Platinum(II) and mixed platinum(II)/gold(I) σ-alkynyl complexes. The first anionic σ-alkynyl metal polymers

Article abstract of DOI:10.1021/om0501273

The alkynes C₆Me₄(C≡CH)₂-1,4, C ₆Me₄(C≡CH)₂-1,2, and C₆Me ₃(C≡CH)₃-1,3,5 react with cis-[PtCl ₂(PAr₃)₂] and NHEt₂ and a catalytic amount of CuI to give complexes trans-[Pt-(C≡CC₆Me ₄C≡CH-4)₂(PAr₃)₂] [Ar = Ph (1a), C₆H₄Me-4 (To) (1b)], trans-[Pt(C≡CC ₆Me₄-C≡CH-2)₂(PAr₃) ₂] [Ar = Ph (2a), To (2b)], and trans-[Pt{C≡CC ₆Me₃(C≡CH)₂-3,5}₂(PAr ₃)₂] [Ar = Ph (3a), To (3b)], respectively. The reactions of [Au(acac)PAr₃] (acac = acetylacetonato) with complex la or lb (2:1) or with 3b (4:1) give the neutral mixed Pt^IIAu^I ₂ or Pt^IIAu^I₄ σ-alkynyl complexes trans- [Pt(C≡CC₆Me₄C≡CAuPAr ₃-4)₂(PAr₃)₂] [Ar = Ph (4a), To (4b)] or trans-[Pt{C≡CC₆Me₃(C≡CAuPTo ₃)₂-3,5}₂(PTo₃)₂] (5b), respectively. Additionally, the replacement of the triarylphosphine ligands present in 1a, 2a, 4b, or 5b with various trialkylphosphines produces the homologous derivatives with PMe₃ (1c, 2c, 4c, 5c), PEt₃ (1d), or P(ⁿBu)₃ (1e), respectively. PPN[Au(acac) ₂] reacts with complex 1a, 1c, or 1e (1:1) to give (PPN) _n[trans-Pt{(C≡CC₆Me₄C≡C-4) ₂Au}(PR₃)₂]_n [R = Ph (6a), Me (6c), ⁿBu (6e)], while its reaction with 3b (2:1) produces (PPN) _2n[trans-Pt{C≡CC₆Me₃(C≡C) ₂-3,5Au₂(PTo₃)₂]_n (7). Complexes 6a, 6c, 6e, and 7 are the first anionic σ-alkynyl metal polymers described so far. The crystal structures of 1a·CHCl₃, 2b·2CHCl₃, and 4b·5CH₂Cl₂ have been determined. Each complex displays crystallographic inversion symmetry.

Full text of DOI:10.1021/om0501273

2764
Organometallics 2005, 24, 2764-2772
Platinum(II) and Mixed Platinum(II)/Gold(I) σ-Alkynyl
Complexes. The First Anionic σ-Alkynyl Metal Polymers
Jose´ Vicente,*,† Mar´ıa-Teresa Chicote, and Miguel M. Alvarez-Falco´n
Grupo de Quı´mica Organometa´lica, Departamento de Quı´mica Inorga´nica,
Universidad de Murcia, Apartado 4021, Murcia, 30071 Spain
Peter G. Jones*,‡
Institut fu¨r Anorganische und Analytische Chemie der Technischen Universita¨t, Hagenring 30,
3300 Braunschweig, Germany
Received February 22, 2005
The alkynes C6Me4(CtCH)2-1,4, C6Me4(CtCH)2-1,2, and C6Me3(CtCH)3-1,3,5 react with
cis-[PtCl2(PAr3)2] and NHEt2 and a catalytic amount of CuI to give complexes trans-[Pt-
(CtCC6Me4CtCH-4)2(PAr3)2] [Ar ) Ph (1a), C6H4Me-4 (To) (1b)], trans-[Pt(CtCC6Me4-
CtCH-2)2(PAr3)2] [Ar ) Ph (2a), To (2b)], and trans-[Pt{CtCC6Me3(CtCH)2-3,5}2(PAr3)2]
[Ar ) Ph (3a), To (3b)], respectively. The reactions of [Au(acac)PAr3] (acac ) acetylacetonato)
with complex 1a or 1b (2:1) or with 3b (4:1) give the neutral mixed PtIIAuI2 or PtIIAuI4
σ-alkynyl complexes trans-[Pt(CtCC6Me4CtCAuPAr3-4)2(PAr3)2] [Ar ) Ph (4a), To (4b)] or
trans-[Pt{CtCC6Me3(CtCAuPTo3)2-3,5}2(PTo3)2] (5b), respectively. Additionally, the replace-
ment of the triarylphosphine ligands present in 1a, 2a, 4b, or 5b with various trialkylphos-
phines produces the homologous derivatives with PMe3 (1c, 2c, 4c, 5c), PEt3 (1d), or P(nBu)3
(1e), respectively. PPN[Au(acac)2] reacts with complex 1a, 1c, or 1e (1:1) to give (PPN)n-
[trans-Pt{(CtCC6Me4CtC-4)2Au}(PR3)2]n [R ) Ph (6a), Me (6c), nBu (6e)], while its reaction
with 3b (2:1) produces (PPN)2n[trans-Pt{CtCC6Me3(CtC)2-3,5Au2(PTo3)2]n (7). Complexes
6a, 6c, 6e, and 7 are the first anionic σ-alkynyl metal polymers described so far. The crystal
structures of 1a‚CHCl3, 2b‚2CHCl3, and 4b‚5CH2Cl2 have been determined. Each complex
displays crystallographic inversion symmetry.
Chart 1
Introduction
Most of the heteronuclear (alkynyl)gold(I) complexes
described in the literature are clusters containing Cu,
Ag, Fe, or Ir,1 and those structurally characterized by
X-ray crystallography show, apart from metal-metal
bonds, interactions between the π-electron density of the
AuCtC group and the other metal center. These bond-
ing interactions are also present in most of the few
noncluster heteronuclear (alkynyl)gold(I) complexes
containing Cu, Ag, Mo, W, or Pt.2-4 Additionally, some
heteronuclear alkynylgold(I) complexes of the type
[Au(CtC-X)L] have been reported,2,5-7 X being an
organometallic fragment in which the second metal is
not coordinated to the CtC moiety (Chart 1). Most such
† E-mail: jvs1@um.es. www: http://www.um.es/gqo.
‡ E-mail: p.jones@tu-bs.de.
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complexes were obtained from organometallic complexes
bearing CtCH units and chlorogold(I) complexes in
basic conditions.5-7 Some of them display NLO5 or
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10.1021/om0501273 CCC: $30.25 © 2005 American Chemical Society
Publication on Web 04/26/2005

The First Anionic σ-Alkynyl Metal Polymers
Organometallics, Vol. 24, No. 11, 2005 2765
luminescent properties,7 or their electrical properties
have been studied with the purpose of designing mo-
lecular wires.7
10,10,20,21 although some heteronuclear22 d6/d8 (Fe/Pd,
Fe/Ni, and Ru/Pd) derivatives are also known. The
overwhelming majority of these polymers present a
linear rigid-rod structure and are neutral. A few cat-
ionic23 and some 2D-graphite-like polymers24 have also
been reported, but anionic polymers were unknown so
far. Our previous experience on the use of the “acac
method”25 for the synthesis of alkynylgold(I) deriv-
atives26-28 prompted us to prepare a family of bis-
(alkynyl)Pt(II) derivatives bearing CtCH units that
could be used as starting materials for the synthesis of
new heteronuclear PtIIAuI alkynyl compounds, including
anionic polymeric species.
Among the great variety of heteropolynuclear σ-
alkynyl complexes of any metal described in the
literature,8-13 we have found only two PtIIAuI deriva-
tives, which contain 1,4-butadiyndiyl4,14 fragments and
were characterized only by elemental analyses and
NMR. We have just preliminarily reported the synthesis
and crystal structure of the σ-alkynyl PtII2AuI triangle
PPN[Au{Pt(PMe3)2}2{µ-C6Me4(CtC)2-1,2}3] starting from
complex 2c.15 In general, polymers based on -CtC-
units and transition metals alternating along the poly-
meric backbone have been found to be of outstanding
interest.16,17 Most such σ-alkynyl polymers are homo-
nuclear species, with metals of groups 8,18 9,10,11,19 and
Experimental Section
The IR spectra, elemental analyses, and melting point
determinations were carried out as described earlier.29 Techni-
cal grade solvents were purified by standard procedures.
Unless otherwise stated, the reactions were carried out at room
temperature without any special precautions to exclude oxygen
or moisture. The complexes cis-[PtCl2(PR3)2] were prepared
from trans-[PtCl2(NCPh)2] and the appropriate phosphine (2:
1, in CH2Cl2, 1 h at room temperature) and [Au(acac)PR3] as
previously described for R ) Ph.30 The syntheses of C6Me4-
(CtCH)2-1,4,28 1,3,5-C6Me3(CtCH)3-1,3,5,31 and PPN[Au(a-
cac)2]30 were previously described. The NMR spectra were
measured in CDCl3 with Bruker Avance 200, 300, or 400
spectrometers. Chemical shifts are referred to TMS (1H), CDCl3
(13C), or H3PO4 (31P). The FAB+ mass spectra were measured
with a Fisons VG-Autospec spectrometer using 3-nitrobenzyl
alcohol as the matrix.
Synthesis of C6Me4(CtCSiMe3)2-1,2. Me3SiCtCH (9 mL,
64 mmol) was added to a mixture of C6Me4I2-1,2,32 (6.24 g, 16
mmol), cis-[PdCl2(PPh3)2] (449 mg, 0.64 mmol), and CuI (245
mg, 1.29 mmol) in degassed NHEt2 (70 mL). The mixture was
stirred under nitrogen for 6.5 days, and the solvent was
removed under reduced pressure. The residue was stirred with
Et2O (120 mL) and filtered. The solution was concentrated to
ca. 50 mL and chromatographed on neutral Al2O3 to give a
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2766 Organometallics, Vol. 24, No. 11, 2005
Vicente et al.
red solution, which was concentrated to dryness. Recrystalli-
zation of the crude product from EtOH (40 mL) gave colorless
needles of the title compound. Yield: 4.3 g, 81%. Mp: 136 °C.
Anal. Calcd for C20H30Si2: C 73.54, H 9.26. Found: C 73.30,
H 9.67. IR (cm-1): ν(CtC) 2150 (s). 1H NMR (200 MHz,
CDCl3): δ 2.42 (s, 6 H, Me), 2.22 (s, 6 H, Me), 0.31 (s, 18 H,
SiMe3). 13C{1H} NMR (50 MHz, CDCl3): δ 136.2 (Ar), 135.6
(Ar), 123.0 (Ar), 103.9 (CSi), 100.7 (CtCSi), 18.5 (Me), 16.7
(Me), 0.2 (SiMe3).
0.18 mmol), 1d (522 mg, 0.48 mmol), or 1e (1.32 g, 1.22 mmol)
in dry THF (10 mL for 1c,d; 15 mL for 1e) was added the
appropriate phosphine (1c, PMe3, 1 mL, 1 M in toluene, 1
mmol; 1d, PEt3, 0.43 mL, 2.9 mmol; 1e, PnBu3, 1.8 mL, 7.32
mmol). The solution was stirred under nitrogen for 15 (1c) or
23 (1d,e) h and concentrated under vacuum to ca. 2 mL. Then
n-pentane (15 mL) was added to precipitate a colorless solid,
which was filtered off, washed with n-pentane (5 mL), and air-
dried. In the case of 1e, concentrating the solution to 1 mL,
adding n-pentane (20 mL), and cooling to -78 °C was neces-
sary; the resulting suspension was filtered and the colorless
solid washed with cold n-pentane and dried at ca.1 mbar for 1
h.
Synthesis of C6Me4(CtCH)2-1,2. A solution of KOH (1 g,
18 mmol) in H2O (3 mL) was added to a suspension of C6Me4-
(CtCSiMe3)2-1,2 (3 g, 9.12 mmol) in MeOH (50 mL), and the
mixture was refluxed for 4 h. After diluting with H2O (50 mL),
the mixture was extracted with Et2O (2 × 50 mL). The
combined extracts were dried over anhydrous MgSO4, and the
solvent was removed under reduced pressure to give a purple
solid, which was washed with cold EtOH (-70 °C, 10 mL),
filtered, and air-dried to give colorless needles of the title
compound. Yield: 1.38 g, 83%. Mp: 102 °C. Anal. Calcd for
C14H14: C 92.26, H 7.74. Found: C 91.99, H 8.04. IR (cm-1):
ν(CH) 3310 (s), 3280 (s), ν(CtC) 2098 (s). 1H NMR (200 MHz,
CDCl3): δ 3.47 (s, 2 H, tCH), 2.42 (s, 6 H, Me), 2.20 (s, 6 H,
Me). 13C{1H} NMR (50 MHz, CDCl3): δ 136.6 (Ar), 136.0 (Ar),
122.3 (Ar), 83.6 (tCH), 82.3 (CtCH), 18.6 (Me), 16.7 (Me).
Synthesis of trans-[Pt(CtCC6Me4CtCH-4)2(PAr3)2] [Ar
) Ph (1a), To (1b)]. A mixture of C6Me4(CtCH)2-1,4 (for 1a:
908 mg, 4.98 mmol; for 1b: 1.22 g, 6.67 mmol), cis-[PtCl2(PR3)2]
(R ) Ph, 985 mg, 1.25 mmol; To, 1.460 g, 1.67 mmol), and CuI
(1a: 24 mg, 0.12 mmol; 1b: 32 mg, 0.17 mmol) in degassed
NHEt2 (1a: 30 mL; 1b: 65 mL) was stirred under nitrogen
for 16.5 (1a) or 65 (1b) h. The solvent was removed under
reduced pressure, and the residue was stirred with CHCl3
(1a: 10 mL; 1b: 13 mL). The resulting suspension was added
slowly dropwise into rapidly stirred EtOH (100 mL) and
filtered. The solid was washed with EtOH (10 mL) and
n-pentane (20 mL). The crude product was stirred in a mixture
of CHCl3 and Et2O (2:1, 90 mL) and the resulting suspension
filtered through Celite. The solution was concentrated under
vacuum until a yellow solid began to precipitate, at which point
n-pentane (50 mL) was added. The suspension was filtered
and the solid was air-dried to give a pale yellow powder. 1b
was additionally dried under reduced pressure (ca. 1 mbar)
for 1 h.
1c: Yield 101 mg, 81%. Mp: 261 °C (dec). Anal. Calcd for
C34H44P2Pt: C 57.54, H 6.25. Found: C 57.24, H 6.63. IR
(cm-1): ν(CH) 3314 (s), 3268 (s), ν(CtC) 2086 (s). 1H NMR
(200 MHz, CDCl3): δ 3.5 (s, 2 H, tCH), 2.46 (s, 12 H, C6Me4),
3
2.41 (s, 12 H, C6Me4), 1.72 (m, 18 H, PMe3, JHPt ) 31 Hz).
APT 13C{1H} NMR (50 MHz, CDCl3): δ 136.2 (Ar), 134.7 (Ar),
129.4 (Ar), 119.2 (Ar), 118.7 (tCPt, 1JCPt ) 31 Hz), 107.7 (Ct
CPt, 2JCPt ) 4 Hz), 84.6 (tCH), 83.5 (CtCH), 19.2 (Me), 18.8
1
(Me), 16.2 (virtual t, Me, PMe3, | JCP + 3JCP| ) 40 Hz, 2JCPt
)
)
45 Hz). 31P{1H} NMR (81 MHz, CDCl3): δ -21.1 (s, JPPt
1
2312 Hz). MS (FAB+), m/z (%): 709 (M+, 26).
1d: Yield 250 mg, 66%. Mp: 185 °C (dec). Anal. Calcd for
C40H56P2Pt: C 60.52, H 7.11. Found: C 60.36, H 7.48. IR
(cm-1): ν(CH) 3306 (s), 3240 (s), ν(CtC) 2082 (s). 1H NMR
(400 MHz, CDCl3): δ 3.46 (s, 2 H, tCH), 2.44 (s, 12 H, C6-
Me4), 2.41 (s, 12 H, C6Me4), 2.08 (m, 12 H, CH2), 1.16 (m, 18
H, Me, PEt3). APT 13C{1H} NMR (100 MHz, CDCl3): δ 135.70
1
(Ar), 134.06 (Ar), 129.49 (Ar), 119.27 (tCPt, JCPt ) 29 Hz),
118.32 (Ar), 108.37 (CCPt), 83.99 (tCH), 83.24 (CtCH), 18.54
1
(Me), 18.41 (Me), 16.29 (virtual t, CH2, | JCP + 3JCP| ) 36 Hz,),
8.27 (Me, PEt3). 31P{1H} NMR (162 MHz, CDCl3): δ 11.36 (s,
1JPPt ) 2385 Hz). MS (FAB+), m/z (%): 793 (53, M+).
1e: Yield 650 mg, 56%. Mp: 120 °C. Anal. Calcd for C52H80P2-
Pt: C 64.91, H 8.38. Found: C 65.07, H 8.29. IR (cm-1): ν-
(CH) 3308 (s), ν(CtC) 2086 (s). 1H NMR (400 MHz, CDCl3): δ
3.46 (s, 2 H, tCH), 2.43 (s, 12 H, C6Me4), 2.41 (s, 12 H, C6-
Me4), 2.03 (m, 12 H, PCH2Pr), 1.57 (m, 12 H, PCH2CH2Et),
1.35 (m, 12 H, P(CH2)2CH2Me), 0.87 (t, 18 H, P(CH2)3Me, 3JHH
) 7 Hz). APT 13C{1H} NMR (100 MHz, CDCl3): δ: 135.6 (Ar),
133.9 (Ar), 129.6 (Ar), 119.2 (Ar), 118.0 (CtCPt), 107.8 (Ct
CPt), 83.9 (tCH), 83.4 (CtCH), 26.5 [P(CH2)2CH2Me], 24.3
1a: Yield 1.16 g, 86%. Mp: 185 °C (dec). Anal. Calcd for
C64H56P2Pt: C 71.03, H 5.22. Found: C 70.79, H 5.35. IR
2
(virtual t, PCH2CH2Et, | JCP + 4JCP| ) 14 Hz), 24.0 (virtual t,
1
1
(cm-1): ν(CH) 3302 (s), ν(CtC) 2094 (s). H NMR (200 MHz,
PCH2Pr, | JCP
+
3JCP| ) 36 Hz), 18.6 (Me), 18.4 (Me), 13.8
CDCl3): δ 7.81-7.71 (m, 15 H, PPh3), 7.27-7.18 (m, 15 H,
PPh3), 3.38 (s, 2 H, tCH), 2.21 (s, 12 H, Me), 1.64 (s, 12 H,
Me). APT 13C{1H} NMR (50 MHz, CDCl3): δ 134.9 (d, o-CH,
PPh3, 2JCP ) 6 Hz), 134.7 (Ar), 133.9 (Ar), 131.3 (d, i-C, PPh3,
1JPC ) 29 Hz), 130.1 (p-CH, PPh3), 127.6 (d, m-CH, PPh3, 3JCP
[P(CH2)3Me]. 31P{1H} NMR (162 MHz, CDCl3): δ 3.48 (s, 1JPPt
) 2366 Hz). MS (FAB+), m/z (%): 963 (52) (M+).
Synthesis of trans-[Pt(CtCC6Me4CtCH-2)2(PAr3)2] [Ar
) Ph (2a), To (2b)]. A mixture of C6Me4(CtCH)2-1,2 (for 2a:
236 mg, 1.29 mmol; for 2b: 454 mg, 2.5 mmol), cis-[PtCl2-
(PR3)2] (for 2a: 256 mg, 0.32 mmol; for 2b: 545 mg, 0.62
mmol), and CuI (for 2a: 6 mg, 0.031 mmol, for 2b: 12 mg,
0.062 mmol) in degassed NHEt2 (for 2a: 20 mL, for 2b: 30
mL) was stirred under nitrogen for 15 (2a) or 26 (2b) h. The
solvent was removed under reduced pressure, the residue was
stirred with CHCl3 (ca. 3 mL), and the resulting suspension
was added slowly dropwise into EtOH (40 mL) with vigorous
stirring. The suspension was filtered and the colorless solid
was air-dried to give 2a or 2b‚0.5H2O. Complex 2b was not
dehydrated after treating it under reduced pressure (1 mbar)
for 0.5 h.
1
) 5 Hz), 129.4 (Ar), 120.9 (tCPt, JCPt ) 30 Hz), 117.4 (Ar),
112.6 (CtCPt, 2JCPt ) 2 Hz), 83.6 (tCH), 18.2 (Me), 17.7 (Me).
31P{1H} NMR (81 MHz, CDCl3): δ 18.94 PPh3 (s, 1JPPt ) 2672
Hz). MS (FAB+), m/z (%): 1083 (M+, 55). Crystals of 1a‚CHCl3
suitable for an X-ray diffraction study were obtained by the
liquid diffusion method using CH2Cl2 and n-pentane.
1b: Yield 1.38 g, 71%. Mp: 218 °C (dec). Anal. Calcd for
C70H68P2Pt: C 72.09, H 5.88. Found: C 71.72, H 5.91. IR
1
(cm-1): ν(CH) 3310 (s), ν(CtC) 2088 (s). H NMR (400 MHz,
CDCl3): δ 7.66-7.61 (m, 12 H, PTo3), 7.00-6.98 (m, 12 H,
PTo3), 3.38 (s, 2 H, tCH), 2.23 (s, 30 H, Me, PTo3, C6Me4),
1.66 (s, 12 H, C6Me4). 13C{1H} NMR (100 MHz, CDCl3): δ 140.1
(m, p-CH, PTo3), 135.0 (d, o-CH, PTo3, 2JCP ) 7 Hz), 134.6 (Ar),
133.8 (Ar), 129.8 (Ar), 128.7 (d, i-C, PTo3, 1JCP ) 30 Hz), 128.3
(m, m-CH, PTo3, 3JCP ) 6 Hz), 117.3 (Ar), 112.8 (CtCPt), 83.7
(tCH), 83.3 (CtCH), 21.2 (Me, PTo3), 18.1 (Me), 17.6 (Me).
31P{1H} NMR (162 MHz, CDCl3): δ 16.91 (s, 1JPPt ) 2644 Hz).
MS (FAB+), m/z (%): 1166 (M+, 26).
2a: Yield 248 mg, 72%. Mp 236 °C (dec). Anal. Calcd for
C64H56P2Pt: C 71.03, H 5.22. Found: C 70.72, H 5.51. IR
1
(cm-1): ν(CH) 3284 (s), ν(CtC) 2102 (s). H NMR (400 MHz,
CDCl3): δ 7.87-7.82 (m, 15 H, PPh3), 7.26-7.20 (m, 15 H,
PPh3), 3.01 (s, 2 H, tCH), 2.31 (s, 6 H, C6Me4), 2.07 (s, 6 H,
C6Me4), 1.98 (s, 6 H, C6Me4), 1.55 (s, 6 H, C6Me4). APT 13C-
{1H} NMR (100 MHz, CDCl3): δ 135.3 (m, m-CH, PPh3), 134.7
(Ar), 134.4 (Ar), 134.1 (Ar), 131.5 (m, i-C, PPh3), 130.5 (Ar),
129.8 (m, p-CH, PPh3), 129.6 (Ar), 127.5 (m, o-CH, PPh3), 120.0
Synthesis of trans-[Pt(CtCC6Me4CtCH-4)2(PR3)2] [R
) Me (1c), Et (1d), nBu (1e)]. To a solution of 1c (190 mg,

The First Anionic σ-Alkynyl Metal Polymers
Organometallics, Vol. 24, No. 11, 2005 2767
(Ar), 118.6 (tCPt, 1JPtC ) 31 Hz), 112.4 (CtCPt, 2JPtC ) 5 Hz),
84.3 (tCH), 81.2 (CtCH), 18.5 (Me), 17.9 (Me), 16.6 (Me), 16.4
(Me). 31P{1H} NMR (162 MHz, CDCl3): δ 17.17 (s, 1JPtP ) 2671
Hz).
(m, 12 H, PTo3), 3.34 (s, 4 H, tCH), 2.46 (s, 6 H, C6Me3), 2.24
(s, 18 H, Me, PTo3), 1.84 (s, 12 H, C6Me3), 1.54 (s, 2H, H2O).
APT 13C{1H} NMR (50 MHz, CDCl3): δ 141.67 (Ar), 140.29
(m, p-C, PTo3), 138.40 (Ar), 134.92 (m, o-CH, PTo3), 128.28 (m,
1
m-CH, PTo3), 128.27 (d, i-C, PTo3, JCP ) 60 Hz), 118.45
2b‚0.5H2O: Yield 467 mg, 65%. Mp: 229 °C (dec). Anal.
Calcd for C70H69O0.5P2Pt: C 71.50, H 5.96. Found: C 71.36, H
5.84. IR (cm-1): ν(CH) 3308, 3284 (s), ν(CtC) 2098 (s). 1H
NMR (400 MHz, CDCl3): δ 7.73-7.69 (m, 12 H, PTo3), 7.00-
6.98 (m, 12 H, PTo3), 3.02 (s, 2 H, tCH), 2.33 (s, 6 H, C6Me4),
2.20 (s, 18 H, Me, PTo3), 2.07 (s, 6 H, C6Me4), 2.01 (s, 6 H,
C6Me4), 1.60 (s, 6 H, C6Me4), 1.53 (s, 1 H, H2O). APT 13C{1H}
NMR (100 MHz, CDCl3): δ 139.6 (p-C, PTo3), 135.1 (m, o-CH,
PTo3), 134.5 (Ar), 134.2 (Ar), 134.0 (Ar), 130.1 (Ar), 129.9 (Ar),
128.7 (d, i-C, PTo3, 1JCP ) 30 Hz), 128.1 (m, m-CH, PTo3), 120.4
(tCPt, 1JCPt ) 31 Hz), 120.0 (Ar), 112.2 (CtCPt, 2JCPt ) 4 Hz),
84.3 (tCH), 81.1 (CtCH), 21.2 (Me, PTo3), 18.5 (Me), 17.8
(Me), 16.6 (Me), 16.3 (Me). 31P{1H} NMR (162 MHz, CDCl3):
(CtCPt), 110.19 (CtCPt), 83.43 (tCH), 81.92 (CtCH), 21.22
(Me, PTo3), 19.61 (Me), 19.58 (Me). 31P{1H} NMR (162 MHz,
CDCl3): δ 17.13 (s, 1JPPt ) 2633 Hz). MS (FAB+), m/z (%): 1186
(M+, 90).
Synthesis of trans-[Pt(CtCC6Me4CtCAuPR3-4)2(PAr3)2]
[Ar ) Ph (4a), To (4b)]. To a solution of trans-[Pt{CtC(C6-
Me4)CtCH-4}2(PAr3)2] [Ar ) Ph (1a) 125 mg, 0.12 mmol; To
(1b) 99 mg, 0.08 mmol] in degassed CH2Cl2 (1a, 20 mL) or
acetone (1b, 20 mL) was added the appropriate [Au(acac)PR3]
complex [R ) Ph (193 mg, 0.35 mmol), To (153 mg, 0.25
mmol)], and the mixture was stirred under nitrogen for 6 (4a)
or 10.5 (4b) h. In the case of 4a a light suspension formed,
which was filtered, the filtrate concentrated under vacuum to
ca. 10 mL, and Et2O (15 mL) added to give a yellow precipitate,
which was filtered, washed with Et2O (2 × 5 mL), and dried
under reduced pressure (ca. 1 mbar) for 1 h to give 4a‚H2O.
In the case of 4b a copious suspension formed, which was
concentrated under vacuum to ca. 10 mL, and the yellow solid
collected upon filtration was air-dried.
1
δ 16.35 (s, JPPt ) 2650 Hz). MS (FAB+) m/z (%): 1166 (M+,
26). Single crystals of 2b‚2CHCl3 suitable for an X-ray dif-
fraction study were obtained by the liquid diffusion method
using CDCl3 and n-pentane.
Synthesis of trans-[Pt(CtCC6Me4CtCH-2)2(PMe3)2]
(2c).15 To a solution of 2a (0.418 g, 0.39 mmol) in dry THF (15
mL) under nitrogen was added PMe3 (1 M in toluene, 2.32 mL,
2.32 mmol). After 14.5 h of stirring, the reaction mixture was
concentrated under vacuum to ca. 3 mL, n-pentane (15 mL)
was added, and after a few minutes of stirring, the suspension
was filtered. The solid was washed with n-pentane (5 mL) and
dried under reduced pressure (ca. 1 mbar) for 1 h to give 2c
as a colorless microcrystalline powder. Yield: 243 mg, 88%.
Mp: 234 °C (dec). Anal. Calcd for C34H44P2Pt: C 57.54, H 6.25.
Found: C 57.71, H 6.67. IR (cm-1): ν(CH) 3234 (s), ν(CtC)
4a‚H2O: Yield 115 mg, 48%. Mp: 174 °C (dec). Anal. Calcd
for C100H86Au2OP4Pt: C 59.56, H 4.30. Found: C 59.38, H,
4.32. IR (cm-1): ν(CtC) 2088 (s). 1H NMR (400 MHz, CDCl3):
δ 7.78-7.19 (m, 60 H, PPh3), 2.35 (s, 12 H, C6Me4), 1.64 (s, 12
H, C6Me4), 1.55 (s, 2 H, H2O). 31P{1H} NMR (162 MHz,
1
CDCl3): δ 42.57 (s, AuPPh3), 18.43 (s, PtPPh3, JPPt ) 2667
Hz).
4b: Yield 152 mg, 88%. Mp: 174 °C (dec). Anal. Calcd for
112H108Au2P4Pt: C 62.08, H 5.02. Found: C 62.01, H 5.25.
1
2084 (s). H NMR (400 MHz, CDCl3): δ 3.32 (s, 2 H, tCH),
C
IR (cm-1): ν(CtC) 2094 (s). 1H NMR (400 MHz, CDCl3): δ
7.67-7.62 (m, 12 H, PTo3), 7.45-7.40 (m, 12 H, PTo3), 7.23-
7.21 (m, 12 H, PTo3), 6.99-6.97 (m, 12 H, PTo3), 2.38 (s, 18 H,
Me, PTo3), 2.36 (s, 12 H, C6Me4), 2.22 (s, 18 H, Me, PTo3), 1.64
(s, 12 H, C6Me4). 13C{1H} NMR (100 MHz, CDCl3): δ 141.6 (d,
p-C, PTo3, 4JCP ) 2 Hz), 140.0 (Ar), 139.9 (m, p-C, PTo3), 135.0
2.48 (s, 6 H, C6Me4), 2.42 (s, 6 H, C6Me4), 2.20 (s, 6 H, C6Me4),
2
2.17 (s, 6 H, C6Me4), 1.77 (virtual t, 18 H, Me, PMe3, | JHP
+
4JHP| ) 8 Hz, JHPt ) 30 Hz). APT 13C{1H} NMR (100 MHz,
3
CDCl3): δ 136.0 (Ar), 135.5 (Ar), 134.7 (Ar), 131.8 (Ar), 129.0
2
(Ar), 120.8 (Ar), 116.0 (CtCPt, JCPt ) 31 Hz), 106.8 (tCPt,
1JCPt ) 267 Hz), 84.8 (tCH), 82.4 (CtCH), 19.0 (Me), 18.6
3
2
(Me), 16.9 (Me), 16.5 (Me), 16.0 (virtual t, Me, PMe3,
(d, m-CH, PTo3, JCP ) 12 Hz,), 134.2 (d, o-CH, PTo3, JCP
)
1
3JCP| ) 40 Hz). 31P{1H} NMR (162 MHz, CDCl3): δ
14 Hz), 133.7 (d, i-C, PTo3, 1JCP ) 86 Hz), 129.7 (d, o-CH, PTo3,
2JCP ) 11 Hz), 128.8 (Ar), 128.5 (Ar), 128.2 (d, m-CH, PTo3,
| JCP
+
-21.62 (s, JPtP ) 2320 Hz). MS (FAB+), m/z (%): 709 (M+,
1
3JCP ) 6 Hz), 127.9 (Ar), 127.2 (d, i-C, PTo3, JCP ) 57 Hz),
1
24).
120.7 (CtC), 120.5 (CtC), 112.8 (CtC), 103.4 (d, tCAu, 2JCP
) 27 Hz), 21.4 (Me, PTo3), 21.3 (Me, PTo3), 18.9 (Me), 17.8
(Me). 31P{1H} NMR: (162 MHz, CDCl3): δ 40.52 (s, AuPTo3),
16.94 (s, PtPTo3, 1JPPt ) 2654 Hz). MS (FAB+), m/z (%): 2167
(M+, 6). Crystals of 4b‚5CH2Cl2 suitable for an X-ray diffraction
study were obtained by the liquid diffusion method using CH2-
Cl2 and n-pentane.
Synthesis of trans-[Pt(CtCC6Me4CtCAuPR3-4)2(PMe3)2]
(4c). To a suspension of 4b (301 mg, 0.14 mmol) in dry THF
(5 mL) was added PMe3 (1 M in toluene, 1.2 mL, 1.2 mmol),
and the mixture was stirred under nitrogen for 25 h. The
resulting suspension was filtered and the colorless solid
collected, washed with n-pentane (2 × 10 mL), and dried
successively in an oven at 80 °C for 0.5 h and under reduced
pressure (ca. 1 mbar) for 0.5 h to give 4c‚1.5THF. Yield: 147
mg, 84%. Mp: 231 °C (dec). Anal. Calcd for C46H72Au2O1.5P4-
Pt: C 40.56, H 5.32. Found: C 40.44, H 5.50. IR (cm-1): ν-
(CtC) 2088 (s). 13H NMR (400 MHz, CDCl3): δ 3.75 (m, 6 H,
THF), 2.50 (s, 12 H, C6Me4), 2.44 (s, 12 H, C6Me4), 1.85 (m, 6
H, THF), 1.72 (m, 18 H, PtPMe3), 1.52 (d, 18 H, AuPMe3, 2JHP
) 10 Hz). APT 13C{1H} NMR (100 MHz, CDCl3): δ 140.2 (Ar),
138.8 (Ar), 135.5 (Ar), 135.2 (Ar), 133.8 (Ar), 127.0 (CtCPt),
Synthesis of trans-[Pt{CtCC6Me3(CtCH)2-3,5}2(PAr3)2]
[Ar ) Ph (3a), To (3b)]. A mixture of C6Me3(CtCH)3-1,3,5
(for 3a: 255 mg, 1.3 mmol; for 3b: 357 mg, 1.86 mmol), the
appropriate cis-[PtCl2(PR3)2] (R ) Ph, 262 mg, 0.33 mmol; To,
406 mg, 0.46 mmol), and CuI (for 3a: 6 mg, 0.033 mmol; for
3b: 9 mg, 0.05 mmol) in degassed NHEt2 (25 mL) was stirred
under nitrogen for 13 (3a) or 22 (3b) h. The suspension was
concentrated to dryness, the residue was dissolved in CHCl3
(5 mL), and the solution was added slowly dropwise into
rapidly stirred EtOH (50 mL). The resulting suspension was
filtered and the solid recrystallized from a 1:1 mixture of
CHCl3/Et2O and n-pentane and dried under reduced pressure
(1 mbar) for 1 h to give 3a‚H2O or 3b‚H2O as colorless powders.
3a‚H2O: Yield 168 mg, 46%. Mp: 212 °C (dec). Anal. Calcd
for C66H54OP2Pt: C 70.77, H 4.86. Found: C 70.74, H 4.88. IR
1
(cm-1): ν(CH) 3304 (s), ν(CtC) 2098 (s). H NMR (400 MHz,
CDCl3): δ 7.78-7.18 (m, 30 H, PPh3), 3.34 (s, 4 H, tCH), 2.45
(s, 6 H, C6Me3), 1.84 (s, 12 H, C6Me3), 1.55 (s, 2 H, H2O). APT
13C{1H} NMR (100 MHz, CDCl3): δ 141.70 (Ar), 138.72 (Ar),
135.02 (m, o-CH, PPh3), 131.19 (m, i-C, PPh3), 130.24 (m, p-CH,
PPh3), 127.63 (m, m-CH, PPh3), 119.84 (Ar), 118.48 (CtCPt),
110.42 (CtCPt), 83.54 (tCH), 81.87 (CtCH), 19.68 (Me), 19.63
(Me). 31P{1H} NMR (162 MHz, CDCl3): δ 18.63 (s, 1JPPt ) 2657
Hz). MS (FAB+), m/z (%): 1102 (M+, 10).
3b‚H2O: Yield 357 mg, 65%. Mp: 248 °C (dec). Anal. Calcd
for C72H66OP2Pt: C 71.80, H 5.52. Found: C 71.55, H 5.77. IR
(cm-1): ν(CH) 3280 (s), 3270 (s), ν(CtC) 2088 (s). 1H NMR
(400 MHz, CDCl3): δ 7.65-7.60 (m, 12 H, PTo3), 7.02-7.00
3
1
122.0 (d, CtCAu, JCP ) 9 Hz), 116.5 (tCPt, JPtC ) 30 Hz),
2
103.3 (d, CAu, JCP ) 29 Hz), 68.0 (CH2, THF), 25.6 (CH2,
1
THF), 19.1 (Me), 18.9 (Me), 15.9 (virtual t, PtPMe3, | JCP
+
3JCP| ) 40 Hz), 15.8 (d, AuPMe3, 1JCP ) 36 Hz). 31P{1H} NMR:
(162 MHz, CDCl3): δ 1.25 (s, AuPMe3), -21.46 (s, PtPMe3, 1JPPt
) 2316 Hz). MS (FAB+), m/z (%): 1252 (M+, 13).

2768 Organometallics, Vol. 24, No. 11, 2005
Vicente et al.
Synthesis of trans-[Pt{CtCC6Me3(CtCAuPTo3)2-3,5}2-
(PTo3)2] (5b). To a suspension of 3b (102 mg, 0.09 mmol) in
a 1:1 CH2Cl2/acetone mixture (10 mL) was added a solution of
[Au(acac)PTo3] (310 mg, 0.52 mmol) in degassed acetone (10
mL). The mixture was stirred under nitrogen for 24 h, the
resulting suspension was filtered and the colorless solid
washed with Et2O (5 mL) and air-dried. Yield: 226 mg, 79%.
Mp: 223 °C (dec). Anal. Calcd for C156H144Au4P6Pt: C 58.78,
H 4.55. Found: C 59.13, H 4.62. IR (cm-1): ν(CtC) 2096 (s).
1H NMR (400 MHz, CDCl3): δ 7.70-7.64 (m, 12 H, Ar, PtPTo3),
7.46-7.41 (m, 24 H, AuPTo3), 7.26-7.22 (m, 24 H, AuPTo3),
6.99-6.97 (m, 12 H, PtPTo3), 2.71 (s, 6 H, C6Me3), 2.39 (s, 36
H, Me, AuPTo3), 2.21 (s, 18 H, Me, PtPTo3), 2.07 (s, 12 H, C6-
Me3). APT 13C{1H} NMR (100 MHz, CDCl3): δ 141.6 (d, p-C,
AuPTo3, 4JCP ) 2 Hz), 140.0 (m, p-C, PtPTo3), 139.3 (Ar), 136.9
CD2Cl2): δ 7.47-7.26 (m, 30 H, PPN), 2.21-2.14 (three s, 24
H, C6Me4), 1.87 (m, 12 H, CH2, Bu), 1.41 (m, 12 H, CH2, Bu),
1.20 (m, 12 H, CH2, Bu), 0.70 (m, 18 H, Me, Bu). APT 13C{1H}
NMR (100 MHz, CD2Cl2): δ 137.70, 134.55 (quaternary carbon
nuclei, C6Me4), 134.16 (m, p-CH, PPN), 133.56, 133.47 (qua-
ternary carbon nuclei, C6Me4) 132.51 (m, m-CH, PPN), 129.90
(m, o-CH, PPN), 127.38 (m, i-C, PPN), 26.91 (s, P(CH2)2CH2-
2
Me), 24.75 (virtual t, PCH2CH2Et, | JCP
+
4JCP| ) 13.6 Hz),
24.32 (virtual t, PCH2Pr, |JCP + 3JCP| ) 34.6 Hz), 19.15, 19.10,
19.07 (s, C6Me4), 14.06 (s, Me, Bu). 31P{1H} NMR (162 MHz,
CD2Cl2): δ 21.13 (s, PPN), 3.53 (br s, P(nBu)3, JPPt ) 2377
1
Hz).
Synthesis of (PPN)2n[trans-Pt{CtCC6Me3(CtC)2-
3,5}2Au2(PTo3)2]n (7). To a solution of 3b (108 mg, 0.09 mmol)
in degassed CH2Cl2 (15 mL) was added a solution of PPN[Au-
(acac)2] (0.179 g, 0.19 mmol) in the same solvent (5 mL), and
the mixture was stirred under nitrogen for 24 h. The resulting
suspension was filtered and the solid washed with CH2Cl2 (2
× 5 mL) and dried under reduced pressure (ca. 1 mbar) for
0.5 h to give a colorless powder insoluble in all common organic
solvents. Yield: 184 mg, 77%. Mp: 206 °C (dec). IR (cm-1):
ν(CtC), 2084(w).
X-ray Structure Determinations. Numerical details are
presented in Table 1. Data were recorded at -140 °C on a
Bruker SMART 1000 CCD diffractometer using Mo KR radia-
tion (λ ) 0.71073 Å). Absorption corrections were based on
multiple scans (program SADABS). Structures were refined
anisotropically on F2 using the program SHELXL-97 (Prof. G.
M. Sheldrick, University of Go¨ttingen). Acetylenic H atoms
were refined freely; other H atoms, using a riding model or
rigid methyl groups. Special features of refinement. 1a: The
chloroform molecule is disordered over an inversion center.
4b: There are three dichloromethane sites, one of which is
disordered over an inversion center.
(Ar), 134.9 (m, o-CH, PtPTo3), 134.2 (d, o-CH, AuPTo3, 2JCP
)
3
14 Hz), 129.7 (d, m-CH, AuPTo3, JCP ) 12 Hz), 128.5 (Ar),
128.2 (m, m-CH, PtPTo3), 127.3 (d, i-C, AuPTo3, 1JCP ) 57 Hz),
127.1 (d, i-C, PtPTo3, 1JCP ) 56 Hz), 126.1 (Ar), 120.8 (d, CCAu,
3JCP ) 2 Hz), 117.7 (CtCPt), 111.8 (CtCPt), 102.6 (d, CAu,
2JCP ) 27 Hz), 21.45 (Me, PTo3), 21.34 (Me, PTo3), 21.14 (Me),
20.46 (Me). 31P{1H} NMR: (162 MHz, CDCl3): δ 40.51 (s,
1
AuPTo3), 17.01 (s, PtPTo3, JPPt ) 2653 Hz). MS (FAB+), m/z
(%): 3184 (M+, 22).
Synthesis of trans-[Pt{CtC(C6Me3)(CtCAuPMe3)2-
3,5}2(PMe3)2] (5c). To a suspension of 5b (105 mg, 0.033
mmol) in dry THF (15 mL) was added PMe3 (1 M in toluene,
0.29 mL, 0.29 mmol), and the mixture was stirred under
nitrogen for 6 h. The solution was concentrated under reduced
pressure to ca. 5 mL, and n-pentane (5 mL) was added to
precipitate a colorless solid, which was filtered, washed with
n-pentane (5 mL), and vacuum-dried (ca. 1 mbar) for 1 h.
Yield: 58 mg, 91%. Mp: 196 °C (dec). Anal. Calcd for C48H72-
Au4P6Pt: C 31.71, H 3.99. Found: C 32.07, H 4.02. IR (cm-1):
1
ν(CtC) 2086 (s). H NMR (300 MHz, CDCl3): δ 2.74 (s, 6 H,
C6Me3), 2.71 (s, 12 H, C6Me3), 1.71 (virtual t, 18 H, PtPMe3,
Results and Discussion
2
4
3
| JHP + JHP| ) 8 Hz, JHPt ) 28 Hz), 1.51 (d, 36 H, AuPMe3,
2JHP ) 10 Hz). APT 13C{1H} NMR (50 MHz, CDCl3): δ 140.6
(Ar), 140.0 (Ar), 139.5 (Ar), 137.6 (Ar), 122.3 (CtCAu), 114.8
Synthesis. The complexes trans-[Pt(CtCC6Me4-
CtCH-4)2(PAr3)2] [Ar ) Ph (1a), To (1b)], trans-[Pt-
(CtCC6Me4CtCH-2)2(PAr3)2] [Ar ) Ph (2a), To (2b)],
and trans-[Pt(CtCC6Me3(CtCH)2-3,5)2(PAr3)2] [Ar )
Ph (3a), To (3b)] were prepared by dehydrohalogenation
reactions, catalyzed by 0.1% mol CuI, between the
appropriate cis-[PtCl2(PR3)2] complexes and excess of
the alkynes C6Me4(CtCH)2-1,4, C6Me4(CtCH)2-1,2, or
C6Me3(CtCH)3-1,3,5 (approximately 1:4 molar ratio),
respectively, in diethylamine (Scheme 1). Some of the
complexes crystallized with half (2b) or one (3a,b)
molecule of water that we could not remove even after
repeated recrystallization from CHCl3/Et2O mixtures.
The PPh3 ligands in complexes 1a and 2a can be
replaced by more basic trialkylphosphines to give the
homologous derivatives with PMe3 (1c, 2c), PEt3 (1d),
or P(nBu)3 (1e) (Scheme 1).
Our previous experience of the synthetic utility of the
“acac method”25 to prepare alkynylgold(I) complexes26,28
from the acetylacetonatogold(I) complexes [Au(acac)-
PAr3] or [Au(acac)2]- and a variety of terminal alkynes
prompted us to study the possibility of preparing
heteronuclear PtIIAuI σ-alkynyl complexes from the
alkynyl derivatives 1-3, which could behave as terminal
alkynes. Thus, the reactions of complexes 1a, 1b, and
3b with an excess of the appropriate [Au(acac)PAr3]
gave, respectively, trinuclear PtIIAuI2 or pentanuclear
PtIIAuI4 σ-alkynyl complexes trans-[Pt(CtCC6Me4Ct
CAuPAr3-4)2(PAr3)2] [Ar ) Ph (4a), To (4b)] or trans-
[Pt{CtCC6Me3(CtCAuPAr3)2-3,5}2(PAr3)2] [Ar ) Ph
(5a), To (5b)], respectively, in good yield (Scheme 2).
2
(CtCPt), 106.9 (CtCPt), 102.9 (d, CAu, JCP ) 30 Hz), 21.87
1
3
(Me), 21.59 (Me), 16.29 (virtual t, PtPMe3, | JCP + JCP| ) 38
1
Hz), 16.20 (d, AuPMe3, JCP ) 36 Hz). 31P{1H} NMR: (121
1
MHz, CDCl3): δ 1.63 (s, AuPMe3), -21.10 (PtPMe3, JPPt
)
2329 Hz). MS (FAB+), m/z (%): 1817 (M+, 10).
Synthesis of (PPN)n[trans-Pt{(CtCC6Me4CtC-4)2Au}-
(PR3)2]n [R ) Ph (6a), Me (6c), nBu (6e)]. To a solution of
the appropriate complex 1 (1a: 161 mg, 0.15 mmol; 1c: 91
mg, 0.13 mmol; 1e: 155 mg, 0.16 mmol) in degassed CH2Cl2
(15 mL) was added a solution of PPN[Au(acac)2] (for 6a: 153
mg, 0.16 mmol; for 6c: 132 mg, 0.14 mmol; for 6e: 158 mg,
0.17 mmol) in the same solvent (10 mL). The mixture was
stirred under nitrogen for 15.5 (6a), 5 (6c), or 26 (6e) h. In
the first two cases a copious precipitate formed, which was
filtered, washed with CH2Cl2 (10 mL), and dried in the air and
then under reduced pressure (ca. 1 mbar) for 0.5 h to give a
bright orange (6a) or bright yellow (6c) powder insoluble in
all common organic solvents; thus further purification proved
impossible. For 6e a solution resulted that was filtered through
Celite, the solvent removed under vacuum to ca. 5 mL, and
n-pentane added (20 mL) to precipitate a colorless solid, which
was filtered, washed with n-pentane (2 × 5 mL), and dried
successively in the air and under reduced pressure (ca. 1 mbar)
for 0.5 h.
6a: Yield 183 mg, 67%. Mp: 159 °C (dec). IR (cm-1):
ν(CtC) 2086(w).
6c: Yield 128 mg, 68%. Mp: 142 °C (dec). IR (cm-1):
ν(CtC) 2082(s). 31P{1H} NMR (121 MHz, solid): δ 21.02 (br,
1
PPN), -22.22 (s, PMe3, JPPt ) 2324 Hz).
6e: Yield 207 mg, 76%. Mp: 194 °C (dec). Anal. Calcd for
C88H108AuNP4Pt: C 62.33, H 6.42, N 0.83. Found: C 62.00, H
1
6.39, N 0.86. IR (cm-1): ν(CtC) 2086(s). H NMR (400 MHz,

The First Anionic σ-Alkynyl Metal Polymers
Organometallics, Vol. 24, No. 11, 2005 2769
Table 1. Crystal Data and Structure Refinement
1a‚CHCl3
65H57Cl3P2Pt
1201.49
triclinic
P1h
2b‚2CHCl3
4b‚5CH2Cl2
formula
fw
cryst syst
space group
a (Å)
b (Å)
c (Å)
C
C72H70Cl6P2Pt
1405.01
triclinic
C117H118Au2Cl10P4Pt
2591.52
triclinic
P1h
P1h
9.0753(6)
11.5861(8
14.3546(11)
96.168(4)
102.756(4)
104.817(4
1401.48(17)
1
10.2862(6)
12.7169(8)
13.5664(11)
77.919(4)
70.307(4)
76.817(4)
1609.71(19)
1
12.3981(11)
15.1902(12)
16.3181(14)
92.748(4)
104.496(4)
107.755(4
2807.8(4)
1
R (deg)
â (deg)
γ (deg)
volume (Å3)
Z
F
calcd (Mg m-3
)
1.424
1.449
2.520
1.533
µ (Mo KR) (mm-1
F(000)
)
2.743
4.190
606
712
1286
cryst size (mm)
θ range (deg)
no. of reflns coll
no. of indep reflns
Rint
0.30 × 0.14 × 0.10
1.48 to 30.03
28 596
0.23 × 0.21 × 0.07
1.61 to 30.03
33 598
0.20 × 0.16 × 0.07
1.30 to 26.37
47 189
8158
9391
11442
0.0260
0.0305
0.0521
max. and min. transmsn
no. of restraints/params
goodness-of-fit on F2
R1 [I>2σ(I)]
0.819 and 0.663
105/343
1.023
0.862 and 0.667
106/378
0.802 and 0.669
198/604
1.037
0.986
0.0275
0.0229
0.0543
0.982 and -0.799
0.0393
0.1101
2.719 and -1.576
wR2 (all reflns)
largest diff peak
0.0688
1.800 and -1.583
and hole (e Å-3
)
Scheme 1
Scheme 2
However, although its NMR spectra show 5a‚2H2O to
be pure, the %C found is low (Anal. Calcd for C138H112
Au4O2P6Pt: C 55.79, H 3.80. Found: C 54.33, H 3.77),
which we could not improve even after repeated recrys-
-

2770 Organometallics, Vol. 24, No. 11, 2005
Vicente et al.
Scheme 3
tallizations. Under the same reaction conditions, the
homologous complexes trans-[Pt(CtCC6Me4CtCAuPAr3-
2)2(PAr3)2] (Ar ) Ph, To) could not be obtained from 2a
or 2b and [Au(acac)PAr3], which we attribute to the
steric hindrance between the ortho-CtCH substituents
in 2a or 2b and the bulky phosphine ligands, as
confirmed by the crystal structure of 2b (see below). The
replacement of the PTo3 ligands in complex 4b or 5b
by PMe3 allowed the synthesis of the homologous
complexes 4c and 5c, respectively (Scheme 2). Similarly,
the reaction of 4b with PEt3 (1:4) gave the corresponding
complex with this ligand, but despite many recrystal-
lizations, its NMR spectra and elemental analyses
(Anal. Calcd for C52H84Au2P4Pt: C 43.92, H 5.95.
Found: C 42.80, H 5.91) showed the presence of some
impurity that we could not remove.
Apart from the metallamacrocyclic PtII2AuI triangle
PPN[Au{Pt(PMe3)2}2{µ-C6Me4(CtC)2-1,2}3], the syn-
thesis and the crystal structure of which has been
recently reported by us,15 complexes [Pt(CtC-CtCH)-
{CtC-CtCAuPPh3}(dppe)]14 and the square metal-
lamacrocycle (PPN)4[Pt(CtC-CtC-Au-CtC-CtC)-
(dppe)]44 are the only mixed PtIIAuI σ-alkynyl complexes
previously reported. They were obtained by reacting [Pt-
(CtC-CtCH)2(dppe)] with nBuLi and [AuCl(PPh3)] or
with PPN[Au(acac)2], respectively, but their crystal
structures are unknown.
The reaction of PPN[Au(acac)2] with 1a, 1c, 1e (1:1)
or 3b (2:1) gave, respectively, the anionic σ-alkynyl
polymers
(PPN)n[trans-Pt{(CtCC6Me4CtC-4)2Au}-
n
(PR3)2]n [R ) Ph (6a), Me (6c), Bu (6e)] and (PPN)2n-
[trans-Pt{CtCC6Me3(CtC)2-3,5}2Au2(PTo3)2]n (7), which
were isolated in good yield (Scheme 3). Among them,
only 6e is soluble in organic solvents so as to allow its
purification and the measuring of its NMR spectra,
while the extreme insolubility of 6a, 6b, and 7 prevented
their recrystallization and, as is usual for this type of
polymeric materials, good elemental analyses (6a: Anal.
Calcd for C100H84AuP4Pt: C 66.15, H 4.66, N 0.77.
Found: C 63.75, H 4.50, N 0.59; 6c: Anal. Calcd for
C70H72AuNP4Pt: C 58.25, H 5.03, N 0.97. Found: C
inversion center at the Pt atoms (Table 1). In all cases
the platinum is in a square planar environment coor-
dinated to two alkynyl fragments and two phosphine
ligands in mutually trans positions, the C-Pt-P angles
being close to 90°. In 4b the gold atoms coordinate to
an alkynyl and a phosphine ligand in a linear environ-
ment [C-Au-P 175.2(2) °]. The CtC [1.214(3) Å (1a,
2b), 1.214 (9), 1.208(8) Å (4b)], C-Pt [1.998(2) Å (1a),
1.9973 (18) Å (2b), 2.007 (6) Å (4b)], P-Pt [2.2967(6) Å
(1a), 2.3094(4) Å (2b), 2.3147(15) Å (4b)], C-Au
[1.996(6) Å (4b)], and P-Au [2.2797(16) (4b) Å] bond
distances are in the ranges previously found in related
complexes.33 The structure of 2b reveals that the
CtCH hydrogen atoms lie between two aryl substitu-
53.29, H 5.09, N 0.50; 7: Anal. Calcd for C144H120
-
Au2N2P6Pt: C 65.18, H 4.56, N 1.06. Found: C 60.96,
H 4.69, N 0.94). A GPC study on 6e gave an average
molecular weight of 7.7 × 105 amu corresponding to a
medium value of 667 monomeric units, a number
considerably higher than those found in other alkynyl
metal-containing polymers.11,13,17,21,22 However, the great
polydispersity value (Ip ) 4.66) is indicative that 6e
contains a wide range of polymeric materials. The
polymers 6 and 7 are (i) the first heteronuclear alkynyl
polymers of any d8/d10 system, (ii) the first anionic
alkynyl polymers prepared to date, and (iii) the first
alkynyl polymers that have been obtained by the “acac
method”, which turns out to be useful for the synthesis
of organometallic polymers with a high degree of po-
lymerization. In the hope of synthesizing soluble alkynyl
AuIPtII polymers homologous to 6 and 7 we have
undertaken the study of the reactivity of the dialkynes
Figure 1. Thermal ellipsoid plot (50% probability) of 1a‚
CHCl3. Selected bond lengths (Å) and angles (deg): Pt-
C(1) 1.998(2), Pt-P 2.2967(6), C(1)-C(2) 1.214(3), C(2)-
C(3) 1.438(3), C(1)#1-Pt-C(1) 180.0, C(1)#1-Pt-P 86.48(6),
C(1)-Pt-P 93.52(6), C(2)-C(1)-Pt 175.8(2), C(1)-C(2)-
C(3) 173.8(2). Solvent and phosphine hydrogens are omitted
for clarity.
C6 Bu4(CtCH)2-1,4 and C6(nC4H9)4(CtCH)2-1,4 toward
t
Pt(II) and “AuI(acac)” complexes.
Crystal Structures of 1a‚CHCl3, 2b‚2CHCl3, and
4b‚5CH2Cl2. The complexes 1a (Figure 1), 2b (Figure
2), and 4b (Figure 3) are centrosymmetric with the

The First Anionic σ-Alkynyl Metal Polymers
Organometallics, Vol. 24, No. 11, 2005 2771
of X-H‚‚‚π hydrogen bond is well-documented.34 The
disordered or poorly resolved solvent of the other two
structures precludes meaningful analysis of correspond-
ing contacts.
Among the many (alkynyl)Pt(II) complexes structur-
ally characterized by X-ray diffraction methods,33 only
a few contain, as do 1a and 2b, CtCH fragments and
most contain the ligand -CtC-CtC-H.14,35,36 Apart
from our recently reported AuIPtII triangle PPN[Au-
2
{Pt(PMe3)2}2{µ-C6Me4(CtC)2-1,2}3],15 4b is the only
heteronuclear PtIIAuI complex structurally character-
ized by X-ray crystallography.
1
NMR Spectra. The H NMR spectra of complexes
1-5 show the resonances expected for the C6Me4-1,4 (1,
4), C6Me4-1,2 (2), or C6Me3-1,3,5 (3, 5) fragments that
they contain (see Experimental Section), and those of
complexes 1-3 show, in addition, a singlet resonance
for the CtCH protons in the range 3.01 (2a) to 3.50 (1c)
ppm. In the 31P{1H} NMR spectra, the Pt(PR3)2 frag-
ment gives rise to a singlet resonance with 195Pt
satellites. The 1JPPt coupling constants are in the range
2312 (1c) to 2667 (4a) Hz, as found in other trans-[Pt-
(alkynyl)2(PR3)2] complexes,35,37 and are greater than
those in the cis-isomers,38 in agreement with the weaker
trans-influence of the phosphine with respect to the
alkynyl ligands. The trans-geometry is confirmed for
complexes 1c, 2c, and 5c by their 1H NMR spectra,
which show virtual triplets with 195Pt satellites for the
PMe3 protons.39 The AuPR3 fragments in complexes 4
and 5 give rise to a singlet resonance in the 31P NMR
spectra. The δ(P) and the JPPt values for a given
phosphine depend only very slightly on the alkynyl
ligand and are not affected by the substitution of the
CtCH hydrogen atoms by AuPAr3.
Figure 2. Thermal ellipsoid plot (40% probability) of 2b‚
2CHCl3. Selected bond lengths (Å) and angles (deg): Pt-
C(1) 1.9973(18), Pt-P 2.3094(4), C(1)-C(2) 1.214(3), C(2)-
C(3) 1.434(2), C(1)#1-Pt-C(1) 180.0, C(1)#1-Pt-P 90.34(5),
C(1)-Pt-P 89.66(5), C(2)-C(1)-Pt 177.70(16), C(1)-C(2)-
C(3) 176.42(19).
The 13C{1H} NMR spectra of all complexes have been
measured (see Experimental Section) with the exception
of 4a, 6a, 6c, and 7, which, because of their insolubility,
do not give any resonance even after 12 h of acquisition.
We have assigned the CâtCRPt resonances only when
the C-Pt coupling was observed, based on the general
assumption that JCPt is greater for the R carbon,
although other authors make opposite assignments40 or
describe both resonances as due to the “CtC-Pt”
fragment.12 In our case the R carbon [δ, 116.5 (4c) to
1
120.9 (1a) ppm; JCPt, 29-31 Hz] is at lower field than
Figure 3. Thermal ellipsoid plot (30% probability) of 4b‚
5CH2Cl2. Selected bond lengths (Å) and angles (deg): Pt-
C(103) 2.007(6), Pt-P(1) 2.3147(15), Au-C(101) 1.996(6),
Au-P(2) 2.2797(16), C(1)-C(102) 1.437(8), C(4)-C(104)
1.445(8), C(101)-C(102) 1.214(9), C(103)-C(104) 1.204(8),
C(103)#1-Pt-C(103) 180.0, C(103)-Pt-P(1)#1 90.86(16),
C(103)-Pt-P(1) 89.14(16), P(1)#1-Pt-P(1) 180.0, C(101)-
Au-P(2) 175.2(2), C(102)-C(101)-Au 171.8(6), C(101)-
C(102)-C(1) 174.7(7), C(104)-C(103)-Pt 176.6(5), C(103)-
C(104)-C(4) 177.6(6). Solvent and H atoms are omitted for
clarity.
the â carbon [δ, 107.7 (1c) to 112.6 (1a) ppm; 2JCPt, 2-4
Hz].
In the heteronuclear complexes 4 and 5, the reso-
nances of the alkynyl carbon nuclei of the CâtCRAuPR3
fragments were assigned on the basis of the JCP values.
(34) Calhorda, M. J. Chem. Commun. 2000, 801, and references
therein.
(35) Onitsuka, K.; Fujimoto, M.; Ohshiro, N.; Takahashi, S. Angew.
Chem., Int. Ed. 1999, 38, 689.
(36) Leininger, S.; Stang, P. J.; Huang, S. Organometallics 1998,
17, 3981. Alqaisi, S. M.; Galat, K. J.; Chai, M.; Ray III, D. G.; Rinaldi,
P. L.; Tessier, C. A.; Youngs, W. J. J. Am. Chem. Soc. 1998, 120, 12149.
Phillips, J. R.; Miller, G. A.; Trogler, W. C. Acta Crystallogr., Sect. C
1990, 46, 1648.
ents of the phosphine, and the restricted access to these
hydrogen atoms could explain why [Au(acac)PR3] failed
to react with 2a and 2b, as mentioned above. In
compound 2b, the chloroform is well-ordered and makes
a very short contact to the centroid of the aromatic ring
C41-46, as shown in Figure 2 [C-H normalized to 1.08
Å; H‚‚‚Cent 2.39 Å, angle C-H‚‚‚Cent 162°]. This type
(37) Mayor, M.; Vonhanisch, C.; Weber, H. B.; Reichert, J.; Beck-
mann, D. Angew. Chem., Int. Ed. 2002, 41, 1183+.
(38) Falvello, L. R.; Fornies, J.; Gomez, J.; Lalinde, E.; Martin, A.;
Moreno, M. T.; Sacristan, J. Chem. Eur. J. 1999, 5, 474.
(39) Parish, R. V. NMR, NQR, EPR, and Mo¨ssbauer Spectroscopy
in Inorganic Chemistry, Ellis Horwood Series in Inorganic Chemistry;
1990.
(40) Sebald, A.; Wrackmeyer, B.; Theocharis, C. R.; Jones, W. J.
Chem. Soc., Dalton Trans. 1984, 747.
(33) CCDC CSD version 5.25 July, 2004.

2772 Organometallics, Vol. 24, No. 11, 2005
Vicente et al.
The R carbons give a doublet [in the range 102.6 (5b)
to 103.4 (4b) ppm] with 2JCP values of 23-30 Hz, while
the â carbons are at lower field [120.8 (5b) to 122.0 (4c)
(1-3, 55-85%) or [AuPR3]+ and [Au(PR3)2]+ (4, 5, 90-
100%). An attempted study of complex 6e by MALDI
using both linear and deflection, positive and negative
modes, did not afford any conclusive results. Complex
6e is only soluble in CHCl3 or CH2Cl2 when freshly
made. However, since a few days later it could not be
dissolved in any of those solvents or in MeOH, the
sample for the MALDI study was prepared by grinding
the solid with a matrix of ditranol. For the low mass
region only the PPN cation was detected, and when a
500 amu deflection was applied, the results show that
fragmentation occurs in the tube of flight of the ana-
lyzer.
Conclusions. We report some of the few mononuclear
PtII bis(σ-alkynyl) complexes of aryl di- and triacety-
lenes. These complexes are appropriate for the synthesis
of the first σ-alkynyl trinuclear PtIIAuI2 and penta-
nuclear PtIIAuI4 complexes by reacting them with [Au-
(acac)PR3] complexes. Using instead PPN[Au(acac)2] it
is possible to isolate the first reported anionic σ-alkynyl
metal polymers described so far.
3
ppm] and give a singlet or a doublet with smaller JCP
value (2-9 Hz).
The 31P{1H} NMR spectrum of 6e, the only soluble
polymer here described, shows one singlet resonance for
the Pt{P(nBu)3}2 fragments, which suggests a high
polymerization degree, in agreement with the mean
molecular weight (Mw ) 7.7 × 105 amu) determined by
GPC, which corresponds to some 667 monomeric units.
This 31P resonance, including the 195Pt satellites, is
appreciably wider than that due to the PPN cations, but
a variable-temperature study of this compound in CDCl3
shows both the 1H and 31P{1H} NMR spectra to be
independent of temperature changes. The resonances
from the CtC nuclei are not observed in the 13C{1H}
NMR spectrum of 6e, which confirms their elusive
detectability, as previously reported.41
IR Spectra. The IR spectra of complexes 1-7 show
the νCtC bands in the range 2102-2082 and those of
complexes 1-3 show, in addition, νCH bands in the range
3314-3240 cm-1, similar to those found in other
(alkynyl)Pt(II) complexes.8,12,42
Mass Spectra. The FAB+ MS of complexes 1-5 (See
Experimental Section) show the molecular peaks with
relative intensities ranging from 6 to 53%, the major
peaks corresponding to the fragments [Pt(PR3)2]2+
Acknowledgment. We are grateful for the financial
support of Ministerio de Ciencia y Tecnolog´ıa, FEDER
(CTQ2004-05396) and Fundacio´n Se´neca (Comunidad
Auto´noma de la Regio´n de Murcia, Spain) for a grant
to M.M.A.F.
Supporting Information Available: Listing of all refined
and calculated atomic coordinates, anisotropic thermal pa-
rameters, and bond lengths and angles for 1a‚CHCl3, 2b‚
2CHCl3, and 4b‚5CH2Cl2. This material is available free of
charge via the Internet at http://pubs.acs.org.
(41) Bruce, M. I.; Grundy, K. R.; Liddell, M. J.; Snow, M. R.; Tiekink,
E. R. T. J. Organomet. Chem. 1988, 344, C49. Bruce, M. I.; Liddell, M.
J. J. Organomet. Chem. 1992, 427, 263. Liau, R. Y.; Schier, A.;
Schmidbaur, H. Organometallics 2003, 22, 3199.
(42) Wong, W.-Y.; Lu, G.-L.; Choi, K.-H. J. Organomet. Chem. 2002,
659, 107.
OM0501273