- ready mentioned above [Ag–N 2.227(6) Å, Ag–P 2.368(2) Å,
pected composition [Ag(L)][BF4] (L = 1–3) according to ele- P–Ag–N 162.8(2)°].[16] Note that for both these compounds
mental analysis. Single-crystals were obtained in each case by the P–Ag–N angle deviates from the ideal value of 180° ex-
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ARTICLE
Waals radii of silver and fluorine (ca. 3.2 Å),[19] but consider-
ably longer than the Ag–F distances in AgF (ca. 2.47 Å),[20]
and it may be concluded that the AgI–anion interaction is
mainly electrostatic in nature.
The surprisingly high solubilities of these silver complexes
of ligands 1–3 in chloroform prompted us to probe their struc-
tures in solution by NMR spectroscopy. Metal N-coordination
1
leads to a diagnostic shift of the H NMR signal(s) due to the
α-pyridyl proton(s). Likewise, metal P-coordination is re-
flected by a shift of the 31P NMR signal due to the PPh2 sub-
stituent of the respective ligand. Pertinent NMR spectroscopic
data are collected in Table 2. Both P- and N-coordination are
clearly indicated by substantial coordination-induced shifts in
each case. The 31P NMR spectra of silver(I) phosphine com-
plexes are typically characterised by a diagnostic doublet of
doublets type pattern, which results from the coupling of phos-
phorus to each of the spin I = ½ silver isotopes (107Ag, 51.8%
natural abundance; 109Ag, 48.2% natural abundance), the
1J(31P,109Ag)/1J(31P,107Ag) ratio being close to the γ(109Ag)/γ
Figure 3. Molecular structure of the cyclic dimer {[Ag(μ-3)][BF4]}2
in the crystal.
(
107Ag) gyromagnetic ratio of 1.149.[21] This coupling is often
unresolved at room temperature, which is due to rapid phos-
phine exchange processes which frequently occur with mono-
dentate phosphine ligands.[22] In our three cases, we are not in
the fast exchange regime, since slightly broadened doublets are
observed, which reflect averaged coupling constants
1J(31P,109/107Ag,), in line with observations reported by Pettin-
ari and co-workers for a large number of P,N-coordinated sil-
ver(I) complexes with a single P-coordination.[12,23] These
coupling constant values are close to 700 Hz (Table 2), which
is nicely compatible with the notion that the AgI atoms exhibit
a single P-coordination.[22–24] Dissolving {[Ag(μ-3)][BF4]}2 in
chloroform most likely leaves the dimeric complex unit
2+
[Ag(μ-3)]2 intact. In the case of the chain-like coordination
polymers {[Ag(μ-1)][BF4]}n and {[Ag(μ-2)][BF4]}n partial de-
Figure 4. Molecular structure of the cyclic dimer {[Ag(μ-2)][BF4]}2
in the crystal.
Table 2. NMR spectroscopic data indicative of the coordination of the
respective P,N-ligand in the silver(I) complexes of the general compo-
sition [Ag(L)][BF4] (L = 1–3) in CDCl3 solution.
pected for a strictly dicoordinate AgI environment. This can
be attributed to weak interactions of the AgI atom with the
perchlorate anion, giving rise to the 2+1 coordination motif
frequently observed with AgI.[5a] In our four cases, an analo-
gous weak interaction of the AgI atom with the tetrafluorobor-
ate anion is reflected by P–Ag–N angles between ca. 149°
and 167°. The smallest angle occurs in the case of
{[Ag(μ-2)][BF4]}2, which exhibits two Ag···F contacts per sil-
ver atom. In the other three cases, a single such contact is
observed and the deviation from linearity correlates roughly
with the Ag···F distance, which ranges from ca. 2.67 Å to ca.
1H NMR signal(s) of α-pyridyl proton(s)
31P NMR signal
1
8.47
–17.7
L = 1 8.87
Δδ
2
L = 2 8.77
Δδ
11.3 (658)a)
29.0
0.40
8.48
–16.2
7.1 (702)a)
23.3
0.29
3
8.61, 8.40
–17.8
L = 3 9.00, 8.08
Δδ 0.39, –0.32
11.1 (691)a)
28.9
2.75 Å. These distances are well below the sum of the van der a) |1J(31P,109/107Ag)| in Hz.
Table 1. Selected bond lengths /Å and angles /° for the silver complexes with general composition [Ag(L)][BF4].
L = 1
{[Ag(μ-1)][BF4]}n
L = 2
{[Ag(μ-2)][BF4]}n
L = 2
{[Ag(μ-2)][BF4]}2
L = 3
{[Ag(μ-3)][BF4]}2
Ag–N
Ag–P
Ag···F
P–Ag–N
2.174(3)
2.3708(8)
2.737(2)
164.21(6)
2.162(6)
2.358(2)
2.752(6)
166.9(2)
2.177(5)
2.3571(16)
2.750(5), 2.987(4)
149.14(11)
2.173(3)
2.3591(10)
2.666(5)
156.61(10)
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Coordination of Ferrocene-based Pyridylphosphine Ligands towards AgI and AuI
polymerisation occurs upon dissolution. In view of the very with respect to the uncoordinated ligand. Not surprisingly, the
similar NMR spectroscopic features of all three compounds, 1H NMR signals diagnostic for N-coordination remain un-
we surmise that in these two cases cyclic oligomers are domi- shifted. N-coordination can be induced by removing the
nant in solution.
chlorido ligand present in these complexes. This was achieved
by reaction with one equivalent of Ag[BF4], which afforded
products of the expected general composition [Au(L)][BF4] ac-
cording to elemental analysis. Owing to their poor solubility,
characterisation by solution NMR spectroscopy was not pos-
sible. Fortuitously, single-crystals were obtained in the case of
L = 1. This was achieved by treating the solid with hot chloro-
form and layering the filtered extract with n-hexane at room
temperature. Apparently, this procedure separated a more solu-
ble minor component from the remaining insoluble, and there-
fore probably polymeric, product. The result of the X-ray dif-
fraction study is shown in Figure 6.
Gold Complexes
The reaction of ligands 1–3 with one equivalent of
[AuCl(tht)] (tht = tetrahydrothiophene) in dichloromethane af-
forded products of the expected composition [AuCl(L)] (L =
1–3) according to elemental analysis. In the case of L = 1,
single-crystals were obtained by recrystallisation from diethyl
ether. In the other two cases, single-crystals were obtained by
liquid phase diffusion of n-hexane into a dichloromethane
solution (L = 2) or of diethyl ether into a chloroform solution
(L = 3) of the respective compound. X-ray diffraction analyses
showed that the three molecular structures are very similar,
and that of [AuCl(1)] is shown in Figure 5 as a representative
example. Pertinent bond parameters are collected in Table 3.
Figure 5. Molecular structure of [AuCl(1)] in the crystal.
Figure 6. Molecular structure of the cationic unit of {[Au(μ-1)][BF4]}2
in the crystal.
Table 3. Selected bond lengths /Å and angles /° for the complexes of
the type [AuCl(L-κP)].
The quality of the crystal structure determination was affec-
ted by weak scattering of the needle-shaped crystal, which re-
sulted in a mediocre ratio of data with I Ͼ 2σ (I) to refined
parameters. The compound adopts a cyclic dimeric molecular
structure, reminiscent of that of the closely related silver com-
L = 1
L = 2
L = 3
Au–P
Au–Cl
P–Au–Cl
2.242(2)
2.296(2)
176.59(6)
2.2371(16)
2.301(2)
176.75(6)
2.2344(12)
2.3047(12)
175.30(4)
The Au bond parameters lie in the range commonly ob- pound {[Ag(μ-3)][BF4]}2 (vide supra). Metal–anion interac-
served for linear dicoordinate complexes of the type tions analogous to those found for the dimeric AgI complex
[AuCl(PR3)]. For example, the parent [AuCl(PPh3)] exhibits are absent here. The Au–P and Au–N bond lengths are
Au-P and Au–Cl bond lengths of 2.235(3) Å and 2.279(3) Å 2.252(4) Å and 2.159(14) Å, respectively, and the gold coordi-
and a P–Au–Cl angle of 179.63(8)°.[25] With PPh2(CH2Ph) as nation angle has a value of 174.5(4)°. The corresponding val-
ligand, the corresponding values are 2.2292(7) Å, 2.2983(7) Å ues for the parent [Au(PPh3)(Py)][BF4] (Py = pyridine) are
and 173.62(2)° for Au–P, Au–Cl and P–Au–Cl, respec- 2.2364(8) Å, 2.073(3) Å and 178.09(8)°,[27] and very similar
tively.[26]
values have been reported for closely related complexes,[28]
Robust P-coordination is indicated in each case by the pro- including also the ferrocenyl (Fc)-containing compound
nounced downfield shift of the 31P NMR signal of ca. 45 ppm [Au(PPh3)(Fc-3-py)](OTf).[29] The Au-N distance of
Z. Anorg. Allg. Chem. 2011, 1824–1833
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ARTICLE
2.159(14) Å found for {[Au(μ-1)][BF4]}2 is at the high end of [(AuCl)2(μ-4-κ2P,P)], which was characterised by NMR spec-
such bond length values for this type of complexes. A com- troscopy and high-resolution mass spectrometry (HRMS). Ro-
parison of the metal bond lengths of {[Au(μ-1)][BF4]}2 and bust P-coordination is clearly indicated by the pronounced
{[Ag(μ-3)][BF4]}2 (Table 1) provides further evidence for the downfield shift of the 31P NMR signal (δ = 28.3) of ca. 46 ppm
notion that the P-philicity of AuI is considerably higher than with respect to uncoordinated 4 (δ = –17.7).
that of AgI (vide supra). Schmidbaur and co-workers have
The mononuclear P,P-coordinated gold(I) complex
shown that the covalent radii of two-coordinate AgI and AuI [Au(4-κ2P,P)][SbF6] was obtained in a one-pot reaction of 4
are 1.33 Å and 1.25 Å, respectively, which means that the ra- in dichloromethane solution with one equivalent of [AuCl(tht)]
dius of gold(I) is smaller than that of silver(I) by 0.08 Å.[30] and subsequently with one equivalent of Ag[SbF6]. The com-
In our case, the M–P bond length difference of ca. 0.11 Å is plex gives rise to a single 31P NMR signal at δ = 42.6, which
significantly larger than this value, while the M–N bond corresponds to a coordination induced shift of ca. 60 ppm. This
lengths are indistinguishable within experimental error.
agrees well with data published for closely related dicoordinate
As a sideline of our investigation of the bidentate P,N-li- complexes of the type [Au(PR3)2]+.[32] Recrystallisation from
gands 1–3 in the coordination chemistry of gold(I), we have dichloromethane afforded single-crystals suitable for an X-ray
also briefly addressed the tridentate P,N,P-analogue 4 in this diffraction study. The molecular structure of the cation is
context. Neutral P,N,P-ligands based on a central pyridine unit shown in Figure 8. The gold atom is in a quasi-linear dicoordi-
are currently attracting great interest as versatile non-innocent nate environment. The Au–P bond lengths are 2.314(4) Å and
scaffolds for homogeneous catalysis.[31] Compound 4 was syn- 2.315(4) Å, and the gold coordination angle is 162.52(13)°.
thesised in analogy to 1 by Negishi cross-coupling of This compares well to values reported for closely related com-
Ph2PfcZnCl with 2,6-dibromopyridine.[4a] It was structurally pounds such as, for example, [Au(PPh3)2][BF4], which exhib-
characterised by single-crystal X-ray diffraction analysis (Fig- its Au–P bond lengths of 2.321(3) Å and 2.322(3) Å and a
ure 7). The quality of the crystal structure determination was P–Au–P angle of 167.3(1)°.[33] The fairly pronounced, but not
affected by weak scattering of the crystal, which resulted in a unusual, deviation of the P–Au–P unit from linearity in
poor ratio of data with I Ͼ 2σ (I) to refined parameters. Al- [Au(4-κ2P,P)][SbF6] is neither due to Au···F nor to Au···N con-
though a detailed discussion of bond parameters is not mean- tacts. The closest interatomic gold-fluorine distance is ca.
ingful, the connectivities are established unequivocally. The 3.60 Å, which is well above the sum of the van der Waals radii
two disubstituted ferrocene units are each in an approximately of gold and fluorine (ca. 3.2 Å), and the intramolecular gold-
eclipsed conformation, one of them synclinal and the other one nitrogen distance of ca. 4.39 Å is even further beyond the sum
anticlinal.
of the corresponding van der Waals radii (ca. 3.3 Å).[19]
Figure 8. Molecular structure of the cation of [Au(4-κ2P,P)][SbF6] in
the crystal.
Ligand 4 is able to act as a trans-spanning P,P-chelate li-
gand. Only a surprisingly limited number of such ligands is
known to date, and most of them have proved useful for appli-
cations in catalysis.[34] The large chelate ring size of 12 atoms
Figure 7. Molecular structure of compound 4 in the crystal.
Reaction of 4 with a slight excess of [AuCl(tht)] in dichloro- present in [Au(4-κ2P,P)]+, although not unprecedented for P,P-
methane afforded the expected dinuclear gold(I) complex chelates,[35] is remarkable. Close relatives of 4 among the
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Coordination of Ferrocene-based Pyridylphosphine Ligands towards AgI and AuI
1
a small amount of pure dichloromethane and then with n-hexane. H
NMR (CDCl3): δ = 3.94 (s, 4 H, fc), 4.17 (s, 4 H, fc), 4.26 (s, 4 H,
fc), 4.88 (s, 4 H, fc), 7.01 (m, 2 H, C5H3N), 7.30–7.38 (m, 21 H, Ph
trans-chelating diphosphine ligands are the biferrocene-based
TRAP ligands introduced by Ito,[36] which, however, form
nine-membered chelate rings.
and C5H3N). 13C{1H} NMR (CDCl3): δ = 68.50 (s), 71.20 (d, JPC
1 Hz), 73.23 (d, JPC = 4 Hz), 74.28 (d, JPC = 15 Hz), 76.72 (d, JPC
=
=
7 Hz), 85.19 (s), 117.04 (s), 128.28 (d, JPC = 7 Hz), 128.61 (s), 133.63
(d, JPC = 20 Hz), 135.93 (s), 139.15 (d, JPC = 10 Hz), 157.60 (s). 31P
NMR (CDCl3): δ = –17.7 (s). MS/MALDI(+): m/z (%) = 815 (100)
[M]+. Elemental analysis: C49H39NFe2P2·¼CH2Cl2 (836.7): C 70.85
(calcd. 70.70), H 4.78 (4.76), N 1.64 (1.67)%.
Conclusions
P,N-ligands 1–3 form coordination polymers or cyclic di-
mers with two-coordinate AgI and AuI. Ligands 1 and 2 had
previously been shown to form chelates with four-coordinate
metal centres, with bite angles ranging from ca. 90° to 125°.[4]
The absence of chelate structures was not unexpected with the
Group 11 metal atoms investigated here, although with low-
coordinate AgI, coordination angles down to, or even slightly
below, 150° have been reported even in the absence of struc-
turally relevant silver-anion interactions.[5a] Owing to the pres-
ence of the methylene bridge between the ferrocene moiety
and the pyridyl group, ligand 2 is more flexible than 1 and 3.
Consequently, its coordination behaviour is more temperamen-
tal, and different structure types can result with the same
metal-ligand fragment. The results obtained with the P,N,P-
ligand 4, which formed gold(I) complexes in a κ2P,P coordina-
tion mode in this preliminary study, augur well for the devel-
opment of a rich coordination chemistry of this compound, and
this issue will be addressed in due course.
Synthesis of [Ag(1)][BF4]: Ag[BF4] (19.5 mg, 0.1 mmol) was added
to a solution of 1 (44.7 mg, 0.1 mmol) in methanol (4 mL). The reac-
tion mixture was stirred in the dark for 5 h. Volatile components were
removed in vacuo. The residue was dissolved in dichloromethane
(2 mL) and n-hexane (15 mL) was added. The precipitate was isolated
by filtration, washed with diethyl ether (3 mL) and n-hexane (3 mL)
and dried in vacuo. Yield: 54.8 mg (85%). Single-crystals suitable for
an X-ray diffraction analysis were obtained by recrystallisation from
1
hot chloroform. H NMR (CDCl3): δ = 4.16 (s, 2 H, fc), 4.34 (s, 2 H,
fc), 4.55 (s, 2 H, fc), 4.90 (s, 2 H, fc), 7.37 (m, 1 H, 2-py), 7.47 (m,
7 H, Ph and 2-py), 7.61 (m, 4 H, Ph), 7.75 (m, 1 H, 2-py), 8.87 (s, 1
H, 2-py). 31P NMR (CDCl3): δ = 6.8 (br. d, JPAg ≈ 712 Hz). MS/
ESI(+): m/z (%) = 556 (100) [Ag(1)]+. MS/ESI(–): m/z (%) = 87 (100)
[BF4]–. Elemental analysis: C27H22NAgBF4FeP (641.9): C 50.50
(calcd. 50.52), H 3.66 (3.45), N 2.17 (2.18)%.
Synthesis of [Ag(2)][BF4]: Ag[BF4] (19.5 mg, 0.1 mmol) was added
to a solution of 2 (46.2 mg, 0.1 mmol) in methanol (5 mL). The reac-
tion mixture was stirred in the dark for 3 h and n-hexane (10 mL) was
added. The precipitate was isolated by filtration, washed with n-hexane
(3 mL) and dried in vacuo. This procedure afforded
[Ag(2)][BF4]·½C6H14. Yield 58.0 mg (89%). Single-crystals of the co-
ordination polymer {[Ag(μ-2)][BF4]}n were obtained by layering a ne-
arly saturated chloroform solution of the product placed in a 5 mm
NMR tube with a small amount of pure chloroform and then with n-
hexane. Layering a dichloromethane solution with diethyl ether af-
forded single-crystals of the cyclic dimer {[Ag(μ-2)][BF4]}2. 1H NMR
(CDCl3): δ = 3.93, 4.06, 4.13, 4.23, 4.54 (5ϫ s, 5ϫ 2 H, fc and CH2),
7.30 (m, 1 H, py), 7.39–7.44 (m, 7 H, Ph and 2-py), 7.50 (m, 4 H,
Ph), 7.79 (m, 1 H, 2-py), 8.77 (s, 1 H, 2-py). 31P NMR (CDCl3): δ =
7.1 (br. d, JPAg ≈ 702 Hz). MS/ESI(+): m/z (%) = 558 (100) [Ag(2)]+.
Experimental Section
Ligands 1–3 were prepared as described previously.[4c,d]
[AuCl(tht)],[37] 1-bromo-1Ј-(diphenylphosphanyl)ferrocene[38] and
[ZnCl2(1,4-dioxane)][39] were prepared according to established pro-
cedures. All other materials were procured from standard commercial
sources and used as received. Reactions were routinely performed un-
der an atmosphere of dry nitrogen by using standard Schlenk tech-
niques or a conventional glove-box. Solvents and reagents were appro-
priately dried and purified. Details concerning methods and instrumen-
tation used for compound characterisation have already been described
in detail elsewhere.[4d]
MS/ESI(–): m/z (%)
=
87 (100) [BF4]–. Elemental analysis:
C28H24NAgBF4FeP·½C6H14 (698.1): C 53.38 (cald. 53.34), H 4.25
(4.33), N 2.25 (2.01)%.
Preparative Work
Synthesis of 4: A 1.58 m solution of n-butyllithium in hexanes
(4.1 mL, 6.5 mmol) was slowly added at –70 °C to a stirred solution of
1-bromo-1Ј-(diphenylphosphanyl)ferrocene (2.89 g, 6.4 mmol) in THF
(40 mL). The mixture was kept at this temperature for 0.5 h.
[ZnCl2(1,4-dioxane)] (1.58 g, 7.1 mmol) was added. After 0.5 h the
mixture was allowed to warm to room temperature and stirred for a
further 2.5 h. 2,6-Dibromopyridine (734 mg, 3.1 mmol) and [Pd(PPh3)4]
(133 mg, 0.1 mmol) were added sequentially. The stirred reaction mix-
ture was heated to 60 °C for 72 h and subsequently allowed to cool to
room temperature. Silica gel (ca. 2 g) was added. Volatile components
were removed in vacuo to afford the crude product adsorbed on silica
gel. The product was purified by column chromatography on silica gel.
Less polar components were removed by elution with a 10:1 mixture
of petroleum ether and diethyl ether. The product was subsequently
eluted with dichloromethane containing 0.5% NEt3. Removal of the
eluent in vacuo afforded the product as a foamy solid. This procedure
afforded 4·¼CH2Cl2. Yield 824 mg (33%). Single-crystals suitable for
Synthesis of [Ag(3)][BF4]: Ag[BF4] (19.5 mg, 0.1 mmol) was added
to a solution of 3 (44.7 mg, 0.1 mmol) in methanol (4 mL). The reac-
tion mixture was stirred in the dark for 14 h. The orange solid was
isolated by filtration, washed with methanol (1 mL), diethyl ether
(3 mL) and finally n-hexane (3 mL) and dried in vacuo. Yield 41.9 mg
(65%). Single-crystals suitable for an X-ray diffraction analysis were
obtained by layering a nearly saturated chloroform solution of the
product placed in a 5 mm NMR tube with a small amount of pure
1
chloroform and then with n-hexane. H NMR (CDCl3): δ = 4.05 (s, 2
H, fc), 4.17 (s, 2 H, fc), 4.75 (s, 2 H, fc), 4.87 (s, 2 H, fc), 7.43 (m, 6
H, Ph), 7.60 (m, 4 H, Ph), 7.66 (s, 1 H, 3-py), 7.92 (s, 1 H, 3-py),
8.08 (s, 1 H, 3-py), 9.00 (br. s, 1 H, 3-py). 31P NMR (CDCl3): δ =
11.1 (br. d, JPAg ≈ 691 Hz). MS/ESI(+): m/z (%) = 556 (100) [Ag(3)]+.
MS/ESI(–): m/z (%)
=
87 (100) [BF4]–. Elemental analysis:
C27H22NAgBF4FeP (641.9): C 50.49 (calcd. 50.52), H 3.46 (3.45), N
2.30 (2.18)%.
an X-ray diffraction analysis were obtained by layering a concentrated Synthesis of [AuCl(1-κP)]: 1 (44.7 mg, 0.1 mmol) was added to a
dichloromethane solution (0.7 mL) placed in a 5 mm NMR tube with solution of [AuCl(tht)] (32.0 mg, 0.1 mmol) in dichloromethane
Z. Anorg. Allg. Chem. 2011, 1824–1833
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1829

ˇ
U. Siemeling, T. Klemann, C. Bruhn, J. Schulz, P. Steˇpnicˇka
ARTICLE
(5 mL) The reaction mixture was stirred for 3 h. The solvent volume
to remove insoluble components. The volume of the filtrate was re-
was reduced to slightly less than half in vacuo and n-hexane (25 mL) duced to slightly less than half in vacuo and diethyl ether (10 mL) was
was added. The precipitate was isolated by filtration, washed with di- added. The precipitate was isolated by filtration, washed with diethyl
ethyl ether (2 mL) and n-hexane (2 mL) and dried in vacuo. Yield ether (2 mL) and dried in vacuo. Yield 28.3 mg (39%). Single-crystals
26.0 mg (38%). Single-crystals suitable for an X-ray diffraction analy-
sis were obtained by recrystallisation from diethyl ether. 1H NMR
(CDCl3): δ = 4.18 (s, 2 H, fc), 4.35 (s, 2 H, fc), 4.44 (s, 2 H, fc), 5.00
(s, 2 H, fc), 7.09 (m, 1 H, 2-py), 7.39 (m, 1 H, 2-py), 7.44 (m, 4 H,
Ph), 7.49 (m, 1 H, 2-py), 7.57 (m, 6 H, Ph), 8.48 (m, 1 H, 2-py).
suitable for an X-ray diffraction analysis were obtained by treatment
of the product with hot chloroform, which dissolved part of the mate-
rial, and layering of the solution obtained after filtration at room tem-
perature with n-hexane. MS/ESI(+): m/z (%) = 1091 (85) [Au(1)2]+,
644 (100) [Au(1)]+. Elemental analysis: C27H22NAuBF4FeP (731.1):
13C{1H} NMR (CDCl3): δ = 69.25 (s), 70.05 (d, JPC = 74 Hz), 72.28 C 44.76 (calcd. 44.36), H 3.07 (3.03), N 2.01 (1.92)%.
(s), 74.78 (d, JPC = 9 Hz), 74.95 (d, JPC = 14 Hz), 85.71 (s), 120.80
Synthesis of [(AuCl)2(μ-4-κ2P,P)]: 4 (32.6 mg, 0.04 mmol) was added
(s), 121.45 (s), 129.70 (d, JPC = 12 Hz), 130.64 (s), 131.19 (s), 131.81
to a solution of [AuCl(tht)] (32.1 mg, 0.1 mmol) in dichloromethane
(5 mL). The reaction mixture was stirred for 22 h. Volatile components
were removed in vacuo. The crude product was dissolved in a minimal
amount of ethyl acetate and purified by column chromatography (neu-
tral alumina, ethyl acetate). The product was obtained as a yellow,
microcrystalline solid. Yield 41.0 mg (80%). 1H NMR (CDCl3): δ =
4.18 (s, 4 H, fc), 4.39 (s, 8 H, fc), 5.00 (s, 4 H, fc), 7.12 (m, 2 H,
C5H3N), 7.41–7.61 (m, 21 H, Ph and C5H3N). 13C{1H} NMR (CDCl3):
δ = 69.16 (s), 72.07 (s), 74.59 (s), 74.72 (s), 74.81 (s), 86.15 (s), 117.89
(s), 128.91 (d, JPC = 12 Hz), 130.76 (d, JPC = 64 Hz), 131.67 (d, JPC
= 2 Hz), 133.52 (d, JPC = 14 Hz), 136.83 (s), 156.25 (s). 31P NMR
(d, JPC = 64 Hz), 133.71 (d, JPC = 14 Hz), 136.79 (s), 149.46 (s),
157.10 (s). 31P NMR (CDCl3): δ = 27.6 (s). MS/APCI(+): m/z (%) =
679 (5) [M]+, 644 (100) [M
–
Cl]+. Elemental analysis:
C27H22NAuClFeP (679.7): C 47.52 (calcd. 47.71), H 3.25 (3.26), N
2.09 (2.06)%.
Synthesis of [AuCl(2-κP)]: 2 (46.1 mg, 0.1 mmol) was added to a
solution of [AuCl(tht)] (32.0 mg, 0.1 mmol) in dichloromethane
(5 mL) The reaction mixture was stirred for 6 h. n-Hexane (25 mL)
was added and the precipitate was isolated by filtration, washed with
diethyl ether (2 mL) and n-hexane (2 mL) and dried in vacuo. Yield
33.4 mg (48%). Single-crystals suitable for an X-ray diffraction analy-
sis were obtained by layering a dichloromethane solution of the prod-
uct (0.7 mL) placed in a 5 mm NMR tube with n-hexane. 1H NMR
(CDCl3): δ = 3.67 (s, 2 H, fc), 4.11 (m, 2 H, fc), 4.27 (m, 4 H, CH2
and fc), 4.51 (m, 2 H, fc), 7.10 (m, 2 H, 2-py), 7.41–7.52 (m, 6 H,
Ph), 7.54–7.62 (m, 5 H, Ph and 2-py), 8.47 (m, 1 H, 2-py). 13C{1H}
NMR (CDCl3): δ = 38.01 (s), 68.91 (d, JPC = 74 Hz), 70.02 (s), 71.01
(s), 73.54 (d, JPC = 9 Hz), 74.19 (d, JPC = 14 Hz), 88.23 (s), 121.36
(s), 122.78 (s), 128.95 (d, JPC = 12 Hz), 130.98 (d, JPC = 63 Hz),
131.62 (d, JPC = 3 Hz), 133.47 (d, JPC = 14 Hz), 136.58 (s), 149.01
(s), 160.27 (s). 31P NMR (CDCl3): δ = 29.2 (s). MS/ESI(+): m/z (%)
= 695 (15) [M]+, 658 (100) [M – Cl]+. Elemental analysis:
C28H24NAuClFeP (693.7): C 48.39 (calcd. 48.48), H 3.53 (3.49), N
1.84 (2.02)%.
(CDCl3):
δ
=
28.3 (s). HRMS/ESI(+): m/z calcd. for
[C49H39NAu2ClFe2NP2]+ ([M – Cl]+) = 1244.0276, found: 1244.0273.
Elemental analysis: C49H39NAu2Cl2Fe2P2 (1280.3): C 45.93 (calcd.
45.97), H 3.15 (3.07), N 0.99 (1.09)%.
Synthesis of [Au(4-κ2P,P)][SbF6]: 4 (81.6 mg, 0.1 mmol) was added
to a solution of [AuCl(tht)] (32.1 mg, 0.1 mmol) in dichloromethane
(5 mL). The reaction mixture was stirred for 22 h in the dark. Ag[SbF6]
(34.3 mg, 0.1 mmol) was added and the reaction mixture stirred in the
dark for 1 h. The mixture was filtered through a 1 cm pad of Celite®.
The filtrate was reduced to dryness in vacuo, affording the product
as a yellow, microcrystalline solid. Single-crystals were obtained by
recrystallisation from dichloromethane. Yield 121 mg (97%). 1H
NMR (CDCl3): δ = 4.01 (s, 4 H, fc), 4.15 (s, 4 H, fc), 4.74 (s, 4 H,
fc), 5.17 (s, 4 H, fc), 7.28 (d, J = 8 Hz, 2 H, C5H3N), 7.51–7.62 (m,
21 H, Ph and C5H3N). 13C{1H} NMR (CDCl3): δ = 69.22 (s), 71.65
(s), 74.54 (t, JPC = 4.5 Hz), 75.68 (t, JPC = 8 Hz), 86.91 (s), 118.81
(s), 129.60 (t, JPC = 6 Hz), 129.97 (t, JPC = 30.6 Hz), 132.44 (s), 133.50
(t, JPC = 7.4 Hz), 137.06 (s), 156.59 (s). 31P NMR (CDCl3): δ = 42.6
(s). HRMS/ESI(+): m/z calcd. for [C49H39Au2Fe2N1P2]+ ([Au(4)]+) =
1212.0922, found: 1212.0917. MS/ESI(–): m/z (%) = 235 (100)
[SbF6]–. Elemental analysis: C49H39NAuF6Fe2P2Sb·½CH2Cl2
(1290.7): C 46.04 (calcd. 46.06), H 3.37 (3.12), N 0.95 (1.09)%.
Synthesis of [AuCl(3-κP)]: 3 (44.7 mg, 0.1 mmol) was added to a
solution of [AuCl(tht)] (32.0 mg, 0.1 mmol) in dichloromethane
(5 mL) The reaction mixture was stirred for 6 h and n-hexane (25 mL)
was added. The precipitate was isolated by filtration, washed with di-
ethyl ether (2 mL) and n-hexane (2 mL) and dried in vacuo. Yield
33.5 mg (49%). Single-crystals suitable for an X-ray diffraction analy-
sis were obtained by layering a chloroform solution of the product
(0.7 mL) placed in a 5 mm NMR tube with diethyl ether. 1H NMR
(CDCl3): δ = 4.20 (s, 2 H, fc), 4.42 (s, 2 H, fc), 4.44 (s, 2 H, fc), 4.71
(s, 2 H, fc), 7.20 (s, 1 H, 3-py), 7.44 (m, 4 H, Ph), 7.49–7.58 (m, 6 H,
Ph), 7.65 (m, 1 H, 3-py), 8.42 (s, 1 H, Ph), 8.54 (s, 1 H, 3-py). 13C{1H}
NMR (CDCl3): δ = 68.34 (s), 70.37 (d, JPC = 73 Hz), 72.03 (s), 74.78
(d, JPC = 9 Hz), 75.06 (d, JPC = 14 Hz), 83.76 (s), 123.77 (s), 129.13
(d, JPC = 12 Hz), 129.31 (d, JPC = 12 Hz), 130.50 (s), 131.02 (s),
131.93 (d, JPC = 3 Hz), 133.59 (s), 133.68 (d, JPC = 14 Hz), 147.29
(s), 147.87 (s). 31P NMR (CDCl3): δ = 28.26 (s). MS/ESI(+): m/z (%)
= 644 (100) [M – Cl]+. Elemental analysis: C27H22NAuClFeP
(679.7): C 47.43 (calcd. 47.71), H 3.27 (3.26), N 2.15 (2.06).
X-ray Crystallography
For each data collection a single-crystal was mounted on a glass fibre
and all geometric and intensity data were taken from this sample. Data
collection using Mo-Kα radiation (λ = 0.71073 Å) was made with a
Stoe IPDS2 diffractometer equipped with a 2-circle goniometer and an
area detector. Absorption correction was done by integration using X-
red[40] except for {[Ag(μ-2)][BF4]}n·CHCl3. Unfortunately, this data
collection remains incomplete because the crystal was lost during the
measurement and no new single-crystal suitable for crystal structure
analysis could be obtained, despite many attempts. The data sets were
Synthesis of [Au(1)][BF4]: 1 (44.7 mg, 0.1 mmol) was added to a corrected for Lorentz and polarisation effects. The structures were
solution of [AuCl(tht)] (32.0 mg, 0.1 mmol) in dichloromethane solved by direct methods (SHELXS97) and refined using alternating
(5 mL) The reaction mixture was stirred for 1.5 h in the dark. Ag[BF4] cycles of least-squares refinements against F2 (SHELXL97).[41] All
(21.3 mg, 0.11 mmol) was added and stirring was continued in the dark non-hydrogen atoms were found in difference Fourier maps and were
for 14 h. Dichloromethane (10 mL) was added and the mixture filtered refined with anisotropic displacement parameters, except for the sol-
1830
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© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 1824–1833

Coordination of Ferrocene-based Pyridylphosphine Ligands towards AgI and AuI
Table 4. Crystal data and structure refinement details for the silver(I) complexes of ligands 1–3.
{[Ag(μ-1)][BF4]}n·2CHCl3
{[Ag(μ-2)][BF4]}n·CHCl3
{[Ag(μ-2)][BF4]}2·CH2Cl2
{[Ag(μ-3)][BF4]}2·2CHCl3
Empirical formula
Molecular weight
T /K
C29H24AgBCl6F4FeNP
880.69
100(2)
C29H25AgBCl3F4FeNP
775.35
298(2)
C57H50Ag2B2Cl2F8Fe2N2P2 C56H46Ag2B2Cl6F8Fe2N2P2
1396.89
100(2)
1522.65
173(2)
Crystal system
Space group
a /Å
b /Å
c /Å
monoclinic
P21/c
10.5259(10)
11.9401(16)
26.573(3)
monoclinic
P21/c
13.2362(14)
11.5572(13)
20.694(3)
triclinic
P1
monoclinic
P21/n
9.1606(5)
21.4054(9)
15.4766(9)
¯
9.0908(10)
13.1685(13)
13.3913(14)
112.067(8)
92.560(8)
106.301(8)
1405.5(3)
1
α /°
β /°
93.193(7)
91.336(11)
93.684(5)
γ /°
V /Å3
3334.6(6)
4
1.754
3164.7(7)
4
1.627
3028.5(3)
2
1.670
Z
Dcalcd. /g·cm–1
μ/mm–1
1.650
1.411
1.596
1.425
1.488
θ range/°
Refl. measured
Unique refl.
Rint
Refl. observed
R1, wR2 (I Ͼ 2σ
(I))
1.53 to 25.00
21156
5720
0.0773
4955
0.0307, 0.0842
1.54 to 25.00
2375
2074
0.0254
1179
0.0321, 0.0494
1.66 to 25.00
11332
4925
0.0762
3271
1.63 to 25.63
19521
5387
0.0304
4463
0.0409, 0.1115
0.0452, 0.0975
R1, wR2 (all data)
0.0377, 0.0903
–-0.867 / 0.974
0.0738, 0.0555
–0.151 / 0.175
0.0735, 0.1052
–0.779 / 0.707
0.0499, 0.1158
–0.746 / 1.418
Δρmin max
/e·Å–3
/
Table 5. Crystal data and structure refinement details for gold(I) complexes of ligands 1–3.
[AuCl(1)]
[AuCl(2)]
[AuCl(3)]
{[Au(μ-1)][BF4]}2
Empirical formula
Molecular weight
T /K
C27H22AuClFeNP
679.69
218(2)
C28H24AuClFeNP
693.72
223(2)
C27H22AuClFeNP
679.69
173(2)
C54H44Au2B2F8Fe2N2P2
1462.10
173(2)
Crystal system
Space group
a /Å
b /Å
c /Å
monoclinic
P21/n
13.8398(9)
10.7636(5)
16.6681(12)
monoclinic
P21/c
9.972(4)
22.351(9)
11.648(4)
triclinic
P1
monoclinic
P21/c
13.332(2)
27.486(4)
8.8823(12)
¯
8.7087(6)
8.9472(7)
16.2538(12)
94.250(6)
103.269(6)
107.591(6)
1160.88(15)
2
α /°
β /°
107.505(5)
105.81(3)
107.523(11)
γ /°
V /Å3
2368.0(3)
4
1.907
2497.9(15)
4
1.845
3103.7(8)
2
1.565
Z
Dcalcd. /g·cm–1
1.944
7.136
μ/mm–1
6.997
6.635
5.278
θ range /°
Refl. measured
Unique refl.
Rint
1.68 to 25.00
10860
4149
1.82 to 25.00
15428
4384
1.30 to 25.20
15146
4115
1.48 to 25.00
19862
5481
0.0607
0.1663
0.0498
0.1531
Refl. observed
R1, wR2 (I Ͼ 2σ (I))
R1, wR2 (all data)
3172
4081
3967
2427
0.0327, 0.0741
0.0461, 0.0766
–2.150 / 1.310
0.0521, 0.1370
0.0550, 0.1400
–3.026 / 2.484
0.0305, 0.0833
0.0316, 0.0841
–2.699 / 2.069
0.0798, 0.1720
0.1504, 0.1948
–0.955 / 2.977
Δρmin max
/e·Å–3
/
vent molecules in {[Au(μ-1)][BF4]}2 and [Au(4-κ2P,P)][SbF6], which probability level, except for the hydrogen atoms, which are drawn as
have been removed from the data set using the squeeze routine from
PLATON.[42] Furthermore, in [Au(4-κ2P,P)][SbF6] the anion appears
to be located on two positions with occupancies of 2/3 and 1/3, respec-
tively. In the minor occupied position the fluorine atoms are disordered
circles of arbitrary radius. Graphical representations were made using
ORTEP-3 win.[43] Pertinent crystallographic data are collected in
Table 4, Table 5 and Table 6. Crystallographic data (excluding struc-
ture factors) for the structures reported in this paper have been de-
over several positions and, hence, do not represent a chemically rea- posited with the Cambridge Crystallographic Data Centre as supple-
sonable result, but may be regarded as a crude approximated model. mental publication CCDC-824177, -824178, -824179, -824180,
The rather high residual electron densities are found close the [SbF6]–
anions. Hydrogen atoms were placed in constrained positions accord-
ing to the riding model with the 1.2 fold isotropic displacement param-
-824181, -824182, -824183, -824184, -824185 and 830433. Copies of
the data can be obtained free of charge on application to The Director,
CCDC, 12 Union Road, Cambridge CB2 1 EZ, UK (Fax: +44-1223-
eters. All figures represent the displacement ellipsoids at the 30% 336-033; E-mail for enquiry: fileserv@ccdc.cam.ac.uk).
Z. Anorg. Allg. Chem. 2011, 1824–1833
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
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ˇ
U. Siemeling, T. Klemann, C. Bruhn, J. Schulz, P. Steˇpnicˇka
ARTICLE
ˇ
[3] a) Ferrocenes: Ligands, Materials and Biomolecues (Ed.: P. Steˇp-
Table 6. Crystal data and structure refinement details for ligand 4 and
[Au(4-κ2P,P)][SbF6].
nicˇka), Wiley, Chichester, 2008; b) R. G. Arrayás, J. Adrio, J. C.
Carretero, Angew. Chem. Int. Ed. 2006, 45, 7674; c) R. C. J. At-
kinson, V. C. Gibson, N. J. Long, Chem. Soc. Rev. 2004, 33, 313.
4
[Au(4-κ2P,P)][SbF6]
ˇ
[4] a) J. Kühnert, M. Dusˇek, J. Demel, H. Lang, P. Steˇpnicˇka, Dalton
Empirical formula
Molecular weight
T /K
Crystal system
Space group
a /Å
b /Å
c /Å
α /°
β /°
C49H39Fe2NP2
815.45
193(2)
triclinic
P1
8.635(2)
12.721(3)
18.684(5)
102.60(2)
91.03(2)
95.93(2)
1990.4(9)
2
1.361
0.845
1.65 to 25.00
12726
6591
0.2092
1956
0.1169, 0.2847
0.2343, 0.3740
–2.106 / 1.059
C49H39AuF6Fe2NP2Sb
1248.17
100(2)
ˇ
Trans. 2007, 2802; b) J. Kühnert, I. Císarˇová, M. Lamacˇ, P. Steˇp-
nicˇka, Dalton Trans. 2008, 2454; c) P. Steˇpnicˇka, J. Schulz, T.
Klemann, U. Siemeling, I. Císarˇová, Organometallics 2010, 29,
3187; d) U. Siemeling, T. Klemann, C. Bruhn, J. Schulz, P. Steˇp-
ˇ
trigonal
ˇ
¯
¯
P3
nicˇka, Dalton Trans. 2011, 40, 4722.
26.9441(10)
26.9441(10)
11.2362(6)
90
90
120
7064.4(5)
6
1.760
4.403
1.51 to 24.98
15917
8296
0.0950
4361
0.0716, 0.1647
0.1299, 0.1881
–4.287 / 2.381
[5] See for example: a) M. A. Carvajal, J. J. Novoa, S. Alvarez, J.
Am. Chem. Soc. 2004, 126, 1465; b) M. C. Gimeno, A. Laguna,
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Coord. Chem. Rev. 2009, 253, 325.
γ /°
V /Å3
Z
Dcalcd. /g·cm–1
μ /mm–1
[7] Seminal paper: H. Schmidbaur, Y. Inoguchi, Z. Naturforsch. 1980,
35b, 1329.
θ range /°
Refl. measured
Unique refl.
Rint
[8] See for example: a) R. D. Hancock, L. J. Bartolotti, N. Kaltsoy-
annis, Inorg. Chem. 2006, 45, 10780; b) P. Schwerdtfeger, H. L.
Herrmann, H. Schmidbaur, Inorg. Chem. 2003, 42, 1334; c) D.-
Y. Wu, B. Ren, Y.-X. Jiang, X. Xu, Z.-Q. Tian, J. Phys. Chem. A
2002, 106, 9042.
[9] For thermodynamic data, see: P. Di Bernardo, A. Melchio, R. Por-
tanova, M. Tolazzi, P. L. Zanonato, Coord. Chem. Rev. 2008, 252,
1270.
Refl. observed
R1, wR2 (I Ͼ 2σ (I))
R1, wR2 (all data)
Δρmin max
/e·Å–3
/
[10] Y. Inoguchi, B. Milewski-Mahrla, D. Neugebauer, P. G. Jones, H.
Schmidbaur, Chem. Ber. 1983, 116, 1487.
Acknowledgments
[11] N. W. Alcock, P. Moore, P. A. Lampe, K. F. Mok, J. Chem. Soc.,
Dalton Trans. 1982, 207.
[12] A. Cingolani, Effendy, D. Martini, C. Pettinari, B. W. Skelton,
A. H. White, Inorg. Chim. Acta 2006, 359, 2183.
[13] K. K. Klausmeyer, F. Hung-Low, Acta Crystallogr., Sect. E 2007,
63, m1931.
This work was supported by the Deutscher Akademischer Austauschdi-
enst (project D/07/01319), the Ministry of Education, Youth and Sports
of the Czech Republic (project MEB100906) and by the Czech Science
Foundation (project no. P207/10/0176). We are grateful to Umicore
AG&Co. KG (Hanau, Germany) for a generous gift of precious metal
compounds.
[14] M. E. Olmos, A. Schier, H. Schmidbaur, Z. Naturforsch. 1997,
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Received: May 5, 2011
Published Online: August 11, 2011
Z. Anorg. Allg. Chem. 2011, 1824–1833
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
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