Gold(I) alkynyl complexes derived from ethynylanilines: Crystal structure of [Au(C≡C-4-C6H4NH2){P(3-tolyl) 3}] a polymer in the solid state via NH?Au contacts

Article abstract of DOI:10.1016/j.ica.2004.06.068

Reaction of [AuCl(SMe₂)] with para-ethynylaniline and para-ethynyl-ortho-toluidine affords oligomers, [Au(CC-4-C₆H ₃RNH₂)]_n (R = H, Me), which in turn react with tertiary phosphines or 2,5-dimethylphenylisocyanide to give monomeric adducts, [Au(C≡C-4-C₆H₃RNH₂)L]. One of these, [Au(CC-4-C₆H₄NH₂){P(3-tolyl)₃}], has been crystallographically characterised and is a polymer in the solid state, being held together via NH?Au contacts.

Full text of DOI:10.1016/j.ica.2004.06.068

Inorganica Chimica Acta 358 (2005) 1386–1392
www.elsevier.com/locate/ica
Gold(I) alkynyl complexes derived from ethynylanilines:
crystal structure of [Au(C„C-4-C6H4NH2){P(3-tolyl)3}] a polymer
q
in the solid state via NHꢀ ꢀ ꢀAu contacts
a,
Graeme Hogarth , Miguel M. Alvarez-Falcon
a,b
´
*
´
a
Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK
´ ´
Departamento de Quımica Inorganica, Facultad de Quimica, Universidad de Murcia, Apartado 4021, Murcia 30071, Spain
b
Received 7 April 2004; accepted 30 June 2004
Dedicated to Professor Gordon Stone in recognition of his contributions to organometallic chemistry
Abstract
Reaction of [AuCl(SMe2)] with para-ethynylaniline and para-ethynyl-ortho-toluidine affords oligomers, [Au(C„C-4-
C6H3RNH2)]n (R = H, Me), which in turn react with tertiary phosphines or 2,5-dimethylphenylisocyanide to give monomeric
adducts, [Au(C„C-4-C6H3RNH2)L]. One of these, [Au(C„C-4-C6H4NH2){P(3-tolyl)3}], has been crystallographically character-
ised and is a polymer in the solid state, being held together via NHꢀ ꢀ ꢀAu contacts.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Gold(I) complexes; Alkynyl complexes; Ethynylanilines; X-ray crystal structure
1. Introduction
building blocks towards the synthesis of multimetallic
arrays [14], especially in which the binding sites are elec-
tronically conjugated and can potentially incorporate
alternating high and low-valent metal centres.
There is continued interest in the chemistry of alkynyl
gold(I) complexes primarily resulting from their physical
properties, such as, luminescence [1–5], non-linear opti-
cal behavior [6–8] and liquid crystalline [9] properties.
Further, the linearity of the M–C„C moiety and the
preference of gold(I) for linear two coordination, makes
alkynyl gold(I) compounds attractive candidates for the
design of rigid-rod molecules [10] or metal-containing
linear-chain polymers with extended electronic conjuga-
tion along the backbone [8,11–13]. One way of building
up extended chains containing these sub-units is to uti-
lise alkynyl ligands with a second metal binding site.
In this context, ethynylanilines are potentially useful
Herein, we describe the synthesis of new alkynyl
gold(I) complexes derived from 4-ethynylaniline and 2-
methyl-4-ethynylaniline by using well-known and
straightforward synthetic pathways such as the ‘‘acac
method’’ [15] and depolymerization reactions [16–18].
In addition, the crystal structure of [Au(C„C-4-
C6H4NH2){P(3-tolyl)3}] is reported which shows that
the molecules pack through N–Hꢀ ꢀ ꢀAu contacts. As
far as we know, this is the first time such contacts have
been shown to play an important role in the molecular
packing of gold complexes.
q
Dedicated to Professor Stone for his inspiring undergraduate
lectures and kind support during my early career.
2. Results and discussion
*
Corresponding author. Tel.: +44 207 679 4603; fax: +44 207 380
7463.
The reactions between [AuCl(SMe2)] and the corre-
sponding ethynylanilines in the presence of triethylam-
E-mail addresses: g.hogarth@ucl.ac.uk (G. Hogarth), miguelaf@
´
um.es (M.M. Alvarez-Falcon).
´
0020-1693/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2004.06.068

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G. Hogarth, M.M. Alvarez-Falcon / Inorganica Chimica Acta 358 (2005) 1386–1392
´
1387
ine afforded in high yields the neutral oligomers
[Au(C„C-4-C6H3RNH2)]n 1a–b as orange solids
(Scheme 1). As a result of the tendency of many com-
plexes of this type to explode on contact when pure
[16–20], we did not attempt any further purification
and due to their extreme insolubility in all common or-
ganic solvents, they could not be characterized by NMR
techniques. Like related (alkynyl)gold(I) complexes [21],
both 1a–b showed a band at around 2000 cmꢁ1 in the IR
spectrum being attributed to the m(C„C) stretching
mode, while elemental analysis were in agreement with
the proposed formulation. We assume that 1a–b adopt
structures similar to other gold complexes of this type,
whereby each gold atom is assumed to be simultane-
ously r-coordinated to one alkynyl fragment and p-
bonded to the carbon–carbon triple bond of an adjacent
molecule [22–24], but cannot rule out the possibility of
amine coordination.
gold(I) polymers, upon addition of good r-donor
ligands such as phosphines, isocyanides or halides. Such
reactions have allowed the synthesis of a huge number
of new neutral [18,25–28] and ionic [29–31] gold(I) alky-
nyl complexes. In this context, we reacted oligomeric
1a–b with tertiary phosphines PR3(R = Ph, C6H4Me-3,
C6H4OMe-4, C6H4F-4) or 2,5-dimethylphenylisocya-
nide (XyNC) to obtain the corresponding mixed (alky-
nyl)gold(I) derivatives, [LAu(C„C-4-C6H3RNH2)]
2a–6a, 3b, 4b and 6b (Scheme 1). All were carried out
in dichloromethane, in which the oligomeric starting
materials 1a–b are completely insoluble. The addition
of the appropriate ligand caused the immediate disap-
pearance of the initial suspension, resulting in solutions
from which the neutral derivatives were isolated in good
to moderate yields (41–77%).
Characterisation was relatively straightforward. All
show molecular ions in their FAB mass spectra,
although for the phosphine complexes the spectra are
dominated by signals corresponding to the [AuPR3]+
(100%) and [Au(PR3)2]+ (90–50%) fragments, as has
One of the most widely used methods of preparing
new (alkynyl)gold(I) compounds centres on the depo-
lymerization reaction of neutral homoleptic alkynyl-
-
H2N
C
C
Au
C
C
NH2
7
[Au(acac) 2]
Me
H
C
C
NH2
H
C
C
NH2
[AuCl(SMe2)]
[AuCl(SMe2)]
Me
Au
C
C
NH2
Au
C
C
NH2
n
n
1a
1b
L
L
Me
L
Au
C
C
NH2
Au
C
C
NH2
L
3b L = P(C6H4OMe-4)3
4b L = P(C6H4F-4)3
6b L = 2,5-Me2C6H3NC
2a L = PPh3
3a L = P(C6H4OMe-4)3
4a L = P(C6H4F-4)3
5a L = P(C6H4Me-3)3
6a L = 2,5-Me2C6H3NC
Scheme 1.

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´
G. Hogarth, M.M. Alvarez-Falcon / Inorganica Chimica Acta 358 (2005) 1386–1392
1388
previously been reported for other alkynyl(phos-
phine)gold(I) complexes [32]. All phosphine complexes
also show a singlet resonance at around 40 ppm in the
31P NMR spectra, being similar to that found for other
alkynyl(phosphine)gold(I) complexes [33–37]. The 1H
NMR spectra of 2a–6a, 3b, 4b, and 6b show the signals
expected for the ethynylanilines as well as the auxiliary
phosphine and isocyanide ligands, and both their num-
ber and relative intensities are in agreement with the
proposed structures (see Section 3). In all cases, no resid-
ual signals attributable to acetylenic hydrogens were ob-
served, proving that in the syntheses of these complexes,
the substitution of acetylenic hydrogens by the corre-
sponding gold(I) fragments has been quantitative. The
13C NMR spectra all show a singlet around 105 ppm,
assignable to one of the carbons of the C„CAu frag-
ment, but in the absence of JCP coupling constants we
cannot unequivocally assign this resonance.
contain these kind of N–Hꢀ ꢀ ꢀAu interactions, the
restrictions [42–45] applied being d(Hꢀ ꢀ ꢀAu)00dVdW + 0.4
˚
A and N–Hꢀ ꢀ ꢀAu angle P135ꢁ, revealed the existence of
only twelve structures [46–56] in which such contacts are
present. Seven [46,49,50,53,54,56] display intermolecular
aurophilic contacts which have been previously reported
to be the main packing forces in a wide variety of gold(I)
compounds [57], whereas the other five [48,51,52,55]
show classical hydrogen bonds of the type N–Hꢀ ꢀ ꢀE
(E = N, O, S). Nevertheless, the authors do not mention
the existence of these N–Hꢀ ꢀ ꢀAu contacts in any of the
papers above mentioned. It is noteworthy that in 5a,
N–Hꢀ ꢀ ꢀAu contacts are the only intermolecular contacts
found so that they could be responsible for the zig-zag
chain packing observed.
Vicente et al. [15] have previously shown the synthetic
versatility of the acetylacetonate (acac) gold(I) com-
plexes as starting materials for the preparation of a wide
variety of both organometallic and coordination gold
compounds, including alkynyl derivatives [10,25,31,
34,35,58,59]. The ‘‘acac method’’ is based on the ability
of gold(I)acac derivatives to deprotonate substrates that
contain an acidic hydrogen. The reactions occur with
the formation of complexes in which the deprotonated
ligands coordinate to the metal centre occupying the va-
cancy generated upon liberation of acetylacetone. This
method has also allowed the synthesis of a range of
homoleptic anionic (alkynyl)gold(I) derivatives of gen-
eral formula PPN[Au(C„CR)2] (R = H, But, SiMe3,
CH2Cl, CH2Br, CH2OH, C„CH, p-C6H4CCC6H5)
[34,35,60].
The crystal structure of 5a has been carried out
(Fig. 1). It shows the expected mononuclear complex
in which the gold atom is coordinated to phosphine
and alkynyl ligands in an approximately linear manner
˚
[C–Au–P 176.21(10)ꢁ]. The C„C [1.198(4) A], C–Au
˚
˚
[1.990(3) A] and AuP [2.2686(8) A] bond distances are
similar to those found in other alkynyl(phosphine)
complexes [25,35,38–40].
Unlike the situation found for many other gold(I)
complexes, intermolecular Auꢀ ꢀ ꢀAu contacts are not ob-
served in 5a. Rather intermolecular contacts N–Hꢀ ꢀ ꢀAu
˚
are seen [dHꢀ ꢀ ꢀAu = 3.114 A, angle N–Hꢀ ꢀ ꢀAu = 152.90ꢁ]
that can be considered as hydrogen bonds (Fig. 2).
A recent paper by Schmidbaur [41] describes the head
to tail packing through intermolecular aurophilic con-
tacts in [Me3PAuC„CAuPMe3] to give a zig-zag chain
analogous to that found in 5a. A search in the Cam-
bridge Crystallographic Data Base for structures that
The reaction of PPN[Au(acac)2] and 4-ethynylaniline
(1:2) in degassed dichloromethane yielded the anionic
complex, PPN[Au(C„C-4-C6H4NH2)2] 7 in quantita-
tive yield (Scheme 1). This was easily characterised on
the basis of analytical and spectroscopic data. Notably,
a molecular anion of 100% relative intensity was seen in
the negative ion FAB mass spectrum and two doublets
were seen in the aromatic region of the 1H NMR
spectrum.
In conclusion, we have shown that a range of gold(I)
para-amino substituted arylacetylide complexes can be
readily prepared in high yields from the corresponding
ethynylanilines, and our future efforts will focus on the
development of multimetallic arrays via functionalisa-
tion of the amino group.
3. Experimental
Technical grade solvents were purified by standard
procedures. Unless otherwise stated, the reactions were
carried out at room temperature without special precau-
˚
Fig. 1. Molecular structure of 5a with selected bond lengths (A) and
1
tions against moisture. H, 13C and 31P NMR spectra
angles (ꢁ); Au(1)–P(1) 2.2686(8), Au(1)–C(1) 1.990(3), C(1)–C(2)
1.198(4), P(1)–Au(1)–C(1) 176.21(10), Au(1)–C(1)–C(2) 166.9(3),
C(1)–C(2)–C(3) 176.1(4).
were recorded in CDCl3 solutions on a Bruker
AMX400 spectrometer at room temperature. Chemical

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G. Hogarth, M.M. Alvarez-Falcon / Inorganica Chimica Acta 358 (2005) 1386–1392
´
1389
Fig. 2. Packing diagram for 5a highlighting the intermolecular NHꢀ ꢀ ꢀAu interactions.
shifts are referenced to H3PO4 (31P) or TMS (1H and
13C). The gold complexes [AuCl(SMe2)] [61], PPN[Au
(acac)2] [62] and the organic ligands 4-ethynylaniline
[63] and 2-methyl-4-ethynylaniline [64] were prepared
as described in the literature.
mg, 0.96 mmol; 4b: 188 mg, 0.6 mmol; 6b: 196 mg,
0.62 mmol) in CH2Cl2 (15–25 mL) was added the appro-
priate ligand (2a: PPh3, 209 mg, 0.8 mmol; 3a:
P(C6H4OMe-4)3, 326 mg, 0.92 mmol; 4a: P(C6H4F-4)3,
276 mg, 0.87 mmol; 5a: P(C6H4Me-3)3, 146 mg, 0.48
mmol; 6a: XylNC, 153 mg, 1.17 mmol; 3b:
P(C6H4OMe-4)3, 337 mg, 0.96 mmol; 4b: P(C6H4F-4)3,
182 mg, 0.6 mmol; 6b: XylNC, 94 mg, 0.7 mmol). The
reaction mixture was stirred for 0.5 (6b) or 1 (2a, 4a,
3b, 4b) or 1.5 (3a) or 2.5 (6a) or 3 (5a) h and filtered
through anhydrous MgSO4. The solution was concen-
trated under vacuum to 1 (2a, 6a, 6b) or 2 (4a, 3b) mL
or to dryness (3a, 5a, 4b) and Et2O (2a, 3a: 20 mL; 6b:
10 mL) or nhexane (4a: 10 mL; 4b: 20 mL) or a mixture
of both (5a: 4:1, 25 mL; 6a: 2:1, 15 mL; 3b: 2:1, 30 mL)
was added. After stirring for 15 min, the suspension was
filtered and the solid was air dried to give a bright yellow
(2a) or orange (3a, 6a, 6b) or pale yellow (4a Æ 2H2O, 5a)
or brown (3b, 4b) solid.
3.1. Synthesis of [AuC„CC6H3(R-2)NH2 ꢁ 4]n[R = H
(1a), Me (1b)]
To a solution of 2-R-4-ethynylaniline (R = H, 192
mg, 1.64 mmol; Me, 213 mg, 1.76 mmol) in CH2Cl2
(20 mL) were successively added NEt3 (1a: 0.4; 1b: 1
mL) and [AuCl(SMe2)] (1a: 483 mg, 1.64 mmol; 1b:
519 mg, 1.76 mmol). The reaction mixture was stirred
for 0.5 (1a) or 1 (1b) h. In the case of R = H, the result-
ing suspension was filtered and the solid washed with
CH2Cl2 (4 · 5 mL) and air dried to give 1a as an orange
powder. For R = Me, the resulting solution was concen-
trated under reduced pressure to ca. 10 mL and MeOH
(10 mL) was added to precipitate a dark-orange powder
which was filtered, washed with Et2O (2 · 5 mL) and air
dried to give 1b.
3.2.1. Compound 2a
Yield: 127 mg, 41%. Anal. Calc. for C26H21AuNP: C,
54.27; H, 3.68; N, 2.43. Found: C, 54.90; H, 3.90; N,
1.85%. IR (cmꢁ1): m(NH), 3450(s), 3350(s); m(C„C),
3.1.1. Compound 1a
1
Yield: 456 mg, 89%. Anal. Calc. for C8H6AuN: C,
30.69; H, 1.93; N, 4.47. Found: C, 29.90; H, 2.40; N,
4.40%. IR (cmꢁ1): m(NH), 3344(br), 3205(br); m(C„C),
1998(w).
2103(s). H NMR (400 MHz, CDCl3): d 7.38–7.51 (m,
15 H, PPh3), 7.31 (d, 2 H, Ar, JHH = 7 Hz), 6.54 (d, 2
3
3
H, Ar, JHH = 7 Hz), 3.66 (brs, 2 H, NH2). 13C NMR
(100 MHz, CDCl3):
1JCP = 15 Hz), 133.6, 131.1 (m, m-+ p-PPh3 ), 129.0 (d,
d 145.3, 134.2 (d, i-PPh3,
2
3.1.2. Compound 1b
o-PPh3, JCP = 11 Hz), 114.6, 114.5, 104.8 (C„C). 31P
Yield: 412 mg, 72%. Anal. Calc. for C9H8Au-
N Æ CH2Cl2: C, 28.98; H, 2.42; N, 3.38. Found: C,
28.12; H, 2.45; N, 3.57%. IR (cmꢁ1): m(C„C), 1988(w).
NMR (162 MHz, CDCl3): d 39.9 (s, PPh3). MS-FAB+
(m/z, %) 575 (M+, 23%).
3.2.2. Compound 3a
3.2. Synthesis of [Au(C„CC6H3(R-2)NH2-4)(L)]
[R = H , L = PPh3 (2a), P(C6H4OMe-4)3 (3a),P
(C6H4F-4)3 (4a), P(C6H4Me-3)3 (5a), XylNC (6a);
R = Me, L = P(C6H4OMe-4)3 (3b), P(C6H4F-4)3
(4b), XylNC (6b)]
Yield: 352 mg, 58%. Anal. Calc. for C29H27AuNO3P:
C, 52.34; H, 4.09; N, 2.11. Found: C, 52.48; H, 4.13; N,
1.67%. IR (cmꢁ1): m(NH), 3459(s), 3345(s); m(C„C),
1
2104(s). H NMR (400 MHz, CDCl3): d 7.47–7.42 (m,
6 H, PR3), 7.33 (d, 2 H, Ar, JHH = 8 Hz), 6.95–6.93
3
3
(m, 6 H, PR3), 6.56 (d, 2 H, Ar, JHH = 8 Hz), 3.83 (s,
To a suspension of 1a (2a: 166 mg, 0.53 mmol; 3a:
290 mg, 0.92 mmol; 4a: 273 mg, 0.87 mmol; 5a: 150
mg, 0.48 mmol; 6a: 230 mg, 0.78 mmol) or 1b (3b: 313
9 H, MeO), 3.69 (brs, 2H, NH2). 13C NMR (100
MHz, CDCl3): d 162.0 (p-PR3), 145.3, 135.6 (d, o-PR3,
1
2JCP = 15 Hz), 133.5; 133.4, 121.4 (d, i-PR3, JCP = 60

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G. Hogarth, M.M. Alvarez-Falcon / Inorganica Chimica Acta 358 (2005) 1386–1392
1390
3
3
PR3), 7.31 (d, 2H, Ar, JHH = 9 Hz), 7.29–7.17 (m, 9
Hz), 114.6 (d, m-PR3, JCP = 13 Hz), 114.5, 104.8
(C„C), 55.3 (MeO). 31P NMR (162 MHz, CDCl3): d
39.4 (s, PR3). MS-FAB+ (m/z, %) 665 (M+, 14%).
3
H, PR3), 6.53 (d, 2H, Ar, JHH = 9 Hz), 3.67 (brs,
NH2, 2H), 2.31 (s, 9H, Me). 13C NMR (100 MHz,
CDCl3): d 145.3, 138.9 (d, PR3, J = 12 Hz), 134.9 (d,
PR3, J = 16 Hz), 133.5, 132.2 (s, PR3), 131.0 (d, PR3,
3.2.3. Compound 3b
1
J = 12 Hz), 130.0 (d, i-PR3, JCP = 55 Hz), 128.8 (d,
Yield: 350 mg, 54%. Anal. Calc. for C30H29AuNO3P:
C, 53.03; H, 4.30; N, 2.06. Found: C, 53.22; H, 4.66; N,
1.76%. IR (cmꢁ1): m(NH), 3458(s), 3346(s); m(C„C),
PR3, J = 12 Hz), 114.6, 114.4, 104.8 (C„C), 21.4 (Me,
PR3). 31P NMR (162 MHz, CDCl3): d 43.5 (s, PR3).
FAB+ (m/z, %) 617 (M+, 35%).
1
2104(s). H NMR (400 MHz, CDCl3): d 7.42–7.37 (m,
6 H, PR3), 7.22 (d, 1 H, Ar, JHH = 2 Hz), 7.19 (dd, 1
4
3
H, Ar, JHH = 8 Hz, JHH = 2 Hz), 6.90–6.88 (m, 6 H,
4
3.2.7. Compound 6a
3
PR3), 6.52 (d, 1 H, Ar, JHH = 8 Hz), 3.80 (s, 9 H,
Yield 230 mg, 70%. Anal. Calc. for C17H15AuN2: C,
45.96; H, 3.40; N, 6.31. Found: C, 45.86; H, 3.56; N,
6.13%. IR (cmꢁ1): m(NH), 3452(s), 3352(s), m(C„N),
2194(s); m(C„C), 2110(s). 1H NMR (400 MHz, CDCl3):
d 7.31–7.25 (m, 3 H, Xyl + Ar), 7.13 (d, 2H, Xyl,
MeO), 3.61 (brs, 2 H, NH2), 2.08 (s, 3 H, MeAr). 13C
NMR (100 MHz, CDCl3): d 161.8 (p-PR3), 143.6,
135.6 (d, o-PR3, JCP = 16 Hz), 134.6, 131.2, 121.8 (d,
2
1
i-PR3, JCP = 60 Hz), 121.7, 114.6 (d, m-PR3,
3
3JHH = 8 Hz), 6.53 (d, 2H, Ar, JHH = 9 Hz), 3.69 (brs,
3JCP = 12 Hz), 114.6, 114.4, 55.4 (MeO), 17.2 (MeAr).
31P NMR (162 MHz, CDCl3): d (ppm): 39.9 (s, PR3).
FAB+ (m/z, %) 679 (M+, 25%).
2H, NH2), 2.40 (s, 6 H, Me). 13C NMR (100 MHz,
CDCl3): d 145.5, 136.1, 133.7, 130.7, 128.4, 124.4
(NCAu), 118.9, 114.5, 114.0, 104.7 (C„C), 18.7 (Me).
FAB+ (m/z, %) 444 (M+, 100%).
3.2.4. Compound 4a
Yield: 421 mg, 77%. Anal. Calc. for C26H22AuF3NO2-
P Æ 2H2O: C, 46.93; H, 3.33; N, 2.11. Found: C, 47.47;
H, 3.23; N, 2.25%. IR (cmꢁ1): m(NH), 3432(s), 3325(s);
m(C„C), 2109(s). 1H NMR (400 MHz, CDCl3): d
3.2.8. Compound 6b
Yield: 150 mg, 55%. Anal. Calc. for C18H17AuN2: C,
47.17; H, 3.74; N, 6.11. Found: C, 47.24; H, 3.79; N,
5.91%. IR (cmꢁ1): m(NH), 3452(s), 3357(s); m(C„N),
2207; m(C„C), 2113(s). H NMR (400 MHz, CDCl3):
d 7.30–7.26 (m, 1H, Xyl), 7.16–7.11 (m, 4H, Ar + Xyl),
3
7.54–7.46 (m, 6 H, PR3), 7.29 (d, 2 H, Ar, JHH = 8
1
Hz), 7.18–7.13 (m, 6 H, PR3), 6.55 (d, 2 H, Ar,
3JHH = 8 Hz), 3.69 (brs, NH2, 2H), 1.66 (s, 4H, H2O).
13C NMR (100 MHz, CDCl3): d 164.9 (d, p-PR3,
3
6.51 (d, 1 H, Ar, JHH = 8 Hz), 3.63 (s, 2H, NH2),
2.39 (s, 6H, Me, Xyl), 2.06 (s, 3H, MeAr). 13C NMR
(100 MHz, CDCl3): d 143.9, 136.0, 134.7, 131.4, 130.7,
128.3, 124.5 (NCAu), 121.6, 118.7, 114.4, 114.0, 105.0
(C„C), 18.7 (Me, Xyl), 17.2 (MeAr). FAB+ (m/z, %)
458 (M+, 100%).
3
1JCF = 260 Hz), 136.3 (dd o-PR3, JCF = 9 Hz,
1
2JCP = 16 Hz,), 133.6, 133.4, 125.3 (di-PR3, JCP = 58
2
3
Hz, ), 116.8 (dd m-PR3, JCF = 21 Hz, JCP = 13 Hz,),
114.6, 114.1. 31P NMR (162 MHz, CDCl3): d 41.8 (s,
PR3). MS-FAB+ (m/z, %) 629 (M+, 25%).
3.2.5. Compound 4b
3.3. Synthesis of PPN[Au(C„CC6H4NH2-4)2] (7)
Yield: 200 mg, 52%. Anal. Calc. for C27H20AuF3NP:
C, 50.41; H, 3.13; N, 2.18. Found: C, 50.70; H, 3.34; N,
2.12%. IR (cmꢁ1): m(NH), 3450(s), 3356(s); m(C„C),
To a solution of 4-ethynylaniline (284 mg, 2.4 mmol)
in CH2Cl2 (30 mL) was added solid PPN[Au(acac)2]
(1.03 g, 1.1 mmol). After 6 h of stirring, the reaction
mixture was filtered through anhydrous MgSO4 and
the solution was concentrated in vacuum to dryness.
Et2O (60 mL) was added, the resulting suspension stir-
red for 1.5 h, filtered, and the solid air dried to give 7
as a yellow powder. Yield: 1.04 g, 98%. Anal. Calc. for
C52H42AuN3P2: C, 64.53; H, 4.37; N, 4.34. Found: C,
64.37; H, 4.33; N, 4.62%. IR (cmꢁ1): m(NH), 3441(s),
3329(s); m(C„C), 2096(s). 1H NMR (400 MHz,
CD2Cl2): d 7.68–7.45 (m, 30 H, PPN), 7.12 (d, 4H, Ar,
1
2109(s). H NMR (400 MHz, CDCl3): d 2.07 (s, 3H,
MeAr), 3.63 (brs, 2H, NH2), 6.52 (d, 1H, Ar,
JHH = 8Hz), 7.12–7.21 (m, 8 H, Ar + PR3), 7.53–7.46
(m, 6 H, PR3). 13C NMR (100 MHz, CDCl3): d 164.9
1
4
(dd, p-PR3, JCF = 253 Hz, JCP = 2 Hz), 143.9 (Ar),
2
136.3 (dd, o-PR3, JCP = 16 Hz, JCF = 9 Hz), 134.6,
1
131.2, 125.2 (d, i-PR3, JCP = 58 Hz), 121.7, 116.8 (dd,
3
2
3
m-PR3, JCF = 21 Hz, JCP = 12 Hz), 114.4, 114.0,
105.3 (C„C), 17.2 (ArMe). 31P NMR (162 MHz,
CDCl3): d 41.6 (s, PR3). FAB+ (m/z, %) 643 (M+, 35%).
3
3JHH = 7 Hz), 6.48 (d, 4H, Ar, JHH = 7 Hz), 3.61 (brs,
3.2.6. Compound 5a
4H, NH2). 13C NMR (100 MHz, CD2Cl2): d 144.6,
134.1 (m, p-PPN), 133.1, 132.6–132.2 (m, m-PPN),
Yield: 211 mg, 71%. Anal. Calc. for C29H27AuNP: C,
56.41; H, 4.41; N, 2.27. Found: C, 56.17; H, 4.55; N,
2.34%. IR (cmꢁ1): m(NH), 3459(s), 3355(s); m(C„C),
3
129.9–129.7 (m, o-PPN), 127.4 (dd, i-PPN, JCP = 2
1
Hz, JCP = 107 Hz), 118.0, 114.8, 114.3, 102.3 (C„C).
1
2108(s). H NMR (400 MHz, CDCl3): d 7.41 (m, 3H,
FABꢁ (m/z, %) 429 (Mꢁ, 100%).

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G. Hogarth, M.M. Alvarez-Falcon / Inorganica Chimica Acta 358 (2005) 1386–1392
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4. X-ray data collection and solution
A single crystal of 5a was mounted on a glass fibre
and all geometric and intensity data were taken from
this sample using a Bruker SMART APEX CCD dif-
fractometer using graphite-monochromated Mo Ka
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˚
radiation (k = 0.71073 A) at 293 2 K. Data reduction
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Organometallics 19 (2000) 5063.
was carried out with SAINT+ and absorption correction
applied using the programme SADABS. The structure
was solved by direct methods and developed by using
alternating cycles of least-squares refinement and differ-
ence-Fourier synthesis. All non-hydrogen atoms were
refined anisotropically. Hydrogens were generally
placed in calculated positions (riding model). Structure
solution used SHELXTL PLUS V6.10 program package.
Crystallographic data for the structural analyses has
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Crystallographic data; yellow block, dimensions
0.15 · 0.13 · 0.12 mm, monoclinic, space group P21/n,
a = 11.2208(7), b = 13.9655(9), c = 16.0613(10) (A),
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3
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b = 97.945(1) (ꢁ), V = 2492.7(3) (A ), Z = 4, F(000) =
1208, Dcalc = 1.645 g cmꢁ3, l = 5.982 mmꢁ1, Tmax
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Tmin = 0.534/0.467. 21779 reflections were collected,
5975 unique [Rint = 0.0251] of which 4888 were observed
[I > 2.0r(I)]. At final convergence, R1 = 0.0275,
wR2 = 0.0634 [I > 2.0r(I)] and R1 = 0.0373, wR2 =
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