The first anionic arenediethynylgold(I) complexes

Article abstract of DOI:10.1016/S0022-328X(02)01621-2

We report synthetic methods for the preparation of mono-, di-, tri- and polyanionic alkynylgold(I) complexes, derived from diethynylarenes. The reaction between PPN[Au(acac)₂] and 1,3-diethynylbenzene [HC≡C(mphen)C≡CH] (1:1 M ratio) afforded the polymeric complex (PPN)_n[Au {C≡C(mphen)C≡C}]n (1) while the monomeric complexes (PPN)[Au{C≡C(Ar)C≡CH}₂] [Ar = mphen (2), mes (3)] resulted when the same dialkyne or 1,3-diethynylmesitylene [HC≡C(mes)C≡CH] were used in a 1:2 M ratio. Complexes PPN[XAu≡C(Ar)C≡CH] [Ar = mphen, X = Cl (4), Ar = mes, X = Cl (5), SCN (6)] were obtained from the metathesis reactions between complexes 2 or 3 and the appropriate PPN[AuX₂] salts. The C≡CH groups in complexes 2 or 4 are acidic enough as to react with [Au(acac)PPh₃] (1:2) or with PPN[Au(acac)₂] (1:1) to give complexes PPN[Au{C≡C(mphen)C≡CAuPPh₃}₂] (7) or (PPN)₃[Au{C≡C(mphen)C≡CAuCl}₂] (8), respectively. Complexes (PPN)₂[XAuC≡C(Ar)C≡CAuX)] [Ar = mphen, X = Cl (9); Ar = mes, X = Cl (10), SCN (11)] have been prepared by reacting [Ph₃PAuC=C(mphen)C=CAuPPh₃] with PPN[AuCl₂] (1:2) (9) or [AuC≡C(mes)C≡CAu]_n with the appropriate PPNX (1:2) salt (10, 11).

Full text of DOI:10.1016/S0022-328X(02)01621-2

Journal of Organometallic Chemistry 663 (2002) 40Á45
/
www.elsevier.com/locate/jorganchem
The first anionic arenediethynylgold(I) complexes
Jose´ Vicente ꢀ,1, Mar´ıa Teresa Chicote, Mar´ıa Dolores Abrisqueta,
Miguel M. Alvarez-Falco´n
Departamento de Qu´ımica Inorga´nica, Grupo de Qu´ımica Organometa´lica, Facultad de Qu´ımica, Universidad de Murcia,
Apartado 4021, Murcia 30071, Spain
Received 22 April 2002; accepted 24 May 2002
Dedicated to Professor Pascual Royo on the occasion of his 65th birthday.
Abstract
We report synthetic methods for the preparation of mono-, di-, tri- and polyanionic alkynylgold(I) complexes, derived from
diethynylarenes. The reaction between PPN[Au(acac)2] and 1,3-diethynylbenzene [HCꢀC(mphen)CꢀCH] (1:1 M ratio) afforded the
polymeric complex (PPN)n[Au{CꢀC(mphen)CꢀC}]n (1) while the monomeric complexes (PPN)[Au{CꢀC(Ar)CꢀCH}2] [Arꢁ
mphen (2), mes (3)] resulted when the same dialkyne or 1,3-diethynylmesitylene [HCꢀC(mes)CꢀCH] were used in a 1:2 M ratio.
Complexes PPN[XAuCꢀC(Ar)CꢀCH] [Arꢁmphen, XꢁCl (4), Arꢁmes, XꢁCl (5), SCN (6)] were obtained from the metathesis
reactions between complexes 2 or 3 and the appropriate PPN[AuX2] salts. The CꢀCH groups in complexes 2 or 4 are acidic enough
as to react with [Au(acac)PPh3] (1:2) or with PPN[Au(acac)2] (1:1) to give complexes PPN[Au{CꢀC(mphen)CꢀCAuPPh3}2] (7) or
(PPN)3[Au{CꢀC(mphen)CꢀCAuCl}2] (8), respectively. Complexes (PPN)2[XAuCꢀC(Ar)CꢀCAuX)] [Arꢁmphen, XꢁCl (9);
Arꢁmes, XꢁCl (10), SCN (11)] have been prepared by reacting [Ph3PAuCꢀC(mphen)CꢀCAuPPh3] with PPN[AuCl2] (1:2) (9) or
[AuCꢀC(mes)CꢀCAu]n with the appropriate PPNX (1:2) salt (10, 11).
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# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Anionic; Arenediethynyl; Gold(I)
1. Introduction
C6H3Me. Three of them [3,6] have been studied by X-
ray diffraction methods and all show infinite chain or
ribbon structures and display interesting photophysical
Metal complexes with bridging
ꢁ
/
Cꢀ
/
C(Ar)Cꢀ
/
Cꢁ
/
spacers (Ar being various aromatic rings) have been
shown to display electrical conductivity, nonlinear
optical or liquid crystalline properties [1]. Among
them, all the reported gold complexes are neutral which
is also the case for the vast majority of alkynylgold(I)
complexes. So far, arenediethynylgold(I) complexes of
properties [6,7]. These have been attributed in part [8Á
/
11] to the existence of short intermolecular AuÁ Á ÁAu
contacts that are present in most of the structurally
characterized luminescent gold(I) complexes [3,6,8,12].
Puddephatt has recently reviewed this chemistry [13].
In this paper we report mono-, di-, tri-, and poly-
anionic alkynylgold(I) complexes of the types
the types [Au{Cꢀ
C(Ar)CꢀCAuL}], (Lꢁ
[2Á4], [AuCꢀC(Ar)CꢀCAu(LL)]n, (LLꢁ
[1,3], diisocyanide) [2,3], [ClAuP(R2)CH2(R2)PAuCꢀ
C(Ar)CꢀCAuP(R2)CH2(R2)PAuCl] [1] and [{AuCꢀ
C(Ar)CꢀCAu}2{m-{CH2(PR2)2}2}] [5] have been de-
scribed Ar being 1,4-C6H4, 1,4-(C6H2Me2-2,5) or 3,5-
/
C(Ar)Cꢀ
/
C}Au]n [2Á
5], isocyanide)
diphosphines
/
4], [LAuCꢀ
/
/
/
phosphine [3Á
/
(PPN)[Au{Cꢀ
CH], PPN[Au{Cꢀ
C(Ar)CꢀCAuX)], (PPN)3[Au{Cꢀ
and (PPN)n[Au{CꢀC(Ar)CꢀC}]n, [PPNꢁ
nyl)phosphoranylidenammonium, Arꢁ
/
C(Ar)Cꢀ
/
CH}2], PPN[XAuCꢀ
CAuL)2], (PPN)2[XAuCꢀ
CAuCl}2],
/
C(Ar)Cꢀ
/
/
/
/
/
/
C(Ar)Cꢀ
/
/
/
/
/
C(Ar)Cꢀ
/
/
/
/
/
/bis(triphe-
/
/
phenylendiyl-
1,3 (mphen), mesitylendiyl-1,3 (mes); Xꢁ
/Cl, SCN,
LꢁPPh3] that we have prepared with the aim of
/
extending the short family of anionic alkynylgold(I)
complexes and with the hope of finding among them
some peculiar structural features. These are the first
ꢀ Corresponding author. Fax: ꢂ34-968-364-143
E-mail address: jvs@um.es (J. Vicente).
1
http://www.scc.um.es/gi/gqo/
/
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 1 6 2 1 - 2

J. Vicente et al. / Journal of Organometallic Chemistry 663 (2002) 40Á
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41
anionic arenediethynylgold(I) complexes and, although
we have unfortunately failed to obtain single crystals
suitable for diffraction studies they have been structu-
rally characterized by NMR techniques.
way to purify 1 which consists in heating the mixture
1ꢂPPN[Au(acac)2] in an oven at 60Á70 8C for 2 h
which causes the PPN[Au(acac)2] to decompose to
metallic gold. After recrystallizing the heated mixture
from CH2Cl2 and Et2O pure 1 could be isolated in 36%
yield.
/
/
2. Results and discussion
The 1:1 reaction between PPN[Au(acac)2] and HCꢀ
/
C(mes)Cꢀ
/
CH, analogous to that leading to 1, gave a
yellow product which 1H-NMR spectrum shows the
expected resonances for the homologous complex
2.1. Synthesis of complexes
We have previously reviewed [14] the ability of
acetylacetonatogold(I) complexes of the types [Au(a-
(PPN)n[AuCꢀ
/
C(mes)Cꢀ
/
C]n [d 2.26 (s, 6H, Me), 2.44
(s, 3H, Me), 6.63 (s, 1H, mes), 7.33Á
/3.62 (m 30H. PPN)]
cac)(PR3)] or PPN[Au(acac)2] (PPNꢁ
/
Ph3Pꢂ
/
Nꢂ/PPh3)
along with other very small singlet resonances at 2.13,
2.33, 2.40 and 6.77 ppm that we attribute to the
formation of a small amount of an open chain oligomer
to deprotonate organic substrates containing even
weakly acidic hydrogen atoms. These reactions gave
rise to a great variety of gold(I) complexes with
phosphorus ylide, methanide, methanediide, sulfur
ylide, amino, amido, nitrido, alkyl, phosphido, thiolato,
hydrosulfido, trithiocarbonato, dithiocarbamato, 1,1-
dithiolato and alkynyl (including ethynyl) ligands. As
an extension of ‘the acac method’, the reactions of
(PPN)nꢂ1[HCꢀ
/
C(mes)Cꢀ
/
C{AuCꢀ
/
C(mes)Cꢀ
/
C}nAuCꢀ
/
C(mes)CꢀCH]. The syntheses of 2 or 3 can be carried
/
out in the presence of an excess of the appropriate
dialkyne, which is removed easily along with the by-
product acacH by washing with Et2O. The low yield in
the synthesis of 3 is due to the necessity of recrystallizing
it from acetone, which is the only way to remove a small
amount of a contaminant observed in its 1H-NMR
spectrum, which we could not identify.
PPN[Au(acac)2] with the dialkynes HCꢀ
/
C(Ar)Cꢀ
/
CH
[ArꢁC6H4-1,3 (mphen) [15], {C6HMe3-2,4,6}-1,3 (mes)
/
[4] allowed us to prepare different alkynylaurategold(I)
complexes depending on the reaction conditions. Thus,
By reacting complexes 2 or 3 with one equivalent of
while
C(mphen)Cꢀ
between PPN[Au(acac)2] and the corresponding dia-
lkyne, the mononuclear derivatives (PPN)2[Au{Cꢀ
C(Ar)CꢀCH}2] [Arꢁmphen (2), mes (3)] were isolated
the
polymeric
complex
(PPN)n[AuCꢀ
/
the
PPN[XAuCꢀ
mes (5); Xꢁ
appropriate
C(Ar)Cꢀ
SCN, Arꢁmes (6); Scheme 2] were
PPN[AuX2]
salt,
complexes
/
C]n (1) results from the 1:1 reaction
/
/
CH] [XꢁCl, Arꢁ
/
/
mphen (4),
/
/
/
obtained in high yield. Metathesis reactions between
dialkynylaurate(I) and dihaloaurate(I) complexes to give
the corresponding alkynyl(halo)aurate(I) derivatives
have been previously described by us [16,17].
/
/
from the 1:2 reactions (Scheme 1). An slight excess of
PPN[Au(acac)2] must be used for the synthesis of 1 (see
Section 3) because otherwise it is contaminated with a
small amount of 2 that cannot be separated. Although
the excess of PPN[Au(acac)2] precipitates along with 1
upon addition of Et2O and it cannot be removed by
recrystallization we fortunately found an alternative
The anionic trinuclear derivative PPN[Au{Cꢀ
C(mphen)CꢀCAuPPh3}2] (7) or (PPN)3[Au{Cꢀ
C(mphen)CꢀCAuCl}2] (8) was obtained in high yield
/
/
/
/
by reacting two equivalents of [Au(acac)PPh3] or half
equivalent of PPN[Au(acac)2] with complexes 2 or 4,
respectively. These reactions provide new examples of
the utility of the ‘acac method’ [14].
The anionic dinuclear complexes (PPN)2[XAuCꢀ
C(Ar)CꢀCAuX] [Arꢁmphen, XꢁCl, (9); Arꢁmes,
XꢁCl (10), SCN (11)] can be obtained by reacting the
appropriate neutral polymer [AuCꢀC(Ar)CꢀCAu]
(Arꢁmphen (12a), mes (12b)) [4] with two equivalents
of the corresponding PPNX salt. Most probably,
complexes 9Á11 result from the cleavage of the weak
p(CꢀC)0Au interactions by the anionic X ligand.
/
/
/
/
/
/
/
/
/
/
/
/
Although this is the most straightforward method to
prepare complex 9, a better yield is achieved (82 vs. 72%)
by reacting [Ph3PAuCꢀ
/
C(mphen)Cꢀ/CAuPPh3] (13) [4]
with two equivalents of PPN[AuCl2]. The success in this
ligand exchange reaction could be attributed in part to
the great stability of the by-product [AuCl(PPh3)] that
can be recovered almost quantitatively from the mother
liquor in which complex 9 precipitates.
Scheme 1.

42
J. Vicente et al. / Journal of Organometallic Chemistry 663 (2002) 40Á45
/
prevented sufficient data acquisition. The C ꢁ
C ꢀCAu resonances appear in the ranges 132Á122 and
128Á98 ppm, respectively, downfield shifted with respect
/
Au and
/
/
/
to their homologous in the free alkyne as previously
observed in other alkynyl complexes [17].
2.2.2. IR spectroscopy
The IR spectra of complexes 1Á
medium absorption assignable to the n(Cꢀ
mode in the range 2090Á2110 (Arꢁmphen) or 2096Á
2106 (Arꢁ
mes) cmꢃ1 very slightly shifted to lower
energy with respect to those in the corresponding free
alkynes (2120 (Arꢁmphen) and 2102 (Arꢁmes)
cmꢃ1). In the spectra of complexes containing Cꢀ
CH
fragments two (2, 3, 5) or one (4) weak bands are
observed in the ranges 3225Á3280 (Arꢁmphen) or
3280Á3320 (Arꢁ
mes) cmꢃ1 that could be assigned to
/11 show one weak or
/
C) stretching
/
/
/
/
/
/
/
/
/
/
/
n(CH). No band assignable to this stretching mode is
observed in the spectrum of 6. Although the AuCl bond
is expected to weaken with increasing negative charge of
the complex and this expectation has been confirmed by
the descent of the corresponding IR absorption [20,21],
the mono- (4, 5), di- (9, 10) and trianionic (8) chlorogold
complexes here described show one n(AuCl) band in the
narrow range 321 (8)Á
derivatives 6 and 11 show one intense n(Cꢀ
tion at 2114 and 2118 cmꢃ1, respectively, which obscure
the corresponding n(CꢀC) band expected in the same
region. The presence of PPh3 in complex 7 is evidenced
by intense bands in the 1100 and 500Á
550 cmꢃ1 regions.
/
326 (5, 10) cmꢃ1. The sulfocyano
N) absorp-
/
/
/
3. Experimental
Scheme 2.
3.1. General
2.2. Structure of complexes
The IR spectra, elemental analyses and melting point
determinations were carried out as described earlier [22].
Technical grade solvents were purified by standard
procedures. Unless otherwise stated, the reactions were
carried out at room temperature (r.t.) without special
precautions against moisture. The 1H- and 31P{1H}-
NMR spectra were recorded in CDCl3 with Varian
Unity 300 or Bruker AC-200 spectrometers. Chemical
shifts, given in ppm, are referred to TMS (1H) or H3PO4
[31P{1H}]. All the anionic complexes show, with very
2.2.1. NMR spectroscopy
In the 1H-NMR spectra of those complexes that
contain Cꢀ
appears at chemical shifts (Arꢁ
Arꢁmes, 3: 3.35; 5: 3.36; 6: 3.38 ppm) similar to the
corresponding dialkynes (Arꢁmphen, 3.05 [15]; mes,
3.40 [4] ppm).
/
C(Ar)Cꢀ
/
CH fragments the acetylene proton
/mphen, 2: 2.93, 4: 2.95;
/
/
The resonances due to the protons in the aromatic
mphen fragments cannot be assigned unambiguously
since they are obscured by those due to the PPh3 ligands
or the PPN cation.
The resonances in the 13C{1H}-NMR spectra have
been assigned (see Section 3) based on those of the
corresponding free alkynes [4,18] and some other
alkynylgold complexes reported previously by us
[17,19] but in some cases the assignment was prevented
due to overlapping with resonances of the PPN cation
(2) or to the limited stability of complexes (1, 7, 8) that
small differences, IR absorptions [1320Á1220 (s, br), 544
/
1
(s), 527 (s) and 491 (s) cmꢃ1] as well as H (7.3Á
/
7.7, m,
3
108 Hz, JCP 1.8
1
ppm) and 13C{1H} [127 (dd, JCP
ꢁ
/
ꢁ
/
Hz, ipso-C), 130 (m, o-C), 132 (m, m-C), and 134 (m, p-
C) NMR resonances assignable to the PPN[N(PPh3)2]
cation which are not given below. Molar conductivities
were measured in acetone solution (ca. 5ꢄ
10ꢃ4 mol
/
lꢃ1) except for complexes 7 and 8 that do not give stable
solutions in this solvent. Diethynylbenzene [15], diethy-

J. Vicente et al. / Journal of Organometallic Chemistry 663 (2002) 40Á
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43
nylmesitylene and complexes 12 and 13 [4] were
prepared by following published procedures.
3.35 (s, 2H, CH), 6.79 [s, 2H (mes)], 7.38Á
/
7.69 (m, 30H,
PPN). 13C{1H}-NMR (75.4 MHz): d 20.3 (Me), 20.9
(Me), 22.1 (Me), 82.7 (CH), 83.1 (Cꢀ
/
CH), 99.0, 118.3,
3.2. Preparation of (PPN)n[Au{Cꢀ
/
C(mphen)Cꢀ/C}]n
125.6 (CAu), 127.1 (CꢀCAu), 136.4, 141.3, 142.7, 144.2.
/
(1)
3.4. Preparation of PPN[XAuCꢀ
/
C(Ar)Cꢀ
/
CH] [Arꢁ
/
PPN[Au(acac)2] [PPNꢁ
/
bis(triphenyl)phosphorany-
mphen, XꢁCl (4), Arꢁmes, Xꢁ
/
/
/
Cl (5), SCN (6)]
lydenammonium, acacꢁacetylacetonato, 775 mg, 0.83
/
mmol] was added to a solution of 1,3-diethynylbenzene
(100 mg, 0.79 mmol) in degassed CH2Cl2 (30 ml) and the
reaction mixture was stirred at r.t. for 5 h. The resulting
suspension was filtered through Celite, the solution was
concentrated under vacuum (2 ml) and Et2O (40 ml) was
added to give a white solid that was heated in an oven at
To a solution of 2 (ca. 0.1 mmol) in CH2Cl2 (30 ml) or
3 (ca. 0.1 mmol) in acetone (15 ml) was added the
appropriate PPN[AuX2] complex in 1:1 molar ratio. The
reaction mixture was stirred for 90 min (4) or 5.5 h (5) or
4.5 h (6) and then filtered through Celite. The solution
was concentrated to ca. 2Á3 ml (4, 6) or to dryness (5)
/
60Á
/
70 8C for 2 h and then recrystallized from CH2Cl2
and Et2O (4, 40 ml) or n-pentane (5, 20 ml) or n-hexane
(6, 40 ml) was added. The resulting suspension was
stirred for a few minutes (4, 5) or 2 h (6) and filtered to
give a white solid which was vacuum filtered and air
dried.
and Et2O to give 1 as a white solid. Yield 36%. M.p.
105 8C. Anal. Calc. for C46H34AuNP2: C, 64.27; H,
3.99; N, 1.63. Found: C, 64.26; H, 4.26; N, 1.74%. IR
(cmꢃ1): n(Cꢀ
7.70 (m, PPNꢂmphen).
1
/
C), 2090. H-NMR (200 MHz): d 7.40Á
/
/
3.4.1. Compound 4
3.3. Preparation of (PPN)[Au{Cꢀ
/
C(Ar)Cꢀ
/
CH}2]
Yield 98%. M.p. 140 8C. Anal. Calc. for C46H35Au-
ClNP2: C, 61.65; H, 3.94; N, 1.56. Found: C, 61.83; H,
3.76; N, 1.70%. LM (Vꢃ1 cm2 molꢃ1): 126. IR (cmꢃ1):
[Arꢁmphen (2), mes (3)]
/
PPN[Au(acac)2] (2: 402 mg, 0.43 mmol; 3: 1307 mg,
1.4 mmol) was added to a solution of the appropriate
diethynylarene (2: 114 mg, 0.90 mmol; 3: 495 mg, 2.94
mmol) in degassed CH2Cl2 (2: 30 ml; 3: 15 ml). The
reaction mixture was stirred at r.t. for 1 (2) or 5 (3) h, the
resulting suspension was filtered through Celite (2) or
anhydrous MgSO4 (3) and the solution was concen-
trated under vacuum to 2 ml (2) or to dryness (3). Et2O
(40 ml) was added, the resulting white suspension was
filtered under vacuum and the solid was air dried.
n(CH), 3273; n(Cꢀ
(200 MHz): d 2.95 (s, 1H, CH), 7.06 [t, 1H, H5 (mphen),
3JHH
8 Hz], 7.19 [m, 1H, H4 (mphen)], 7.36 [m, 1H,
H6 (mphen)], 7.42Á7.69 [m, 31H, PPNꢂH2 (mphen)].
13C{1H}-NMR (50.3 MHz): d 83.78 (ꢀ
CH), 97.12 (Cꢀ
CH), 121.19 [C3 (mphen)], 126.65 (CAu), 127.49 [C5
CAu), 128.72 [C1 (mphen)], 132.70
/
C), 2106; n(AuCl), 324. 1H-NMR
ꢁ
/
/
/
/
/
(mphen), 127.66 (Cꢀ
/
[C4 (mphen)], 135.64 [C2 (mphen)].
3.4.2. Compound 5
Yield 87%. M.p. 80 8C. Anal. Calc. for C49H41Au-
Compound 2 was recrystallized from CH2Cl2Á
/Et2O.
Both complexes are white solids.
ClNP2×
61.47; H, 4.31; N, 1.52%. LM (Vꢃ1 cm2 molꢃ1): 111.
C), 2106; n(AuCl),
/
H2O: C, 61.54; H, 4.53; N, 1.47. Found: C,
3.3.1. Compound 2
IR(cmꢃ1): n(CH), 3288, 3228; n(Cꢀ
/
1
Yield 93%. M.p. 112 8C. Anal. Calc. for C56H40Au-
NP2: C, 68.23; H, 4.09; N, 1.42. Found: C, 67.94; H,
3.91; N, 1.59%. LM (Vꢃ1 cm2 molꢃ1): 105. IR (cmꢃ1):
326. H-NMR (200 MHz): d 1.65 (s, 2H, H2O), 2.33 (s,
3H, Me), 2.41 (s, 3H, Me), 2.59 (s, 3H, Me), 3.36 (s, 1H,
CH), 6.79 (s, 1H, mes), 7.40Á
/
7.70 (m, 30H, PPN). 13C-
NMR (50.3 MHz): d 20.6 (Me), 21.3 (Me), 22.3 (Me),
n(CH), 3268, 3234; n(Cꢀ
/
C), 2091. 1H-NMR (200 MHz):
3
d 2.93 (s, 2H, CH), 7.04 [t, 2H, H5 (mphen), JHH
ꢁ
/
8
82.8 (ꢀ
/
CH), 83.8 (Cꢀ
/
CH), 95.1, 118.8, 119.1, 127.6 (C ꢀ
/
Hz], 7.16 [m, 2H, H4 (mphen)], 7.35 [m, 2H, H6
(mphen)], 7.39Á7.65 [m, 32H, PPNꢂH2 (mphen)].
13C{1H}-NMR (50.3 MHz): d 83.97 (ꢀ
CH), 101.56
(CꢀCH), 121.13 [C3 (mphen)], 127.47 [C5 (mphen)],
127.68 (CꢀCAu), 128.53 [C1(mphen)], 132.76 [C4
CAu), 137.2, 141.2, 143.2.
/
/
/
3.4.3. Compound 6
Yield 78%. M.p. 65 8C. Anal. Calc. for C50H41Au-
/
/
N2P2S×
/
H2O: C, 61.35; H, 4.43; N, 2.86; S 3.28. Found:
C, 60.84; H,4.38; N, 3.10; S 3.68%. LM (Vꢃ1 cm2
(mphen)], 135.67 [C2 (mphen)].
1
N), 2114. H-NMR (200
molꢃ1): 131. IR (cmꢃ1): n(Cꢀ
MHz): d 1.61 (s, 2H, H2O), 2.35 (s, 3H, Me), 2.42 (s,
/
3.3.2. Compound 3
Yield 31%. M.p. 198 8C. Anal. Calc. for C62H52N-
AuP2: C, 69.60; H, 4.90; N, 1.31. Found: C, 69.25; H,
5.12; N, 1.54%. LM (Vꢃ1 cm2 molꢃ1): 84. IR(cmꢃ1):
3H, Me), 2.60 (s, 3H, Me), 3.38 (s, 1H, CH), 6.82 (s, 1H,
mes), 7.41Á
d 20.2 (Me), 21.0 (Me), 21.9 (Me), 82.2 (ꢀ
CH), 96.6, 118.6 (SCN), 124.4, 126.8, 127.3 (C ꢀ
137.4, 140.7, 142.8.
/
7.70 (m, 30H, PPN). 13C-NMR (50.3 MHz):
/
CH), 83.6 (Cꢀ
/
n(CH), 3284, 3318; n(Cꢀ
/
C), 2096. 1H-NMR (200MHz):
/
CAu),
d 2.33 (s, 6H, Me), 2.41 (s, 6H, Me), 2.59 (s, 6H, Me),

44
J. Vicente et al. / Journal of Organometallic Chemistry 663 (2002) 40Á45
/
3.5. Preparation of PPN[Au{Cꢀ
/
C(mphen)Cꢀ
/
added to give a solid, which was recrystallized, from
CH2Cl2 and Et2O to give 9 in 82% yield.
CAuPPh3)2] (7)
M.p.: 140 8C (dec.). Anal. Calc. for C82H64Au2Cl2-
N2P4: C, 59.11; H, 3.87; N, 1.68. Found: C, 58.64; H,
To a solution of 2 (98 mg, 0.10 mmol) in CH2Cl2 (30
ml) was added [Au(acac)PPh3] (112 mg, 0.20 mmol).
The reaction mixture was stirred for 4.5 h and then
filtered through Celite. The solution was concentrated
under vacuum (to ca. 2 ml), Et2O (40 ml) was added, the
3.97; N, 1.74%. LM (Vꢃ1 cm2 molꢃ1): 231.4. IR (cmꢃ1):
1
C), 2110; n(AuCl), 324. H-NMR (200 MHz): d
n(Cꢀ
/
3
6.81 [t, 1H, H5 (mphen), JHH
ꢁ5.2 Hz], 7.06 [dd, 2H,
/
3
4
H4ꢂ
[t, 1H, H2 (mphen), JHH
(75.4 MHz): d 98.10 (s, CCAu); 109.32 [s, C1ꢂ
(mphen)], 126.71 (s, CAu), 135.58 [s, C2 (mphen)].
/
H6 (mphen), JHH
ꢁ
/
5.2 Hz, JHH
1.3 Hz]. 13C{1H}-NMR
C3
ꢁ/1.3 Hz], 7.19
4
resulting suspension was stirred in an iceÁ
/
water bath for
ꢁ
/
20 min and then filtered to give 7 as white solid. Yield
73%. M.p.: 135 8C. Anal. Calc. for C92H68Au3NP4: C,
58.09; H, 3.60; N, 0.74. Found: C, 57.97; H, 3.56; N,
/
0.92%. IR (cmꢃ1): n(Cꢀ
/
C), 2091. 1H-NMR (200 MHz):
3
d 7.13 [t, 2H, H5 (mphen), JHH
3.8. Preparation of (PPN)2[XAuCꢀ
/
C(mes)Cꢀ
/
CAuX]
ꢁ8 Hz], 7.37 [dd, 4H,
/
3
4
[XꢁCl (10), SCN (11)]
/
H4ꢂ
7.68 [m, 62H, PPh3ꢂ
NMR (121 MHz): d 42.50 (s, PPh3), 21.39 (s, PPN).
/H6 (mphen), JHH
ꢁ
/
8 Hz, JHH
ꢁ
/
1.5 Hz], 7.39Á
/
/
PPNꢂ
/
H2 (mphen)]. 31P{1H}-
To a suspension of [AuCꢀ
/
C(mes)Cꢀ/CAu]n (ca. 0.8
mmol) in acetone (20 ml) was added the appropriate
PPNX salt in 1:2 M ratio. The reaction mixture was
refluxed for 0.75 (10) or 1.75 (11) h and the resulting
suspension was filtered through Celite. The solution was
concentrated under vacuum to dryness (10) or to 10 ml
(11) and Et2O (10, 40 ml; 11, 15 ml) was added. The
resulting suspension was stirred at r.t. (10) or in a cold
bath (11, 0 8C) for 15 min and filtered. After recrys-
tallization from acetone and Et2O 10 and 11 were
obtained as white solids.
3.6. Preparation of (PPN)3[Au{Cꢀ
/
C(mphen)Cꢀ
/
CAuCl}2] (8)
To a solution of 4 (98.5 mg, 0.11 mmol) in CH2Cl2 (30
ml) was added PPN[Au(acac)2] (51.3 mg, 0.055 mmol),
the reaction mixture was stirred for 15 h and then
filtered through Celite. The solution was concentrated
under vacuum (ca. 2 ml) and Et2O (40 ml) was added to
give 8 as a yellow solid, which was filtered, and air dried.
Yield 93%. M.p. 102 8C. Anal. Calc. for C128H98Au3-
Cl2N3P6: C, 60.87; H, 3.91; N, 1.66. Found: C, 61.14; H,
3.8.1. Compound 10
Yield 75%. M.p. 130 8C. Anal. Calc. for C85H70Au2-
Cl2N2P4: C, 59.77; H, 4.13; N, 1.64. Found: C, 59.37; H,
3.77; N, 1.74%. IR (cmꢃ1): n(Cꢀ
/
C), 2104; n(AuCl), 321.
1H-NMR (200 MHz): d 6.82 [t, 2H, H5 (mphen),
3
H6 (mphen), JHH
3JHH
8 Hz, JHH
(mphen)].
ꢁ
/
8 Hz], 7.06 [dd, 4H, H4ꢂ
/
ꢁ
/
4.29; N, 1.68%. LM (Vꢃ1 cm2 molꢃ1): 213. IR (cmꢃ1):
4
1
C), 2106; n(AuCl), 326. H-NMR (200 MHz): d
2.32 (s, 6H, Me), 2.47 (s, 3H, Me), 6.64 [s, 1H (mes)],
ꢁ
/
2 Hz], 7.42Á
/
7.68 [m, 92H, PPNꢂH2
/
n(Cꢀ
/
7.38Á
/
7.69 (m, 60H, PPN): 13C{1H} (50.3 MHz): d 20.9
(Me), 21.8 (Me), 95.9, 123.9, 136.5.
3.7. Preparation of (PPN)2[ClAuCꢀ
CAuCl)] (9)
/
C(mphen)Cꢀ
/
3.8.2. Compound 11
3.7.1. Method a
PPNCl (379 mg, 0.66 mmol) was added to a suspen-
sion of [AuCꢀC(mphen)CꢀCAu]n [4] (171 mg, 0.33
mmol) in acetone (30 ml) and the mixture was refluxed
for 6.3 h. When cold, the solution was filtered through
Celite and the filtrate was concentrated to dryness. The
pale yellow residue was washed with Et2O (25 ml),
filtered and air dried to give 9 as a pale yellow solid in
72% yield.
Yield 47%. M.p. 170 8C. Anal. Calc. for C87H70Au2-
N4P4S2: C, 59.59; H, 4.02; N, 3.20; S, 3.66. Found: C,
59.41; H, 4.04; N, 3.14; S, 3.30%. LM (Vꢃ1 cm2 molꢃ1):
/
/
207. IR (cmꢃ1): n(Cꢀ
/
N), 2118. 1H-NMR (200 MHz): d
2.35 (s, 6H, Me), 2.45 (s, 3H, Me), 6.69 [s, 1H, (mes)],
7.38Á
/
7.69 (m, 60H, PPN). 13C{1H}-NMR (50.3 MHz):
d 20.8 (Me), 21.6 (Me), 97.5, 120.2 (SCN), 123.3, 124.7,
126.5, 137.0, 141.9.
3.7.2. Method b
PPN[AuCl2] (147.6 mg, 0.183 mmol) was added to a
Acknowledgements
solution of [Ph3PAuCꢀ
/
C(mphen)Cꢀ
/
CAuPPh3] [4] (96
mg, 0.092 mmol) in CH2Cl2 (30 ml). The reaction
mixture was stirred for 45 h and the resulting suspension
was filtered through Celite. The solution was concen-
trated under vacuum (to ca. 5 ml) and Et2O (40 ml) was
We thank DGES (PB97-1047), MCyT (SPAIN) and
FEDER (BQU2001-0133) for financial support.
M.M.A.-F. thanks Fundacio´n Se´neca (Comunidad
Auto´noma de la Regio´n de Murcia, Spain) for a Grant.

J. Vicente et al. / Journal of Organometallic Chemistry 663 (2002) 40Á
/45
45
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