Synthesis, spectroscopic and structural characterisation of copper, silver and gold complexes of the mixed P/O-donor ligand Ph2P(CH2)2O(CH2)2O(CH2)2PPh2

Article abstract of DOI:10.1016/S0277-5387(00)00291-6

Reaction of L¹ (L¹ = Ph₂P(CH₂)₂O(CH₂)₂O(CH₂)₂PPh₂) with [Cu(MeCN)₄]PF₆ or AgBF₄] in CH₂Cl₂ solution yields the complexes [Cu(L¹) ] PF₆ and [Ag(L¹) ] BF₄ respectively as white solids. Spectroscopic measurements are consistent with coordination via the P-donors and the crystal structure of [Ag(L¹)]BF₄ confirms that L₁ acts as a trans-chelate giving an unusual example of approximately linear P₂-coordination at Ag (I) (angleP-Ag-P = 164.66 (4)°) and, despite the availability and proximity of the ether O atoms, these remain essentially uncoordinated (Ag···O = 2.95 A?), thus reflecting the low affinity of the soft Ag (I) ion for hard O-donor ligands. [ AuCl (tht) ], L¹ and TIPF₆ react in a 1:1:1 molar ratio in MeCN solution to yield the analogous Au (I) species [Au (L¹) ] PF₆, the structure of which also shows linear P₂-coordination and once again the O-donors are non-coordinating, at a distance of ca. 3.16 A?. from Au (I). The neutral dinuclear species [ (AuCl)₂(L¹) ] is readily formed by reaction of [AuCl(tht)] with L¹ in a 2:1 molar ratio in MeCN. Confirmation of the coordinated Cl ligands comes from IR spectroscopy, ν(Au-Cl) = 324 cm^-1, and δ(³¹P) which is indicative of a PCl donor set at Au(I). This arrangement is confirmed in the solid state from the crystal structure. The related phosphathia complex [(AuBr)₂L²)] (L²=Ph₂P(CH₂)₂S(o-C₆H₄)S(CH₂)₂PPh₂) is prepared similarly from [AuBr(tht)] and L² in MeCN solution and its structure reveals the AuBr units each coordinated to one P-donor and directed to the same side as the o-C₆H₄ unit. (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0277-5387(00)00291-6

www.elsevier.nl/locate/poly
Polyhedron 19 (2000) 743–749
Synthesis, spectroscopic and structural characterisation of copper,
silver and gold complexes of the mixed P/O-donor ligand
Ph2P(CH2)2O(CH2)2O(CH2)2PPh2
*
Bjorn Heuer, Simon J.A. Pope, Gillian Reid
Department of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, UK
Received 8 September 1999; accepted 3 January 2000
Abstract
Reaction of L1 (L1sPh2P(CH2)2O(CH2)2O(CH2)2PPh2) with [Cu(MeCN)4]PF6 or AgBF4 in CH2Cl2 solution yields the complexes
[Cu(L1)]PF6 and [Ag(L1)]BF4 respectively as white solids. Spectroscopic measurements are consistent with coordination via the P-donors
and the crystal structure of [Ag(L1)]BF4 confirms that L1 acts as a trans-chelate giving an unusual example of approximately linear P2-
coordination at Ag(I) (/P–Ag–Ps164.66(4)8) and, despite the availability and proximity of the ether O atoms, these remain essentially
1
˚
uncoordinated (Ag∆Os2.95 A), thus reflecting the low affinity of the soft Ag(I) ion for hard O-donor ligands. [AuCl(tht)], L and TlPF6
react in a 1:1:1 molar ratio in MeCN solution to yield the analogous Au(I) species [Au(L1)]PF6, the structure of which also shows linear
˚
P2-coordination and once again the O-donors are non-coordinating, at a distance of ca. 3.16 A from Au(I). The neutral dinuclear species
[(AuCl)2(L1)] is readily formed by reaction of [AuCl(tht)] with L1 in a 2:1 molar ratio in MeCN. Confirmation of the coordinated Cl
ligands comes from IR spectroscopy, n(Au–Cl)s324 cmy1, and d(31P) which is indicative of a PCl donor set at Au(I). This arrangement
is confirmed in the solid state from the crystal structure. The related phosphathia complex [(AuBr)2(L2)] (L2sPh2P(CH2)2S(o-
C6H4)S(CH2)2PPh2) is prepared similarly from [AuBr(tht)] and L2 in MeCN solution and its structure reveals the AuBr units each
coordinated to one P-donor and directed to the same side as the o-C6H4 unit.
q2000 Elsevier Science Ltd All rights reserved.
Keywords: Copper complexes; Silver complexes; Gold complexes
3
˚
1. Introduction
weak interactions to the thioether donors at ca. 3.0 A. L can
also act as a bridging ligand, e.g. in [Au2(L3)2]Cl2, which
adopts a helical metallocyclic cavity which hosts one of the
Cly anions [2–4]. In view of the unusual structures adopted
by these phosphathia ligand complexes we were interested to
investigate the effect of substituting the thioether functions
for the much harder ether functions, since the combination of
hard and softdonorsmayleadtootherunusualcharacteristics.
A variety of transition metal complexes of the mixed P/O-
donor ligand Ph2P(CH2)2O(CH2)2O(CH2)2PPh2 (L1) are
known, including cis- and trans-[MX2(L1)] (MsNi, Pd
or Pt, XsCl, Br or I) [5–7], and the Rh(I) species
[Rh(L1)(EtOH)(CO)]PF6 [8]. Gray and co-workers have
also investigated metallocyclic species containing the related
P2On-donor ligands L (LsPh2P{(CH2)2O}n(CH2)2PPh2,
ns3–5), e.g. cis-[Mo(CO)4(L)][9], whichinvolvebiden-
tate P2-coordination with the O-donors non-coordinating.
The Pt(II) species [PtX2(L)] also show P2-coordinationand
treatment of these species with a halide abstractor affords the
species [Pt(H2O)(L)]2q, which involve coordination of L
Our interest in multidentate mixed P/S-, P/N- and P/O-
donor ligands, in which the phosphine functions are located
at the termini, stems mainly from the fact that complexes of
these ligands offer a wide structural diversity, and incorpo-
ration of two different donor types within a single ligand may
lead to unusual properties. Phosphine ligation may enhance
the binding properties of the poorer thioether functions or of
the hard amine or ether functions or, alternatively, thesefunc-
tions may simply act as spacers between the phosphines. To
date, our work has mainly focused on the phosphathia ligands
and we have shown, for example, that Ph2P(CH2)2S-
(CH2)2S(CH2)2PPh2 (L3) coordinates to Pt(II) and Pt(IV)
via both the P and the S donor atoms in [Pt(L3)]2q and
[PtX2(L3)]2q, generating square planar and octahedral spe-
cies respectively [1]. In contrast, in the Au(I) species
[Au(L3)]PF6 we observe primary P2-coordination, with
* Corresponding author. Tel.: q44-1703-593609; fax: q44-1703-
593781; e-mail: gr@soton.ac.uk
0277-5387/00/$ - see front matter q2000 Elsevier Science Ltd All rights reserved.
PII S0277-5387(00)00291-6
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B. Heuer et al. / Polyhedron 19 (2000) 743–749
to Pt(II) via both P-donor atoms and one ether O-donor
[10]. The closely related metallocrown ether complex
[PdX2{Ph2P(CH2CH2O)4CH2CH2PPh2–P,P’}]n (XsCl or
I) shows a unique and reversible mode of molecular recog-
nition in which PdX2 units are incorporated into the metal-
locrown ether ring via a ring-expansion [11].
We describe herein the preparation and characterisationof
a series of transition metal complexes incorporating the
mixed P/O-donor ligand L1, including the crystal structures
of [Ag(L1)]BF4, [Au(L1)]PF6 and [(AuCl)2(L1)]. The
crystal structure of the phosphathia ligand complex
[(AuBr)2(L2)] is also included.
The 31P{1H} NMR spectrum of this species shows (Fig. 1)
two doublets at y3.4 ppm with 1J(109Ag–P)s601 Hz and
1J(107Ag–P)s523 Hz. These data are consistent with coor-
dination of L1 to Ag(I) via the two P-donor atoms [12]. The
coupling constants for this species are larger than those
observed for the phosphathia ligand analogues, e.g.
[Ag{Ph2P(CH2)2S(CH2)2S(CH2)2PPh2}]q which gave
1
1J(109Ag–P)s510 Hz and J(107Ag–P)s445 Hz [2–4],
although the 1J(107Ag–P):1J(109Ag–P) ratio of 0.87 is
the same, and this is consistent with the ratio expected
from the respective nuclear magnetic moments of the two
nuclei. 1J(107Ag–P) for the two-coordinate species
[Ag{P(tol)3}]2PF6 and [Ag(PtBu3)2]BF4 are reported as
496 and 444 Hz respectively [12,13], while the crystallo-
graphically authenticated two-coordinate[Ag{P(NMe2)3}2]-
BPh4 shows 1J(107Ag–P)s610 Hz [14].
2. Results and discussion
The ligand L1 was prepared using a modification of the
literature procedure [6]. LiPPh2 was generated in situ by
reaction of Li metal with PPh3 in thf solution. The LiPh
In order to confirm the 1:1 Ag:L1 stoichiometry and to
establish unequivocally the coordination mode of L1 to
Ag(I), a single crystal structure determination was under-
taken. The crystal structure of [Ag(L1)]BF4 confirms (Fig.
2, Table 1) that L1 functions essentially as a trans-chelating
ligand, giving an approximately linear arrangement at Ag(I)
t
byproduct was then destroyed by addition of BuCl and
Cl(CH2)2O(CH2)2O(CH2)2Cl was added. The resulting
mixture was refluxed for 1 h. After work-up and recrystallis-
ation of the product from CH2Cl2/hexane, L1 was obtained
in good yield. When the reaction was attempted without
refluxing, 31P{1H} NMR studies showed considerable
amounts of starting material, along with some mono-substi-
tuted product and traces of L1.
˚
with d(Ag–P)s2.402(1) A, and with a P–Ag–P angle of
˚
164.66(4)8. The Ag∆O distances of ca. 2.95 A are possibly
indicative of very weak interactions, but are probably simply
a consequence of the bite angle of the diphosphine unit in L1.
Both the large P–Ag–P angle and the observation that the P,
O and Ag atoms are approximately co-planar, provide strong
evidence that the O-donor atoms are not coordinating. L1 is
expected to be sufficiently flexible to accommodate a distor-
tion towards the tetrahedral geometry usually favoured by
four coordinate Ag(I). Both the cation and the BF4y anion
have crystallographic two-fold symmetry, with the Ag and B
atoms sitting on two-fold axes. Although Ag(I) has a much
greater affinity for soft donor atoms such as phosphinesrather
Treatment of [Cu(MeCN)4]PF6 with one molar equiva-
lent of L1 in CH2Cl2 solution, followed by precipitation with
Et2O, yields a white solid. Electrospray mass spectrometry
shows peaks at 549 and 551 indicative of [63/65Cu(L1)]q,
with no significant peaks at higher m/z. The IR spectrum
shows no evidence for any remaining coordinated MeCN,
but peaks corresponding to coordinated L1 and free PF6y are
clearly evident. 1H NMR spectroscopy and microanalysesare
consistent with theformulation[Cu(L1)]PF6 fortheproduct.
The 31P{1H} NMR spectrum shows a singlet at y16.2 ppm
(broadened owing to direct bonding to quadrupolar 63/65Cu)
arising owing to the coordinated L1 and a septet due to the
y
PF6 anion centred at y146 ppm. The NMR spectra were
recorded using thoroughly degassed solvents, since upon the
introduction of air to the solution the 31P{1H} NMR spectrum
also shows a resonance at q29.5 due to oxidised phosphine.
These data indicate the formulation [Cu(L1)]PF6 for the
product, and suggest that coordination to Cu(I) is via the P-
donors.
The corresponding Ag(I) species, [Ag(L1)]BF4, was
obtained as a white, light-sensitive solidbyreactionofAgBF4
with L1 in MeCN in a foil-wrapped flask, followed by con-
centration of the solution and addition of Et2O. The IR spec-
trum shows peaks indicative of coordinated L1 as well as
y
peaks at ca. 1053 and 525 cmy1, corresponding to free BF4
anion. The APCI mass spectrum shows peaks at m/z 593 and
595, corresponding to [107/109Ag(P2O2)]q. These data,
1
together with H NMR spectroscopic and microanalytical
data, indicate the formulation [Ag(L1)]BF4 for the product.
Fig. 1. 31P{1H} (145.8 MHz, CDCl3) NMR spectrum of [Ag(L1)]BF4.
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B. Heuer et al. / Polyhedron 19 (2000) 743–749
745
centrated solution. The IR spectrum confirms the presence of
L1 and a peak at 327 cmy1 is attributed to n(Au–Cl). This
compares with 324 cmy1 for [(AuCl)2(L2)] [2–4]. The
APCI mass spectrum shows peaks with the correct isotopic
distribution at m/z 915, corresponding to [Au2(L1)Cl]q.
Further peaks at lower m/z correspond to loss of Cl or Au
from the complex. The 31P{1H} NMR spectrum shows a
single resonance at q23.3 ppm, which is comparable with
d(31P) for the previously synthesised [(AuCl)2(L2)] (25.3
ppm) [2–4].
The crystal structure of [(AuCl)2(L1)] shows (Fig. 3,
Table 2) each gold atom coordinated to one P-donor from L1
and one Cl ligand, giving essentially linearcoordination,with
no interaction between the Au centres and the O-donoratoms.
The Cl–Au–P angles are 174.2(2) and 174.1(3)8. The L1
backbone adopts a twisted conformation with the AuCl units
pointing in the same direction.
We have reported previously the preparation and spec-
troscopic characterisation of the species [(AuCl)2(L)]
(LsL2, L3 or L4) (L4sPh2P(CH2)2S(CH2)3S(CH2)2-
PPh2) although their structures were not authenticated crys-
tallographically [2–4]. In order to provide a comparisonwith
Fig. 2. View of the structure of [Ag(L1)]q with the numbering scheme
adopted. Atoms marked * are related by a crystallographic two-fold axis.
Ellipsoids are drawn at the 40% probability level and H atoms are omitted
for clarity.
Table 1
1
˚
Selected bond lengths (A) and angles (8) for [Ag(L )]BF4
Ag(1)–P(1)
2.402(1)
P(1)–Ag(1)–P(1*)
Ag(1)–P(1)–C(1)
Ag(1)–P(1)–C(4)
Ag(1)–P(1)–C(10)
164.66(4)
113.9(1)
109.0(1)
116.8(1)
than hard ether functions, significant Ag–O(ether) interac-
tions have been observed, for example, in the mixed thia/oxa
macrocyclicspecies[Agn([15]aneS2O3)n](PF6)n ([15]ane-
S2O3s1,4,7-trioxa-10,13-dithiacyclopentadecane) (Ag–O
˚
s 2.492(4)–2.690(4) A) [15] and {[Ag2([18]ane-
S2O4)2]2}(PF6)4 ([18]aneS2O4s1,4,7,10-tetraoxa-13,16-
˚
dithiacyclohexadecane) (Ag–Os2.458(7)–2.661(6) A)
[16], hence there is no inherent reason for the O-donors not
interacting with the Ag(I) ion. Only two mononuclearAg(I)
complexes involving genuine P2-coordination have been
structurally characterised previously, [Ag(trimesitylphos-
˚
phine)2]PF6 (P–Ag–Ps179.4(5)8, Ag–Ps2.461(6) A)
[17,18]
and
[Ag{P(NMe2)3}2]BPh4
(P–Ag–Ps
˚
166.9(1)8, Ag–Ps2.395(2), 2.393(2) A) [14]. Several
y
Fig. 3. View of the structure of [(AuCl)2(L1)] with numbering scheme
adopted. Ellipsoids are drawn at 40% probability and H atoms are omitted
for clarity.
bis(phosphine)–silver(I) species involving ClO4
or
y
NO3 are known, although these also involve coordination
via the O-donors of the anions and this results in a much
smaller P–Ag–P angle, e.g. [Ag{PPh2(C5H9)}2]ClO4, Ag–
Table 2
˚
˚
1
Ps2.397(2)–2.432(2) A, Ag∆Os2.662(5), 2.709(5) A,
˚
Selected bond lengths (A) and angles (8) for [(AuCl)2(L )]
/P–Ag–Ps145.1(1), 153.0(1)8 [19], [Ag(PCy3)2-
˚
(NO3)], Ag–Ps2.440(3), 2.445(3) A, Ag–Os2.45(1),
Au(1)–Cl(1)
Au(2)–Cl(2)
2.295(5)
2.279(5)
Au(1)–P(1)
Au(2)–P(2)
2.231(5)
2.219(5)
˚
2.73(1) A, /P–Ag–Ps139.04(9)8 [20], [Ag(PCy3)2]-
˚
˚
ClO4, Ag–Ps2.429(1), 2.432(1) A, Ag∆Os2.720(7) A,
/P–Ag–Ps147.34(3)8 [20].
Cl(1)–Au(1)–P(1)
Au(1)–P(1)–C(1)
Au(1)–P(1)–C(13)
Au(2)–P(2)–C(18)
Au(2)–P(2)–C(25)
174.2(2)
113.7(6)
110.8(8)
113.4(7)
115.5(6)
Cl(2)–Au(2)–P(2)
Au(1)–P(1)–C(7)
Au(2)–P(2)–C(19)
174.1(3)
112.9(8)
110.7(7)
Reaction of L1 with [AuCl(tht)] in a 2:1 molar ratio in
MeCN gave the neutral dinuclear species [(AuCl)2(L1)]
which was isolated by precipitation with Et2O from a con-
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B. Heuer et al. / Polyhedron 19 (2000) 743–749
[(AuCl)2(L1)] above, we have prepared the species
[(AuBr)2(L2)] similarly from L2 and [AuBr(tht)] in
MeCN. The Au–Br stretching vibration occurs at 315 cmy1
for this species and d(31P) occurs as a singlet at 28.0 ppm,
consistent with coordination of an AuBr fragment to each P-
donor of L2. A single crystal X-ray structure determination
was also undertaken on a weakly diffracting crystal of
[(AuBr)2(L2)]. The structure shows (Fig. 4) a dinuclear
molecule with each Au(I) ion coordinated linearly to one P-
donor from L2 and one Br atom, with the S-donor atoms
remaining non-coordinating. The molecule has crystallo-
˚
graphic C2 symmetry and the Au–P distances of 2.16(1) A
are slightly shorter than those in [(AuCl)2(L1)] above,
although since the structure quality is rather poor, geometric
parameters should be treated with caution. The P–Au–Br
angle is177.5(4)8. The L2 backbone adoptsanapproximately
planar arrangement and the AuBr units lie on the same side
of the backbone as the o-phenylene unit.
Fig. 4. View of the structure of [(AuBr)2(L2)] with numbering scheme
adopted. Ellipsoids are drawn at 40% probability. Atoms marked * are
related by a crystallographic two-fold axis and H atoms are omitted for
˚
clarity. Au(1)–P(1)s2.16(1) A, /P(1)–Au(1)–Br(1)s177.5(4)8.
The 1:1 Au:L1 complex, [Au(L1)]PF6 was prepared read-
ily by treatment of [AuCl(tht)] with one molar equivalent
of L1 and TlPF6 in MeCN to give a white precipitate (TlCl)
and a colourless solution. Following removal of the TlCl by
filtration through Celite, concentration of the solution and
addition of Et2O, a white precipitate was obtained. The IR
spectrum of this product provides evidence for the presence
of L1 and PF6y (840, 555 cmy1), and there is no evidence
for an Au–Cl stretching vibration. The highest mass peak in
the APCI mass spectrum appears at m/z 683, corresponding
to [Au(L1)]q. These data, together with 1H NMR spectro-
scopic and microanalytical data, suggest the formulation
[Au(L1)]PF6 for the product. The 31P{1H} NMR resonance
due to the coordinated L1 occurs at 32.5 ppm, i.e. a higher
frequency than that for [(AuCl)2(L1)], and is indicative of
y
a P2-donor set at Au(I). The septet due to the PF6 anion
occurs at y146.0 ppm.
This crystal structure of [Au(L1)]PF6 shows (Fig. 5,
Table 3) L1 acting as a trans-chelating ligand, bonded to
Fig. 5. View of the structure of [Au(L1)]q with numbering schemeadopted.
Ellipsoids are drawn at 40% probability and H atoms are omitted for clarity.
˚
Au(I) by the two P-donors (Au–Ps2.308(2), 2.311(2) A),
with theAu∆Odistancesca. 3.15Aindicatingnointeraction,
Table 3
˚
1
˚
Selected bond lengths (A) and angles (8) for [Au(L )]PF6
and demonstrating the indifference of Au(I) towardsthehard
O-donor atoms. Thus, this geometry is similar to that
observed for [Ag(L1)]q above. The Au–P distances in this
cation are slightly shorter than the Ag–P distances in
[Ag(L1)]q and the P–Au–P angle of 171.85(9)8 is larger
than the corresponding P–Ag–P angle in theanalogousAg(I)
species. Schmidbaur and co-workers have previously dem-
onstrated that for the isomorphous species [Ag(trimesityl-
phosphine)2]BF4 and [Au(trimesitylphosphine)2]BF4,
Au(1)–P(1)
2.308(2)
Au(1)–P(2)
2.311(2)
117.4(3)
P(1)–Au(1)–P(2)
Au(1)–P(1)–C(7)
Au(1)–P(2)–C(6)
171.85(9) Au(1)–P(1)–C(1)
113.5(3)
115.5(3)
Au(1)–P(1)–C(13) 107.9(3)
Au(1)–P(2)–C(19) 114.3(3)
Au(1)–P(2)–C(25) 109.2(3)
3. Experimental
˚
d(Ag–P))d(Au–P) by almost 0.1 A [18]; a similar trend
Infrared spectra were recorded as KBr or CsI disks using
a Perkin-Elmer 983 spectrometer over the range 4000–200
cmy1. Mass spectra were run by positive electrospray or by
APCI (atmospheric pressure chemical ionisation) in MeCN
solution using a VG Biotech platform. 1H and 13C{1H} NMR
spectra were recorded in CDCl3 using a Bruker AM300 spec-
is observed here. The structure of the analogous phosphathia
complex [Au(L2)]PF6 shows similar primary Au–P inter-
˚
actions of 2.284(7) and 2.302(7) A, although in this case
long-range, weak Au∆S interactions of ca. 3.0 A are also
˚
observed in the solid state [2–4].
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B. Heuer et al. / Polyhedron 19 (2000) 743–749
747
trometer. 31P{1H} NMR spectra were recorded in CH2Cl2
containing ca. 10–15% CDCl3 using a Bruker AM360 spec-
trometer operating at 145.8 MHz and are referenced to 85%
H3PO4. Microanalyses were performed by the University of
Strathclyde microanalytical service. L2 was prepared accord-
ing to the literature procedure [6].
4.4%. Electrospray mass spectrum (MeCN): found m/z 595,
593, 487; calc. for [109Ag(L1)]q m/z 595, [107Ag(L1)]q
593, [L1]q 486. 1H NMR: d 7.4–7.7 (m, Ph, 20H), 3.7 (m,
CH2O, 8H), 2.8 (m, CH2P, 4H). 31P{1H} NMR: d –3.4 (d,
1
1J109(Ag–31P)s601 Hz, d, J107(Ag–31P)s523 Hz). IR
spectrum (CsI disk): 3055w, 2960w, 2917w, 2869w, 1572w,
1481m, 1461w, 1434m, 1410w, 1365m, 1350m, 1309w,
1284w, 1099s, 1053s, 1005s, 998s, 976w, 885m, 856m,
3.1. Preparations
790w, 760s, 746s, 712m, 698s, 692s, 673w, 525m cmy1
.
L1: PPh3 (30 g, 114 mmol) was dissolved in dry, degassed
thf (300 cm3) and freshly crushed Li (3 g, 432 mmol) was
added in small pieces at room temperature. This reaction
mixture was stirred for 12 h, before the remaining pieces of
[Au(L1)]PF6: To a solution of L1 (0.100 g, 0.206 mmol)
in degassed MeCN (20 cm3) was added [AuCl(tht)] (0.066
g, 0.206 mmol). After stirring this mixture for 15 min, TlPF6
(0.072 g, 0.206 mmol) was added and the reaction mixture
was stirred for ca. 12 h. The resultingwhiteprecipitate(TlCl)
was removed by filtration and the filtrate was concentrated in
vacuo. Addition of Et2O gave a white precipitate which was
filtered, washed with Et2O and dried in vacuo. Yield 0.054
g, 32%. Anal. Calc. for [C30H32AuF6O2P3]: C, 43.5; H, 3.9.
Found: C, 43.5; H, 3.6%. Electrospray mass spectrum
(MeCN): found m/z 683, 487; calc. for [Au(L1)]q m/z 683,
[L1]q 486. 1H NMR: d 7.5–7.8 (m, Ph, 20H), 3.8(m, CH2O,
4H), 3.6 (s, CH2O, 4H), 2.9 (m, CH2P, 4H). 31P{1H} NMR:
d 32.5 (s, L1), y146.0 (spt, PF6y). IR spectrum (CsI disk):
3061w, 2980w, 2925w, 2866w, 1560w, 1482m, 1458w,
1435s, 1406w, 1362m, 1227w, 1186w, 1134s, 1114m, 1104s,
1063m, 1012m, 836vs, 789m, 744m, 713s, 696s, 690s, 558s,
t
lithium were filtered off. BuCl (9.9 cm3, 91 mmol) was
added dropwise and the mixture was stirred for 1 h at room
temperature. Cl((CH2)2O)2(CH2)2Cl (7.5 cm3, 0.4 equiv.,
46 mmol) was added slowly and the mixture was heated to
reflux for 1 h until it decolourised and a white precipitate
formed. After cooling, degassed water (30 cm3) was added
dropwise. The organic layer was separated, the aqueous layer
was washed with Et2O and the combined organic extracts
were dried over MgSO4. The MgSO4 was filtered off under
nitrogen and the solvent was removed in vacuo. The residue
was taken up in a small amount of CH2Cl2, then hexane was
added. The mixture was stirred for a few minutes and sub-
sequent cooling yielded a white precipitate which wasfiltered
and dried in vacuo. Yield 10.7 g, 39%. Anal. Calc. for
529m, 509m 463m, 438w cmy1
.
1
C30H32O2P2: C, 74.1; H, 6.6. Found: C, 73.7; H, 6.9%. H
[(AuCl)2(L1)]: To a solution of L1 (0.100 g, 0.206
mmol) in degassed MeCN (30 cm3) was added [AuCl(tht)]
(0.130 g, 0.411 mmol). The mixture wasstirredfor1hbefore
being concentrated in vacuo. Et2O was then added to yield
a white solid which was filtered, washed with Et2O and
dried in vacuo. Yield 0.060 g, 31%. Anal. Calc. for
[C30H32Au2Cl2O2P2]: C, 37.9; H, 3.4. Found: C, 38.0; H,
3.4%. Electrospray mass spectrum (MeCN): found m/z 915,
683, 487; calc. for [Au235Cl(L1)]q m/z 915, [Au(L1)]q
683, [L1]q 486. 1H NMR: d 7.4–7.8 (m, Ph, 20H), 3.8 (m,
CH2O, 4H), 3.5 (s, CH2O, 4H), 2.8 (m, CH2P, 4H). 31P{1H}
NMR: d q23.3 (s, L1). IR spectrum (CsI disk): 3049w,
2945w, 2911w, 2857w, 1560w, 1482m, 1433s, 1395w,
1368m, 1351m, 1289w, 1158w, 1129s, 1100s, 1009m, 998w,
980m, 905w, 864w, 763m, 744s, 698s, 690s, 544m, 525m,
NMR: d 7.41–7.52 (m, 20H, Ph), 3.58 (m, 4H, OCH2), 3.51
(s, 4H, OCH2), 2.40 (m, 4H, CH2P) ppm. 13C{1H} NMR:
d 28.9 (CH2P), 68.7 (CH2CH2P), 70.2 (OCH2CH2O),
128.6 (para-C), 128.8 (meta-C), 132.8 (ortho-C), 138.5
(ipso-C) ppm. 31P{1H} NMR: d y21.3.
[Cu(L1)]PF6: L1 (0.100 g, 0.206 mmol) was dissolved
in CH2Cl2 (30 cm3) and [Cu(CH3CN)4]PF6 (0.077 g, 0.206
mmol) was added in one portion. The mixture was stirred for
1 h and the volume was reduced to ca. 2 cm3 in vacuo. Et2O
was then added to afford a white solid which was collected
by filtration and dried in vacuo. Yield 0.085 g, 60%. Anal.
Calc. for C30H32O2P3F6Cu: C, 51.8; H, 4.6. Found: C, 52.4;
1
H, 4.6%. H NMR: d 7.17–7.49 (m, 20H, Ph), 3.62–3.77
(m, 8H, CH2), 2.59 (m, 4H, CH2) ppm. 31P{1H} NMR: d
y16.2 (s, L1), y146.2 (spt, PF6y) ppm. APCI mass spec-
trum: found m/z 551, 549, 487; calc. for [65Cu(L1)]q m/z
551, [63Cu(L1)]q 549, [L1]q 486. IR spectrum (CsI disk):
3058w, 2985w, 2922w, 2873w, 1574w, 1485m, 1438s,
1403w 1360m, 1310w, 1161m, 1133s, 1101s, 999m, 841vs,
487m, 476w, 327m cmy1
.
[(AuBr)2(L2)]: To a solution of L2 (0.08 g, 0.0141
mmol) in degassed MeCN (30 cm3) wasadded[AuBr(tht)]
(0.103 g, 0.242 mmol). The resulting mixture was stirred for
1 h. The reaction volume was concentrated to 2 cm3 in vacuo
and Et2O was added to give a white solid. Yield 0.115 g,
73%. Anal. Calc. for [C34H32Au2Br2P2S2]PEt2O: C, 38.1; H,
3.3. Found: C, 37.8; H, 3.0%. Electrospray mass spectrum
(MeCN): found m/z 763, 566; calc. for [Au(L2)]q m/z 763,
[L2]q 566. 1H NMR: d 7.1–7.7 (m, aromatic H, 24H), 2.6–
3.2 (m, CH2S, 8H). 31P{1H} NMR: d 28.0 (s, L1). IR spec-
744s, 696s, 558m, 508m, 478m cmy1
.
[Ag(L1)]BF4: To a degassed solution of L1 (0.100 g,
0.206 mmol) in MeCN (20 cm3) at 08C was added AgBF4
(0.040 g, 0.206 mmol) and the resulting mixture was stirred
for 1 h at room temperature in a foil-wrapped flask. The
solution was then concentrated in vacuo to ca. 5 cm3 andEt2O
was added to afford a white solid which was filtered, washed
with Et2O and dried in vacuo. Yield 0.096 g, 69%. Anal. Calc.
for [C30H32AgBF4O2P2]: C, 52.9; H, 4.7. Found: C, 52.6; H,
trum (Nujol mull): 315 cmy1
.
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748
B. Heuer et al. / Polyhedron 19 (2000) 743–749
Table 4
Crystallographic data
[Ag(L1)]BF4
[Au(L1)]PF6
[(AuCl)2(L1)]
[(AuBr)2(L2)]P2CH2Cl2
Formula
M
Crystal system
C30H32AgBF4O2P2
681.20
monoclinic
C2/c
15.822(7)
13.157(7)
15.76(1)
90
118.11(5)
90
C30H32AuF6O2P3
828.46
triclinic
P-1
10.670(3)
15.458(4)
10.135(3)
107.97(2)
97.75(3)
75.39(2)
1535.6(8)
2
C30H32Au2Cl2O2P2
951.37
monoclinic
Pn
9.285(2)
11.905(2)
14.276(1)
90
96.54(1)
90
C36H32Au2Br2Cl4P2S2
1286.27
monoclinic
C2
13.203(5)
13.038(4)
12.250(6)
90
95.02(3)
90
2100(1)
2
Space group
˚
a (A)
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
3
˚
U (A )
2894(3)
4
8.58
1567.8(5)
2
96.16
Z
m(Mo Ka) (cmy1
)
50.27
93.64
Transmission factors (max. and min.)
1.000, 0.850
5112
0.075
1.000, 0.667
5400
0.050
1.000, 0.490
2917
0.064
1.000, 0.499
3973
0.170
Unique observed reflections
R
int (based on F2)
Observed reflections with Io)ns(Io)
4469, ns2
182
0.053
4191, ns2
379
0.045
2169, ns2
343
0.035
1118, ns2
117
0.063
No. of parameters
R a
Rw
b
0.073
0.057
0.040
0.069
a Rs8(NFobsNiyNFcalcNi)/8NFobsNi.
b Rws6[8wi(NFobsNiyNFcalcNi)2/8wiNFobsNi ].
2
3.2. X-Ray crystallography
[Au(L1)]PF6: All non-H atoms were refined anisotropi-
cally while H-atoms were placed in fixed, calculated posi-
tions. Selected bond lengths and angles are given in Table 3.
[(AuCl)2(L1)]: All non-H atoms were refined anisotrop-
ically and H atoms were included in fixed, calculated posi-
tions. Selected bond lengths and angles are given in Table 2.
[(AuBr)2(L2)]P2CH2Cl2: The data were collected from
a weakly diffracting crystal, hence the structure quality is not
as high as normal. The molecule possesses crystallographic
C2 symmetry and hence only half the molecule is present in
the asymmetric unit. A CH2Cl2 solvent molecule was also
identified in the asymmetric unit. At isotropic convergence a
DIFABS [23] absorption correction was applied. In view of
the weak data, only the Au, Br, S and P atoms were refined
anisotropically. The H atoms were included in fixed, calcu-
lated positions.
Details of the crystallographic data collection and refine-
ment parameters are given in Table 4. The crystals were
grown by vapour diffusion of diethyl ether onto solutions of
the complexes in CH2Cl2 at ca. y158C or by slow evapora-
tion from a solution of the complex in CH2Cl2/EtOH
([Ag(L1)]BF4). Data collection used a Rigaku AFC7S
four-circle diffractometer equipped with an Oxford Systems
open-flow cryostat operating at 150 K, using graphite-
˚
monochromated Mo Ka X-radiation (ls0.71073 A). The
structures were solved by heavy atom methods [21] and
developed by iterative cycles of full-matrix least-squaresand
difference Fourier synthesis [22]. The weighting scheme
wy1ss2(F) gave satisfactory agreement analyses.
[Ag(L1)]BF4: During data collection an 8.2% decrease in
the intensity of the standard reflections was observed and
hence a linear decay correction was applied. The initial cell
was triclinic, and was solved to reveal one [Ag(L1)]q cation
and one BF4y anion occupying general positions. However,
further analysis suggested a C-centred monoclinic cell,which
Supplementary data
Supplementary data are available from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK (fax: q44-1223-336033; e-mail: deposit@
ccdc.cam.ac.uk) on request, quoting the deposition numbers
134142–134145.
y
was solved to reveal a half [Ag(L1)]q cation and half BF4
anion, both with crystallographic two-fold symmetry.
Although the final residuals for the monoclinic version are
slightly higher (Rs0.053 versus 0.045) than for the triclinic
solution, it does appear that the correct solution is as mono-
clinic C-centred. All non-H atoms were refined anisotropi-
cally while H-atoms were placed in fixed, calculated
positions. Selected bond lengths and angles are given in
Table 1.
Acknowledgements
We thank the EPSRC and the University of Southampton
for support and Johnson Matthey plc for generous loans of
gold salts. We also thank the crystallographic referee for
suggesting the higher symmetry cell for [Ag(L1)]BF4.
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B. Heuer et al. / Polyhedron 19 (2000) 743–749
749
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