Some mixed transition metal compounds of 1,3-diyne with metallacycles derived by cross-coupling of alkynyl ligands and sequential C-C bond coupling between 1,3-diyne and carbon monoxide

Article abstract of DOI:10.1021/om0492754

By treating cis-Pt(C≡CPh)₂(dppe) (1) with Mn ₂(CO)₉(CH3CN) in refluxing toluene, cross-coupling of alkynyl ligands occurs to afford mixed transition metal compound of 3,4-diphenyl-1,3-butadiyne, [Mn₂Pt(μ₃-η ¹:η¹:η²:η⁴ - PhCCCCPh)(CO)₆(dppe)] (2) in 19-38% isolated yield. 2 has a structure formed by an unprecedented heterometal complexation of 1-manganacyclo-2,3,4-pentatriene. The Pt(II) acetylide, by treating with Ru ₃(CO)₉(PPh₃)₃, directly converts into a π-complex of 1,3-diyne, Pt(η²-PhCCCCPh)(dppe) (4), in 38% yield. By reacting π-alkyne compound Pt(η ²-PhCC-C≡CPh)(PPh₃)₂ with Fe(CO) ₅ and Ru₃(CO)₁₂, bimetallic [FePt(μ ₃-¹:η¹:η²-COC ₄Ph₂)(CO)₃(PPh₃)₂] (5a) and triangular cluster [MPt₂(μ₃-η ¹:η¹:η²-PhCC-C≡CPh)-(CO) ₂(PPh₃)₂] (6a) have successionally been isolated in considerable yields. A dimetallic analogue of alkyne [FePt{μ ₂-η¹:η¹:η²-C(O)C ₂H₂}(CO)₃(Ph₃)₂] (5b) and trimetallic [MPt₂(μ₃-η¹:η ¹:η²-R¹CCR²)(CO) _7-n(PPh₃)_n] (6b-f) {R¹ = Ph, R ² = C=CPh, n = 3, M = Fe, 6b; R¹ = R² = H, n = 3, M = Fe, 6c; R¹ = R² = Ph, n = 2, M = Fe, 6d and iso-6d; R¹ = R² = OCOCH₃, n = 2, M = Fe, 6e; M = Ru, 6f} have consecutively been prepared. Crystal structures of five of the compounds have been determined.

Full text of DOI:10.1021/om0492754

20
Organometallics 2005, 24, 20-27
Articles
Some Mixed Transition Metal Compounds of 1,3-Diyne
with Metallacycles Derived by Cross-Coupling of Alkynyl
Ligands and Sequential C-C Bond Coupling between
1,3-Diyne and Carbon Monoxide
Shinsaku Yamazaki,*,† Zenei Taira,‡ Toshiaki Yonemura,§ and
Anthony J. Deeming
Chemistry Laboratory, Kochi Gakuen College, 292 Asahi Tenjin-cho, Kochi 780-0955 Japan,
Faculty of Pharmaceutical Sciences, Tokushima Bunri University,
180 Nishihama Yamashiro-cho, Tokushima 770-8055 Japan, Faculty of Material Sciences,
Kochi University, 2-5-2 Akebono-cho, Kochi 780-8520 Japan, and
Christopher Ingold Laboratory, University College London, 20 Gordon Street,
London WC1H OAJ, U.K.
Received September 17, 2004
By treating cis-Pt(CtCPh)2(dppe) (1) with Mn2(CO)9(CH3CN) in refluxing toluene, cross-
coupling of alkynyl ligands occurs to afford mixed transition metal compound of 3,4-diphenyl-
1,3-butadiyne, [Mn2Pt(µ3-η1:η1:η2:η4-PhCCCCPh)(CO)6(dppe)] (2) in 19-38% isolated yield.
2 has a structure formed by an unprecedented heterometal complexation of 1-manganacyclo-
2,3,4-pentatriene. The Pt(II) acetylide, by treating with Ru3(CO)9(PPh3)3, directly converts
into a π-complex of 1,3-diyne, Pt(η2-PhCCCCPh)(dppe) (4), in 38% yield. By reacting π-alkyne
compound Pt(η2-PhCC-CtCPh)(PPh3)2 with Fe(CO)5 and Ru3(CO)12, bimetallic [FePt(µ3-
η1:η1:η2-COC4Ph2)(CO)3(PPh3)2] (5a) and triangular cluster [MPt2(µ3-η1:η1:η2-PhCC-CtCPh)-
(CO)5(PPh3)2] (6a) have successionally been isolated in considerable yields. A dimetallic
analogue of alkyne [FePt{µ2-η1:η1:η2-C(O)C2H2}(CO)3(PPh3)2] (5b) and trimetallic [MPt2(µ3-
η1:η1:η2-R1CCR2)(CO)7-n(PPh3)n] (6b-f) {R1 ) Ph, R2 ) CtCPh, n ) 3, M ) Fe, 6b; R1 ) R2
) H, n ) 3, M ) Fe, 6c; R1 ) R2 ) Ph, n ) 2, M ) Fe, 6d and iso-6d; R1 ) R2 ) OCOCH3,
n ) 2, M ) Fe, 6e; M ) Ru, 6f} have consecutively been prepared. Crystal structures of five
of the compounds have been determined.
Introduction
in the presence of CuX (X ) Cl, I) and primary amines
such as diethylamine and piperydine), Eglinton coupling
using Cu2(OAc)2 in pyridine, and Cardiot-Chodkiewicz
coupling3 between lithiated alkynyls and halogenated
alkyne.
On the other hand, metallacycles of alkyne(s) may be
involved in important reactions such as the syntheses
of carbocyclic and heterocyclic compounds.4e,9 It should
be noticed that σ-acetylide is well known to function as
a ligand,5 and many mixed metal clusters composed of
Oxidative coupling of alkynyl ligands may be one of
the significant reactions studied more recently in the
methodical syntheses of one-dimensional allotropes of
the polyyne (-CtC-) unit with nonlinear optical prop-
erties.1 These nanomolecules and macrocyclic organo-
metallic compounds2 have mostly been derived by the
tail-to-tail coupling of the terminal carbon atoms on the
metal-assisted alkynyls, intermolecularly, using several
oxidizing reagents (e.g., a stoichiometric amount of O2
(3) (a) Qaisi, A. L.; Galat, K. J.; Chaim, M.; Ray, D. G., III; Rinaldi,
P. L.; Tessier, C. A.; Youngs, W. J. J. Am. Chem. Soc. 1998, 120, 12149.
(b) Eastmond, R.; Walton, D. R. M. Tetrahedron 1972, 28, 4591.
(4) Intramolecular C-C bond coupling of alkynyl ligands in mono-
nuclear compounds: (a) Field, L. D.; George, A. V.; Purches, G. R.;
Slip, I. H. M. Organometallics 1992, 11, 3019. (b) Takahashi, T.; Xi,
Z.; Obora, Y.; Suzuki, N. J. Am. Chem. Soc. 1995, 117, 2665. (c) Xi, Z.;
Fischer, R.; Hara R.; Sun, W.; H, Obora, Y.; Suzuki, N.; Nakajima.,
K.; Takahashi, T. J. Am. Chem. Soc. 1997, 119, 12842. (d) Yamazaki,
S.; Taira, Z. J. Organomet. Chem. 1999, 578, 61. (e) Choukroun, R.;
Donnadieu, B.; Zhao, J.-S.; Cassoux, P.; Lepetit, C.; Silvi, B. Organo-
metallics 2000, 19, 1901. Intermolecular C-C bond coupling of alkynyl
ligands on clusters: (f) Corrigan F.; Doherty, S.; Taylor, N. J.; Carty,
A. J. Organometallics 1992, 11, 3160. (g) Giordano, R.; Sappa, E.;
Cauzzi, D.; Predieri, G.; Tripiccio, A. J. Organomet. Chem. 1996, 511,
263.
* To whom correspondence should be addressed. Tel: 81-088-840-
1121. Fax: 81-088-840-1123. E-mail: yamazaki@kochi-gc.ac.jp.
† Kochi Gakuen College.
‡ Tokushim Bunri University.
§ Kochi University.
An Emeritus Professor, University College London.
(1) (a) Marder, T. B.; Lesley, G.; Yuan Z.; Fyfe, H. B.; Chow, P.;
Stringer, G.; Jobe, I. R.; Taylor, N. J.; Williams, I. D.; Kurz, S. K.
Materials for Non-linaer Optics: Chemical Perspectives; 1991; Chapter
40, p 605. (b) Sonogashira, K.; Ohga, Hagihara, K. J. Organomet. Chem.
1980, 188, 237.
(2) (a) Wunz, U. H. F.; Roidl, Altman, G. M.; Enkelmann, V.;
Shimizu, K. D. J. Am. Chem. Soc. 1999, 121, 10719. (b) Zhou, Y.; Seyler,
J. W.; Weng, W.; Arif, A. M.; Gladysz, J. A. J. Am. Chem. Soc. 1993,
115, 8509. (c) D’Amato, R.; Fratoddi, I.; Cappotto, A.; Altamura, P.;
Delfini, M.; Bianchetti, C.; Bolasco, A.; Polzonetti, G.; Russo, M. L.
Organometallics 2004, 23, 2860.
(5) Yasufuku, K.; Yamazaki, H. Bull. Chem. Soc. Jpn, 1972, 45,
2664.
10.1021/om0492754 CCC: $30.25 © 2005 American Chemical Society
Publication on Web 12/08/2004

Heterometallacycles of 1,3-Butadiyne
Organometallics, Vol. 24, No. 1, 2005 21
Scheme 1. Five-Membered Metallacycles of
1,3-Diyne
Scheme 2. Frameworks of Metallacycles of
1,3-Diyne Derived by Cross-Coupling of Acetylides
the versatile alkynyls have been prepared.5 1,3-B-
utadiyne can function as a greater electron supplier,
which enables formation of up to a four-metal cluster
bridged by its unusual linkages.6 Metallacycles of 1,3-
butadiyne formed by the head-to-head C-C bond cou-
pling of σ-acetylides are known in mono- and dinuclear
complexes.4
Scheme 3. Frameworks of Metallacycles of
1,3-Diyne Derived by Cross-Coupling of Acetylides
and Successive C-C Bond Coupling between
1,3-Diyne and Carbon Monoxide
Small cyclic alkynes are usually unstable because of
ring strain. 1-Metallacyclo-2,4-diene 1 (Scheme 1) is well
known.4e,6b 1-Metallacyclo-3-pentyne compound 27 was
recently isolated by treating zirconocene dichloride with
Bu-Li, followed with cumulenes having bulky substit-
uents, (Z)-1,4-bis(trimethylsilyl)-1,2,3-butatriene and
(Z)-2,2,7,7-tetramethyl-3,4,5-octatriene, or by a photo-
reaction of zirconocene dichloride in the presence of 1,4-
dichloro-2-butyne and magnesium. Titanocene and zir-
conocene compounds 3 are five-membered metallacyclo-
cumulenes, in which the 1,3-butadiyne compound was
derived through an intramolecular C-C bond coupling
of bis(σ-acetylide) by sunlight treatment.8 Owing to the
multiple-bond character of the C2-C3 bond, complex-
ation of both 2 and 3 occurs to form heterodinuclear
complexes composed of 3 and 1, respectively. These
metallacycles had a planar C4 unit6f,7c,8 contributed of
hybrid resonance, suggesting an intermediate9 in the
cleavage of the C-C single bond of 1,3-butadiyne,
interestingly. These reports of metallacycles that are
formed by alkyne(s) are mostly concentrated on mono-
nuclear and dinuclear complexes of titanium and zir-
conium. However, complexation of 2 or 3 of the electron-
rich transition metals (Mn, Ru, Pt) forming tri- and
tetranuclear complexes is elusive.
(PhCCCCPh)(CO)6(dppe)] (2), has been prepared by
reacting the bis(σ-acetylide)platinum(II) with Mn2(CO)9-
(CH3CN). The crystal structure of 2 reveals an unprec-
edented metallacycle of 1,3-diyne, which is discussed in
comparison of 3 and iso-3, newly determined in this
paper. Σ-Acetylides in 1, by treating with Ru3(CO)9-
(PPh3)3 in refluxing toluene for 1 h, directly convert into
the π-1,3-diyne compound Pt(η2-PhCCCCPh)(dppe) (4),
in 38% isolated yield,11 as shown in Scheme 2. Succes-
sive reactions of Pt(η2-R1CCR2)(PPh3)2 (R1 ) Ph, R2 )
-CtCPh; R1 ) R2 ) H) with Ru3(CO)12 and Fe(CO)5
have led to the isolation of a dimetallacyclic compound,
[FePt(µ2-η1:η1: η2-C(O)R1CdCR2)(CO)3(PPh3)2] (5) (R1 )
Ph, R2 ) CtCPh, 5a; R1 ) R2 ) H, 5b), through C-C
bond coupling between 1,3-diyne and carbon monoxide,
and then a triangular cluster, [M2Pt(µ3-η1:η1:η2-R1-
CCR2)(CO)5(PPh3)2] (6) (M ) Fe, R1 ) Ph, R2 ) CtCPh;
R1 ) R2 ) H, Ph, COOCH3; M ) Ru, R1 ) Ph, R2 )
CCPh).
In our goal of alkyne oligomerization,4d we have
utilized bis(acetylide) Pt(II) complexes and achieved
acyclic dimeriztion of alkynyls through the head-to-head
C-C bond coupling of acetylides in cis-Pt(CtCPh)2-
(dppe) (1) by using metal carbonyls in refluxing toluene.
Simultaneously, mixed metal compounds of 1,3-diyne
with unusual metallacycles have been obtained as
shown in Scheme 2, in which 3 and iso-3, [PtRu3-
(PhCCCCPh)(CO)10(dppe)], are in an anomalous form
given by complexation of 1-metalla-2,4-pentadiene as
published elsewhere.10 A new compound, [Mn2Pt-
Experimental Section
Preparation of [Mn2Pt(µ3-η1:η1:η2:η4-PhCCCCPh)(CO)6-
(dppe)], 2. To Mn2(CO)9(CH3CN) in toluene {in situ prepared
by treating Mn2(CO)10 (0.17 g) in CH2Cl2 with NMe3dO‚H2O
(0.05 g) and CH3CN (0.1 g)} in a two-necked flask with a
condenser was added Pt(CCPh)2(dppe) (0.15 g). The mixed
solution was then refluxed for 45 min, cooled, and evaporated.
The residue was separated by column chromatography (SiO2).
A red band was collected and rechromatographed {TLC(SiO2)}
using CH2Cl2. From an eluent of a deep orange band in CH2Cl2,
followed by recrystallization of the product from CH3CN in 253
K, crystals of deep orange plates were obtained (0.077 g, 38%/
(6) (a) Bruce, M. I.; Low, P. J. Adv. Organomet. Chem. 2001, 48, 71.
(b) Bruce, M. I.; Zaitseva, N. N.; Skelton, B. W.; White, A. H. Inorg.
Chim. Acta 1996, 250, 129. (c) Liu, L.; Chang, K.; Wen, Y. J. Chin.
Chem. Soc. 1997, 44, 33. (d) Okazaki, M.; Ohtani, T.; Inomata, S.;
Takagi, N.; Ogino, H. J. Am. Chem. Soc. 1998, 120, 9135.
(7) (a) Suzuki, N.; Nishihara, M.; Wakatsuki, Y. Science 2002, 295,
660. (b) Lam K. C.; Lin, Z. Organometallics 2003, 22, 3466. (c) Suzuki,
N.; Aihara, N.; Takahara, H.; Watanabe, T.; Iwasaki, M.; Saburi, M.;
Hashizume, D.; Chihara, T. J. Am. Chem. Soc. 2004, 126, 60.
(8) (a) Pellny, P.-M.; Kirchbauer, F. G.; Burlakov, V. V.; Baumann,
W.; Spannenberg, A.; Rosenthal, U. J. Am. Chem. Soc. 1999, 121, 8313.
(b) Jemmis, E. D.; Phukan, A. K.; Jiao, H.; Rosenthal, U. Organome-
tallics 2003, 22, 4958. (c) Rosenthal, U. Angew. Chem., Int. Ed. 2003,
42, 1794.
(9) Rosenthal, U. Angew. Chem., Int. Ed. 2004, 43, 3882.
(10) Yamazaki, S.; Taira, Z.; Yonemura, T.; Deeming, A. J.; Nakao,
A. Chem. Lett. 2002, 1174.
(11) (a) Leadbeater, N. E. J. Organomet. Chem. 1999, 573, 211. (b)
Leadbeater, N. E.; Raithby, P. R. J. Coord. Chem. 2001, 53, 311, 17.

22 Organometallics, Vol. 24, No. 1, 2005
Yamazaki et al.
platinum atom). Anal. Found: C, 53.24; H, 3.40. Calc for C48
Å) were corrected for Lorentz and polarization effects and for
absorption by semiempireral methods based on ψ scans.
Structure solutions were performed by direct methods using
SHELXL-97,14 with refinement by full-matrix least-squares on
Fo . All non-hydrogen atoms were refined anisotropically with
H atoms in the calculated positions riding on C atoms with
C-H fixed at 0.96 Å.
H34O6P2Mn2Pt: C, 53.69; H, 3.19. IR (Nujol mull): ν˜ (cm-1
)
2020s, 1990vs, 1949vs, 1929vs (M-CO). 13C NMR (CDCl3): δ
(ppm) 29.7(CH2- of dppe), 143.9(PhCC-CCPh), 175.2 (PhC-
CCCPh), 223.5 (Mn-CO). 31P NMR (CDCl3): δ (ppm) 53.22
(JPt,P ) 3140 Hz).
2
Preparation of [Pt(η2-PhCCCCPh)(dppe)], 4. To Pt-
(CCPh)2(dppe) (0.24 g) (1) in toluene was added Ru3(CO)9-
(PPh3)311 (0.4 g), and the mixed solution was refluxed for 1 h,
cooled, and evaporated. The deep red residue was separated
by column chromatography (SiO2) using CH2Cl2. From an
eluent of a red band, red crystals of unreacted Ru3(CO)9(PPh3)3
were recovered (0.096 g, 24%/Ru atom). An orange band was
collected and rechromatographed {TLC(SiO2)}. A colorless
eluent, by recrystallization from toluene, gave pale yellow
crystals of Pt(PhCCCCPh)(dppe) (0.09 g, 38% yield/Pt atom).
Anal. Found: C, 63.03; H, 4.31. Calc for C42H34P2Pt: C, 63.39;
H, 4.31. IR (Nujol mull): ν˜ (cm-1) 2108.6m{ν(CtC)nonbonding of
1,3-diyne}, while ν(CtC)bonding could not be detected. 31P NMR
(CDCl3): δ (ppm) 49.93(JPt,P ) 3074 Hz), 48.31(JPt,P ) 3304
Hz).
Crystal Structure Data of C48H34O6P2Mn2Pt, 2. A single
crystal was obtained from CH3CN-hexane at 248 °C: mono-
clinic, space group P121/c1, a ) 11.0250(50) Å, b ) 16.2310(50)
Å, c ) 24.4320(50) Å, R ) 90.000(5)°, â ) 97.889(5)°, γ )
90.000(5)°, V ) 4330.65(39) Å3, Z ) 4, Dc ) 1.65 g‚cm-3, R1 )
0.0658, wR2 ) 0.3141, Goof(S) ) 1.4790 for 9939 independent
reflections, in the range 0° < 2θ < 54.99°, with Fo > 4σ(Fo)
refining 5160 parameters.
Crystal structure data of C52H34O10P2PtRu3, iso-3:
orthorhombic, space group Pcab, a ) 19.5170(50) Å, b )
23.4600(50) Å, c ) 31.0440(50), R ) 90.000(5)°, â ) 90.000(5)°,
γ ) 90.000(5)°, V ) 14214(5) Å3, Z ) 8, Dc ) 1.289 g‚cm-3, R1
) 0.047, wR2 ) 0.1921, Goof(S) ) 1.5710 for 13 074 indepen-
dent reflections, in the range 0° < 2θ < 51.36°, with Fo > 4σ(Fo)
refining 9738 parameters.
Crystal structure data of C42H34P2Pt, 4: triclinic, space
group P1h, a ) 196(5) Å, b ) 21.201(5) Å, c ) 9.352(5) Å, R )
93.142(5)°, â ) 111.401(5)°, γ ) 87.661(5)°, V ) 1878.9(14) Å3,
Z ) 2, Dc ) 1.406 g‚cm-3, R1 ) 0.0934, wR2 ) 2746, Goof(S) )
1.2490 for 8620 independent reflections, in the range 0° < 2θ
< 55.00°, with Fo > 4σ(Fo), refining 5961 parameters. Selected
bond distances (Å) and angles (deg): Pt1-C1 2.02(3), Pt1-
C3 1.98(3), C1-C2 1.39(4), C1-C3-C1 1.34(4), C2-C4
1.18(4): C1-Pt1-C3 39.0(11), Pt1-C1-C3 68.8, Pt1-C3-C1
72.1(19), Pt1-C3-C71 148.9(19), C1-C3-C71 139(3),
C2-C1-C3 143(3), C1-C2-C4 172(3).
Preparationof[FePt{µ3-η1:η1:η2-C(O)C4Ph2}(CO)3(PPh3)2],
5a. To Pt(η2-PhCCCCPh)(PPh3)2 (0.25 g) in benzene was added
Fe(CO)5 (0.053 g). The solution was refluxed for 5 min, cooled,
and evaporated. The residue was separated by column chro-
matography (Al2O3) using CH2Cl2. An eluent of a deep orange
band gave deep orange crystals (0.282 g, 95% yield/platinum
atom). Anal. Found: C, 62.36; H, 3.74; P, 5.32. Calc. for
C56H40O4P2FePt: C, 61.72; H, 3.70; P, 5.69. IR (Nujol mull): ν˜
(cm-1) 1953.5vs{ν(CO)}, 1929.5vs{ν(CO)}, 2011.4vs{ν(CO)},
1720.0m{ν(CdO)}. FABMS (m-nitrobenzyl alcohol as a ma-
trix): m/z 1090(M+), 1006(M+ - 3CO), 978(M+ - 4CO), 775
(M+ - 4CO - 1,3-diyne)}. 31P NMR (CDCl3): δ (ppm) 25.60{JPt,P
) 3996.2 Hz}, 29.08{JPt,P ) 2782 Hz}. 13C NMR (CDCl3):
Crystal structure data of C56H40FeO4P2Pt, 5a: M )
1089.76, orange crystal, 0.50 × 0.25 × 10 mm, triclinic, space
group P1h, a ) 11.540(5) Å, b ) 12.275(5) Å, c ) 21.489 (12) Å,
R ) 96.13(3)°, â ) 92.65(3)°, γ ) 117.88(3)°, V ) 2659(2) Å3, Z
δ
(ppm) 216.6{FeC(O)C(Ph)dC(CCPh)}, 204{Fe(CO)3},
83.0{PhC(Pt)dC(Pt)-CtCPh},98.4{PhC-(Pt)dC(Pt)-CtCPh},
147{PhCtC-C(Pt)dC(Pt)-Ph}, 166{PhCtC-C(Pt)dC(Pt)Ph,
JPt-C not well resolved}. An analogous reaction by extending
the period in refluxing toluene up to 30 min considerably
decreased its yield to 27%.
) 2, Dc ) 1.361 g‚cm-3, F(000) ) 1084, µ(Mo KR) ) 34.52 cm-1
,
R1 ) 0.0584, wR2 ) 0.1544, goof ) 1.085 for 7128 reflections
in the range 5° < 2θ < 45° with I > 2σ(I0) refining 577
parameters.
Preparation of [FePt{µ2-η1:η1:η2-C(O)C2H2}(CO)3(PPh3)2],
5b. Into a benzene solution of Pt(PPh3)4 (1.1 g), acetylene was
bubbled for a few minutes, during which the canary yellow
solution turned colorless. Fe(CO)5 (0.17 g) was then added into
the solution. The mixed solution was refluxed for 30 min,
cooled, and evaporated. The residue was separated by column
chromatography (Al2O3) using CH2Cl2. An eluent of a yellow
band gave yellow microcrystals (0.37 g, 46% yield/platinum
atom). Anal. Found: C, 55.78; H, 4.03. Calc for C42H32O4P2-
FePt: C,55.21: H,3.53.IR(Nujolmull): ν˜ (cm-1)2014.6vs{ν(CO)},
1946.5vs{ν(CO)}, 1749.5s{ν(CdO)}. 13C NMR (CDCl3): δ (ppm)
234.335{Fe-(CdO)-HCCH}, 221.55{Fe(CO)3}, 221.09{Fe-
(CO)3}, 220.18{Fe(CO)3}, 154.376{-C(dO)-C(Pt)HdCH(Pt),
Results and Discussion
Dialkynyl compound cis-Pt(CCPh)2(dppe) reacts with
Ru3(CO)12 to undergo intramolecular C-C bond cou-
pling of alkynyl ligands to afford a mixed metal com-
pound of 1,3-diyne, the racemate [PtRu3(PhCCCCPh)-
(CO)10(dppe)] (3) and its isomer iso-3.10 Cross-coupling
of alkynyl ligands has also been achieved by reacting
Pt(CtCPh)2(dppe) with Mn2(CO)9(CH3CN) in refluxing
toluene for 1 h, and a heterometal compound of 1,3-
diyne, [Mn2Pt(PhCCCCPh)(CO)6(dppe)] (2), was ob-
tained in 19-38% yield. 31P NMR of 2 showed a single
resonace at 53.22 ppm with JPt,P ) 3140 Hz, suggesting
a symmetrical arrangement of the Pt(dppe) group. 13C
NMR spectra showed that two alkynyl carbons from Pt-
(CCPh)2(dppe) are also symmetrically arranged, and two
resonances at 143.9 and 175.2 ppm were observed. A
single crystal of 2 was obtained from CH3CN-hexane
at 253 K, and its crystal structure was determined. An
intriguing molecular structure of 2 is shown in Figure
1 (phenyl rings of dppe are omitted for clarity). Α carbon
of the alkynyls in Pt(CtCPh)2(dppe) undergoes cross-
coupling, forming 1,4-diphenylbuta-1,3-diyne, whose
alkyne carbons newly bond to the Mn2(CO)6 group in a
(η1:η1:η2:η4)-fashion and the central carbon of 1,3-diyne
JPt ) 695.8 Hz}, 155.29{-C(dO)-CH (Pt)dC(Pt)H}.
-C
Crystallographic Determination of 2, iso-3, and 4.
Intensity data collected by θ/2θ scans at 298 K using a MXC
18 diffractometer (Mac Science) and Mo KR radiation were
corrected for Lorentz and polarization effectes, but not for
absorption. Structure solutions were by direct methods using
CRYSTAN SIR STAN, with refinement by full-matrix least-
2
squares on Fo . All diagrams and calculations were performed
using CRYSTAN (MacScience, Japan) or by DIRDIF 9912 and
WinGX 3.0.13
Crystal Structure Determination of 6a, 6c, 6d, and iso-
6d. Intensity data collected by ω-2θ scans at 20 °C on a
Nicolet R3v/m instrument using Mo KR radiation (λ ) 0.7103
(12) Beurskens, P. T.; Beurskens, G.; de Gelder, R.; Garcia-Granda,
S.; Gould, R. O.; Israel, R.; Smits, J. M. M. The DIRDIF-99 program
system; Crystallography Laboratory, University of Nijmegen: The
Netherlands, 1999.
(14) Sheldrick, G. M. SHELXL-97; University of Gottingen: Ger-
many, 1997.
(13) Farrugia, L. J. J. Appl. Crystallogr. 1999, 32, 837-838.

Heterometallacycles of 1,3-Butadiyne
Organometallics, Vol. 24, No. 1, 2005 23
Figure 1. ORTEP plot (50% probability thermal ellipsoids)
for Mn2Pt(µ3-η1:η1:η2:η4-PhCCCCPh)(CO)6(dppe)4, 2. Phenyl
rings of dppe are omitted for clarity.
Figure 3. ORTEP plot (50% probability thermal ellipsoids)
for PtRu3(µ4-η1:η1:η1:η1:η4-PhCCCCPh)(CO)10(dppe), iso-3.
Phenyl rings of dppe are omitted for clarity.
3-pentyne compounds of zirconocene and 1.33(4) Å of
the C-C triple-bond distance in η2-bonding 1,3-diyne,10
but rather approaching close to 1.444(8) Å of the C-C
double-bond length in a π-bonding stylene compound15
or 1.45(2) Å of the C-C single-bond distance in 3.10 The
bond angles C1-C2-C4 (120(2)°) and C2-C1-C3
(127(2)°) in the present case are fairly expanded from
113.7(15)° and 115.6(11)° of the corresponding angles
of 1-metallacyclopenta-2,4-diene (3), but much narrower
than 155.9(7)° and 156.2(6)° of the mononuclear
1-metallacyclopentyne7a and 136.78(3)° and 140.6(3)° of
the corresponding dinuclear complex.7c
Atomic distances C1-C3 (1.37(3) Å) and C2-C4
(1.40(3) Å), on the other hand, are close to those of vinyl
carbons {1.398(18) and 1.404(17) Å of iso-3, vide infra},
although they are slightly longer than 1.30-1.36 Å of
the corresponding distances of the rhodium-cumulene
complex RhCl(PiPr3)2(η2-H2CCCCCCPh2),16 which may
be caused by the distortion of the metallacycles. The 1,3-
diyne in 2 can, therefore, be viewed as a double
complexation form of either a five-membered (a) met-
allacyclotriene or (b) metallacyclodiene, rather than an
electron localized form of (c) 1-metallacyclopentyne
geometry.7-9 The actual structure may be close to (a),
which may largely be contributed from (b). The crystal
structure of iso-3, obtained as an isomer of 3,10 was
newly determined, which is in Figure 3 (phenyl rings
of bridging dppe are omitted for clarity). 1,4-Diphe-
nylbuta-1,3-diyne in iso-3 cross-links mixed metal
nuclei by a (µ4-η1:η1:η1:η1:η4) bond, forming a 1-ruth-
enacyclopenta-2,4-diene framework, while dppe in iso-3
bridges over Pt1 and Ru1 atoms and one carbon
monoxide now bonds to the Pt1 atom, as expected.10 The
geometry around the platinum atom is in good planar-
ity. Atomic distances of Pt-C, Ru-C, and Ru-Ru bonds
in iso-3 do not significantly differ from those of 3,
although the bridging dppe of iso-3 results in formation
of fairly expanded bond angles Pt1-P1-C5 (120.9(5)°),
Ru1-P2-C6 (117.1(5)°), P1-C5-C6 (111.4(9)°), and
P2-C6-C5 (112.8(9)°) from 108.5(7)° {107.8(6)°},
Figure 2. Structure of 2 with complexation of (a) mana-
ganacyclocumulene; (b) manganacyclopentadiene; (c) man-
ganacyclopentyne.
is now also bound to the Pt(dppe) group by an η2-bond.
Bond lengths Mn1-C3 (2.06(2) Å), Mn1-C4 (2.05(3) Å),
Mn2-C3 (2.03(2) Å), and Mn2-C4 (2.00(3) Å) are
consistent with a Mn-C σ-bond,13 while all bond lengths
Mn1-C1 (2.20(2) Å), Mn1-C2 (2.23(2) Å), Mn2-C1
(2.21(2) Å), and Mn2-C2 (2.28(2) Å) are consistent with
η2-bonds. Bond lengths Pt-C1 (2.04(2) Å) and Pt-C2
(2.03(2) Å) may also be comparable with 2.041(7) and
2.036(8) Å of Pt(η2-PhCCCCPh)(PPh3)2,17 but they do
not significantly differ from 2.07 to 2.09 Å of a pure
Pt-C σ-bond.10,11 The geometry around the Pt atom in
2 is in good planarity, and C1, C2, C3, and C4 are
coplanar {dihedral angles: C3-C1-C2-C4, 4(4)°, and
P1-Pt1-C2-C1, 1.63°}. The structure appears to con-
tain a crystallographically symmetrical plane, through
which Mn1 and Mn2 atoms are equivalently positioned
with bond length Mn1-Mn2 of 2.5798(60) Å. It should
be noticed that the C1-C2 bond distance (1.45(3) Å) is
longer than 1.206(7)7a and 1.336(4) Å7c of the 1-metalla-
(15) Zhang, X.; Yu, K.; Carpenter, G. B.; Sweigard, D. A. Organo-
metallics 2000, 19, 1201.
(16) Kovacik, I.; Laubender, M.; Werner, H. Organometallics 1997,
16, 5607.
(17) Yamazaki, S.; Speel, D. M.; Deeming, A. J. Organometallics
1998, 17, 755.

24 Organometallics, Vol. 24, No. 1, 2005
Yamazaki et al.
Table 1. Selected Bond Distances (Å) and Angles
(deg) for
Mn2Pt(µ3-η1:η1:η2:η4-PhCCCCPh)(CO)6(dppe)4, 2
bond distance
bond angle
Pt1-C1
2.04(2)
2.03(2)
1.37(3)
1.45(3)
2.20(2)
2.23(2)
1.40(3)
2.06(2)
2.05(3)
2.21(2)
2.28(2)
2.02(2)
2.00(3)
Pt1-C1-Mn1
129.3(11)
120.8(11)
128.4(11)
127.0(2)
69.6(13)
69.9(13)
68.5(12)
120.0(2)
68.8(13)
71.9(13)
73.9(13)
123.8(11)
60.5(13)
Pt1-C2
C1-C3
Pt1-C2-Mn2
Pt1-C2-Mn1
C2-C1-C3
C1-C2
Mn1-C1
Mn1-C2
C2-C4
Pt1-C2-C1
Mn1-C2-C1
Mn2-C2-C1
C1-C2-C4
Pt1-C1-C2
Mn1-C1-C2
Mn2-C1-C2
Pt1-C1-Mn2
Mn2-C2-C4
Mn1-C3
Mn1-C4
Mn2-C1
Mn2-C2
Mn2-C3
Mn2-C4
Table 2. Selected Bond Distances (Å) and Angles
(deg) for
PtRu3(µ3-η1:η1:η1:η1:η4-PhCCCCPh)(CO)10(dppe),
iso-3 and 3
Figure 4. ORTEP plot (50% probability thermal ellipsoids)
of [FePt{µ2-η1:η1:η2-C(O)C4Ph2}(CO)3(PPh3)2], 5a. Phenyl
rings of PPh3 are omitted for clarity.
iso-3
3
Pt1-Ru1
Ru2-Ru3
Pt1-C1
Ru1-C2
Ru2-C3
Ru2-C4
Ru3-C1
Ru3-C2
Ru3-C3
Ru3-C4
C1-C2
2.7360(14) Pt1-Ru1
2.7165(18) Ru2-Ru3
2.055(12) Pt1-C1
2.088(13) Ru1-C2
2.105(13) Ru2-C3
2.107(16) Ru2-C4
2.286(12) Ru3-C1
2.3556(12) Ru3-C2
2.236(14) Ru3-C3
2.253(16) Ru3-C4
1.465(18) C1-C2
1.398(18) C1-C3
1.406(17) C2-C4
2.732(15) 2.7394(14)
2.722(2) 2.709(2)
2.100(16 2.074(14)
2.130(16) 2.137(18)
For 5a, one alkyne carbon atom of the 1,3-diyne still
remains intact as a dangling triple bond,21 as assesed
by 13C NMR spectra: Resonances due to 1,3-diyne were
observed by four resonances at 83.9, 98.4, 146, and 166
ppm. The former two resonances are due to nonbonding
alkyne carbons, while the other two to a bonding group.
2.09(2)
2.126(18)
2.171(16) 2.144(16)
2.355(15) 2.387(14)
2.365(17) 2.333(17)
2.224(14) 2.289(16)
2.262(18) 2.240(17)
1.45(2)
A strong stretching band was observed at 1720.0 cm-1
,
which is due to an organic ketonic carbonyl, and the
corresponding 13C NMR resonance appeared at 216.6
ppm.18,19 31P NMR resonances were observed at 25.60
{JPt,P ) 3996.2 Hz} and 29.08 {JPt,P ) 2782 Hz},
suggesting that two phosphorus atoms in the Pt(PPh3)2
group are unsymmetrically arranged. 5b may have an
analogous structure to 5a, and a strong IR absorption
band due to the organic ketonic carbonyl was observed
at 1750 cm-1 and 13C NMR resonance at 234.33 ppm,
respectively. The acetylene carbons are also unsym-
metrically arranged, and two resonances at 154.4 ppm
(JPt,C ) 696 Hz) and 166 ppm are consistent with a Pt-C
σ bond and an Fe-C σ bond, respectively. The crystal
structure of 5a is shown in Figure 4. An end carbon
atom of 1,3-diyne newly undergoes a C-C bond cou-
pling19,20 with carbon monoxide from the Fe(CO)4 group
{Fe-C(1) distance 2.024(12) Å}, resulting in formation
of an iron-acyl group. The other carbon atom of the
bonding alkyne group also forms a pure Pt-C σ bond
{bond distance Pt-C(3) 2.098(10) Å}. Bond distances
Fe(1)-C(2) (2.153(10) Å) and Fe(1)-C(3) (2.146(9) Å) are
consistent with η2-bonding. One alkyne group of the 1,3-
diyne forms a dimetallacycle in which the bond distance
C1-C3
1.44(2)
1.41(3)
1.43(2)
1.45(2)
C2-C4
Pt1-C1-C2 107.5(8)
Ru1-Pt1-C1 72.4(3)
Pt1-Ru1-C2 71.2(3)
Pt1-C1-C2 106.0(12) 104.6(11)
Ru1-Pt1-C1 73.4(5)
Pt1-Ru1-C2 71.0(4)
74.8(4)
69.0(4)
Ru1-C2-C4 138.2(10) Ru1-C2-C4 138.1(12 132.5(12)
C1-C2-C4
Ru1-C2-C1 107.2(8)
C2-C1-C3
113.2(11) C1-C2-C4
113.6(15) 116.8(15)
Ru1-C2-C1 108.3(11) 110.6(11)
115.6(11) C2-C1-C3
114.9(13) 113.2(13)
107.1(12)°, and 108.1(12)° of the corresponding angles
of 3, respectively (Table 2).
Reactions of the platinum(II) acetylide with Ru3(CO)9-
(PPh3)3 in refluxing toluene for 1 h afforded pale yellow
Pt(η2-PhCCCCPh)(dppe) (4) in 30-38% yield. From the
reaction products, deep red crystals of Ru3(CO)9(PPh3)3
were unexpectedly recovered in 40% yield, while any
mixed metal compounds could not be isolated. The
details of reductive elimination of the complex are still
uncertain. The crystal structure of 4 showed that the
geometry around the η2-bonding 1,3-diyne does not
significantly differ from that of the corresponding PPh3
complex.17 The corresponding PPh3 complex, Pt(η2-R1-
CCR2)(PPh3)2, reacts with an equimolar amount of Fe-
(CO)5 {and Ru3(CO)12} in refluxing C6H6 or toluene to
undergo an incorporation of an Fe(CO)4 group with the
π-alkyne-Pt complex to afford the heterobimetallic
compound [PtFe(µ2-η1:η1:η2-C(O)C4Ph4)(CO)3(PPh3)2] in
95% yield and then the heterotrimetallic triangular
cluster [MPt2(µ3-η1:η1:η2-PhCCCCPh)(CO)5(PPh3)2] (6a)
in considerable yields. The dimetallic analogue [FePt-
(µ2-η1:η1:η2-HCC(O)dCH)(CO)3(PPh3)2] (5b) and trime-
tallic [MPt2(µ3-η1:η1:η2-PhCCCCPh)(CO)7-n(PPh3)n] (n )
3, M ) Fe, R1 ) Ph, R2 ) CCPh, 6b; n ) 3, M ) Fe, R1
) R2 ) H, 6c; n ) 2, R1 ) R2 ) Ph, M ) Fe, 6d and
iso-6d; n ) 2, R1 ) R2 ) OCOCH3 M ) Fe, 6e; Ru, 6f)
have been correlatively prepared.
(18) (a) Burn, M. J.; Kiel, G.-Yu.; Seils, F.; Takats, J.; Washington,
J. J. Am. Chem. Soc. 1989, 111, 6950. (b) Ball, R. G.; Burke, M. R.;
Takats, J. Organometallics 1987, 6, 1918. (c) Gagne´, M. R.; Takats, J.
Oraganometallics 1988, 7, 561.
(19) (a) Fontain, X. L. R.; Jacobsen, G. B.; Shaw, B. L.; Thornton-
Pett, M. J. Chem. Soc., Dalton Trans. 1988, 741. (b) Nuller, F.; Han,
I. M.; van Koten, G.; Vrieze, K.; Heijdenrijk, D.; van Mechelen, J.; Stam,
C. H. Inorg. Chim. Acta 1989, 99, 158.
(20) (a) Farrugia, L. F.; Howard, J. A. K.; Mitprachacon, P.; Stone,
F. G. A.; Woodward, P. J. Chem. Soc., Dalton Trans. 1981, 162. (b)
Adams, R. D.; Wunz, U. H. F.; Fu, W.; Reidl, G. J. Organomet. Chem.
1999, 578, 55.
(21) (a) Low, P. J.; Bruce, M. I. Adv. Organomet. Chem. 2001, 48,
71. (b) Bruce, M. I.; Low, P. J.; Werth, A.; Skelton, B. W.; White, A. H.
J. Chem. Soc., Dalton Trans. 1996, 1551. (c) Bruce, M. I.; Skelton, B.
W.; White A. H.; Zaitseva, N. N. Aust. J. Chem. 1996, 49, 155.

Heterometallacycles of 1,3-Butadiyne
Organometallics, Vol. 24, No. 1, 2005 25
η1:η2-PhCCCCPh)(CO)4(PPh3)3] (6b)23 was obtained by
treating Pt(η2-PhCCCCPh)(PPh3)2 with Fe(CO)5 directly
in refluxing toluene for 30 min in 13% yield, although
the main products was 6a (62% yield). 6b and 6c24
consist of a Fe(CO)2(PPh3) group attached to [Pt2(µ2-η1:
η1-C4Ph2)(CO)2(PPh3)2]. For 6b, a 31P NMR resonance
arising from the Fe(CO)2(PPh3) group was observed at
65.7 ppm, while resonances arising from the Pt2-
(PhCCCCPh)(CO)2(PPh3)2 group appeared at 29.94 (1JPt,P
) 2841.8 Hz) and 25.11 ppm (1JPt,P ) 3991.5 Hz) with
a nuclear spin system A2M2,25 but 2JPt,P as observed for
6a could not be discerned in this case. Clusters with a
disymmetrical alkyne, [Pt2M(C2R2)(CO)5(PPh3)2] (M )
Fe, R ) Ph, 6d and iso-6d; R ) OCOCH3, M ) Fe, 6e;
R ) OCOCH3, M ) Ru, 6f) were analogously prepared,
except for the cases of 6e and 6f, which were prepared
by addition reactions of a M(CO)3 (M ) Fe, Ru) group
to the Pt(I) dimer, [Pt2{µ2-η1:η1-C2(CO2CH3)2}(CO)2-
(PPh3)2].26 6d has already been prepared by Adams et
al.27 We have, however, obtained 6d as a mixture with
isomer iso-6d,28 as 31P NMR spectra show with relative
intensities (3:2), which could not, however, be separated
by the TLC(SiO2) method. The NMR of 6 also suggests
that the arrangement of two phosphorus atoms in each
Pt2(CO)2(PPh3)2 group is directly related with the long-
distance coupling 2JPt,P: the 31P NMR of the isomer 6d
Table 3. Selected Bond Distances (Å) and Angles
(deg) of [FePt{µ2-η1:η1:η2-C(O)C4Ph2}(CO)3(PPh3)2],
5a
bond distance
bond angle
Pt(1)-C(3)
2.098(10)
2.608(2)
2.309(3)
2.350(3)
1.194(13)
1.49(2)
1.441(14)
1.51(2)
1.426(14)
1.22(2)
2.153(10)
2.146(9)
2.024(12)
1.835(14)
1.793(11)
1.824(13)
2.608(2)
P(1)-Pt(1)-P(2)
99.64(9)
52.9(2)
Pt(1)-Fe(1)
Pt(1)-P(1)
Pt(1)-P(2)
C(1)-O(1)
C(2)-C(1)
C(2)-C(3)
C(2)-C(12)
C(3)-C(4)
C(4)-C(5)
Fe(1)-C(2)
Fe(1)-C(3)
Fe(1)-C(1)
Fe(1)-C(20)
Fe(1)-C(21)
Fe(1)-C(22)
Pt(1)-Fe(1)
Fe(1)-Pt(1)-C(3)
Pt(1)-Fe(1)-C(2)
Pt(1)-C(3)-C(2)
Fe(1)-C(2)-C(3)
Fe(1)-C(3)-C(4)
Fe(1)-C(1)-C(2)
C(12)-C(2)-C(3)
C(2)-C(3)-C(4)
C(3)-C(4)-C(5)
C(2)-C(1)-O(1)
75.2(3)
110.2(7)
70.2(5)
129.7(7)
73.7(6)
128.8(9)
121.0(9)
177.3(12)
140.0(11)
Fe(1)-Pt(1) is 2.608(2) Å. The other alkyne of the 1,3-
diyne remains intact, as expected. The geometry around
the platinum atom is planar.
The C(1)-O(1) bond distance of 1.194(13) Å is con-
siderably shorter than the normal organic ketones
(1.215 Å).
Bond distances C(2)-C(1) (1.49(2) Å) and C(3)-C(2)
(1.441(14) Å) in 5a do not significantly differ from the
1.461(5) and 1.423(6) Å of the corresponding distances
in [Ru2(CO)(µ-CO){µ-σ:η2-C(O)C2Ph2}(η-C5H5)2].20 The
structure of 5 could be viewed either as a dimetallacy-
clopentenone (a) or a bridging carbene with a ketene sub-
stituent (b), as depicted in Figure 5. The actual structure
may be approaching an electron delocalized form (c)
with an allylic bond, but may be rather close to (a).
The dimetallacyclopenetenone has recently been es-
tablished for Os-Ir, Os-Fe, Os-Rh,18 Fe-Pt,19 Fe2, and
Ru2 systems,20 which have mostly been obtained by the
reactions of dinuclear complexes with alkynes. It is also
known that the π-bonding alkyne in the Pt(0) compound
displays an acidic nature which is susceptible to an
attack of nucleophile such as carbon monoxide or metal-
carbonyl to lead to the isolation of clusters.20,21 Pt-
(diyne)(PPh3)2 itself did not react with carbon monoxide.
Instead, by treatment of 5a with Pt(diyne)(PPh3)2 in
refluxing toluene, 6a17 was obtained in 75% yield (/Pt
atom of the dimer), while the same reaction in the
presence of carbon monoxide gave 6a in 55% yield. For
the transformation of 5a to 6a, the primary step may
be supposed as a reductive elimination, which may
proceed via C-C bond scission of the bridging organic
ketonic carbonyl in the Fe(CO)4 group.22 [FePt2(µ3-η1:
(22) (a) Dyke, A. F.; Knox, S. A. R.; Naish, P. J.; Taylor, G. E. J.
Chem. Soc., Dalton Trans. 1982, 1297. (b) Dyke, A. F.; Knox, S. A. R.;
Morris, M. J.; Naish, P. J. J. Chem. Soc., Dalton Trans. 1983, 1417.
(23) 6b was prepared as follows: Reactions of Pt(diyne)(PPh3)2 (0.25
g) with Fe(CO)5(0.05 g) in refluxing toluene for 5 min, followed by
separation of the products by TLC(SiO2) using CH2Cl2, gave three
products, which were respectively identified as 6a (13% yield/platinum
atom); 5a (27% yield/platinum atom); and [FePt2(µ3-η1:η1:η2-PhCCCCPh)-
(CO)4(PPh3)3], 6b. Anal. Found: C, 57.63; H, 3.65. Calc for C74H55O4P3-
FePt2: C, 57.44; H, 3.59. FABMS (m-nitrobenzyl alcohol as a matrix):
m/z 1548(M+) 1463(M+ - 3CO) 1239(M+ - 4CO). 31P NMR (CDCl3): δ
(ppm) 65.72(Fe-PPh3), 29.94{Pt1-PPh3, JPt-P ) 2841.8 Hz}, 25.11{Pt2-
PPh3, JPt,P ) 3991.5 Hz}. 13C NMR (CDCl3): δ (ppm) 227.8{Fe-CO},
220.6{Fe-CO}, 219.7{Pt-CO}, 216.54{Pt-CO}, 83.0{PhC(Pt)dC(Pt)-
CtCPh}, 98.4{PhC(Pt)dC(Pt)-CCPh}, 146.0{PhCtC-C(Pt)dC(Pt)-
Ph}, 166.0{PhCtC-C(Pt)dC (Pt)Ph}.
(24) 6c was obtained as follows: In the same TLC separation
processes isolating 5b, an eluent of another deep orange band gave
deep orange crystals of Pt2Fe(µ3-η1:η1:η2-HCCH)(CO)4(PPh3)3, 6c (0.28
g, 54%/platinum atom). Anal. Found: C, 52.54; H, 3.53. Calc for
C
60H47O4P2FePt2: C, 52.56; H, 3.30. IR (Nujol mull): ν˜ (cm-1) 2021.9vs,
1964.8vs, 1916.0vs, 1979.9vs cm-1 13C NMR (CDCl3): δ (ppm) 219.66-
.
{Fe(CO)2}, 198.6(Pt-CO, 195Pt satellites not discerned), 150.86(Pt-
CHdCH-Pt, 195Pt satellites not discerned).
(25) (a) Moore, A.; Pregosin, P. S.; Venanzi, L. M. Inorg. Chim. Acta
1981, 48, 153. (b) Moore, A.; Pregosin, P. S.; Vananzi, L. M. Inorg.
Chim. Acta 1982, 61, 135.
(26) (a) Koie, Y.; Shinoda, S.; Fitzgerald, B. J.; Pierpondt, C. G.
Inorg. Chem. 1980, 19, 770. (b) Koie, Y.; Shinoda, S.; Saito, Y. Inorg.
Chem. 1981, 20, 4408. (c) The starting compound, [Pt{C2(COOMe)2}-
(PPh3)2], was prepared and characterized as follows. To Pt(PPh3)4 (1.21
g) in C6H6 was added dmad (dimethylacetylene dicarboxylate, 0.138
g). The solution was stirred at room temperature for 5 min and
evaporated. The residue, after washing by hexane and diethyl ether,
was recrystallized from C6H6-hexane to give colorless crystals (0.43
g, 51%). Anal. Found: C, 59.02; H, 4.10; P, 6.77. Calc for C42H36O4P2-
Pt: C, 58.54; H, 4.21; P, 7.19. 31P{1H} NMR (CDCl3): δ (ppm) 24.18(s)
(JPt, ) 3727.57 Hz). 1H NMR (CDCl3): δ (ppm) 3.30(Me of dmad).
13C{1PH} NMR (CDCl3): δ (ppm) 51.68 (COOCH3), 165.60(t, -COOMe;
3JP, ) 20.12 Hz). (d) Crystal structure data of C42H36O4P2Pt: M )
C
789.70, colorless crystal, 0.35 × 0.3 × 0.2 mm, monoclinic, space group
P21/n, a ) 20.309(9) Å, b ) 15.355(7) Å, c ) 11.777(3) Å, â ) 97.89(3)°,
V ) 3637.89 Å3, Z ) 4, Dc ) 0.994 g‚cm-3, R1 ) 0.032, wR2 ) 0.042,
goof(S) ) 1.360 for 4410 reflections in the range 1° < θ < 30° with I >
3.00σ(I0) refining 550 parameters. Selected distances (Å) and angles
(deg): Pt(1)-P(2) 2.280(3), Pt(1)-P(3) 2.285(3), Pt(1)-C(6) 2.055(12),
Pt(1)-C(9) 2.023(13), C(6)-C(9) 1.302(18), C(6)-C(30) 1.433(18), C(9)-
C(17) 1.467(19), P(2)-Pt(1)-P(3) 105.2(1), P(2)-Pt(1)-C(9) 107.3(4),
C(6)-Pt(1)-C(9) 37.2(5), C(6)-Pt(1)-P(3) 110.6(4), C(9)-C(6)-C(30)
143.4(13), C(6)-C(9)-C(17) 141.2(12).
Figure 5. Geometry of 5a with metallacycle of 1,3-
butadiyne in resonante structures of (a) 1,2-dimetalla-3-
pentene-4-one; (b) η2-bonding carbene with a ketene sub-
stituent; (c) allylic bond.
(27) Adams, R. D.; Wunz, U. H. F.; Captain, B.; Fu, W.; Steffen, W.
J. Organomet. Chem. 2000, 614-615, 75.

26 Organometallics, Vol. 24, No. 1, 2005
Yamazaki et al.
unsymmetrical, and one Pt-PPh3 bond is perpendicular
to the Pt- - -Pt bond {bond length Pt1-Pt2 2.998(2) Å},
which does not significantly differ from 2.981(1) Å of
6d and 6e, but these are longer than 2.6345(8) Å found
in [Pt2{µ2-η1:η1-C2(CO2Me)2}(CO)2(PPh3)2].21 The other
selected bond lengths and angles around the (µ3-η1:η1:
(28) (a) 6d and iso-6d were prepared as follows: To Pt(PhCCPh)-
(PPh3)2 (0.25 g) in toluene was added Fe(CO)5. The mixed solution was
refluxed for 30 min, cooled, and evaporated. The deep orange residue
was separated by column chromatography (Al2O3) in CH2Cl2. An eluant
of a deep orange band was collected and recrystallized from C6H6 to
give deep orange crystals (0.29 g, 81% yield/platinum atom). Anal.
Found: C, 54.24; H, 3.31. Calc for C55H40O5P2FePt2-(C6H6): C, 53.59;
H, 3.39. IR (Nujol mull): ν˜ (cm-1) 2036.2vs, 2010.9vs, 1980.8vs, 1930.4vs
,
1900.7vs cm-1. FABMS (m-nitrobenzyl alcohol as a matrix): m/z 1288.6-
(M+), 1203.6(M+ - 3CO), 1176(M+ - 4CO), 1147.7(M+ - 5CO). 31P
1
2
NMR (CDCl3): δ (ppm) 17.37{6c, JPt,P ) 3640.9 Hz, JPt, ) 212.1
P
1
2
Hz}, 17.676{iso-6c, JPt-P ) 3757.2 Hz, JPt-P ) 348.9 Hz}, 22.332-
1
2
{iso-6c, JPt,P ) 2415.3 Hz, JPt,P not observed}. 13C{1H} NMR
(CDCl3): δ (ppm) 217.05{Fe(CO)3, 6c or iso-6c}, 216.7{Pt-CO, 6c or
iso-6c}, 165.2{(Pt)-C(Ph)dC(Ph)-(Pt), 6c or iso-6c}, 150{(Pt)-C(Ph)d
C(Ph)-(Pt), 6c or iso-6c}. (b) Crystal structure data of C55H40FeO5P2-
Pt2, iso-6d: A single crystal of iso-6d was obtained from acetone-
C6H6: M ) 1288.84, deep orange crystal, 0.46 × 0.35 × 0.20 mm,
monoclinic, space group P2(1), a ) 13.827(10) Å, b ) 11.825(4) Å, c )
18.198(9) Å, R ) 90°, â ) 110.92 (5)°, γ ) 90°, V ) 2779(3) Å3, Z ) 2,
Dc ) 1.540 g‚cm-3, F(000) ) 1244, µ(Mo KR) ) 34.52 cm-1, R1 ) 0.0635,
wR2 ) 0.1550, goof ) 1.093 for 5385 reflections in the range 5° < 2θ
< 50° with I > 2σ(I0) refining 521 parameters. Selected bond distances
(Å) and angles (deg): Pt(1)-Pt(2) 2.998(2) Pt(1)-Fe(1) 2.640(3) Pt-
(2)-Fe(1) 2.605(4) Pt(1)-C(1) 2.09(2) Pt(2)-C(2) 2.04(3) Fe(1)-C(1)
2.10(2) Fe(1)-C(2) 2.11(2) C(1)-C(2) 1.44(4) Pt(1)-Pt(2)-C(2) 66.3(7)
Pt(2)-Pt(1)-C(1) 69.2(7). (c) A single crystal of 6d was obtained from
C6H6. Crystal structure data for 6d: C55H40FeO5P2Pt2, M ) 1288.84,
deep orange crystal, 0.40 × 0.35 × 0.10 mm, orthorhombic, space group
Pcab, a ) 20.337(9) Å, b ) 121.664(14) Å, c ) 24.651(8) Å, R ) â ) γ
) 90.0°, V ) 10857(9) Å3, Z ) 8, Dc ) 1.575 Mg/m3, F(000) ) 14976,
µ(Mo KR) ) 34.52 cm-1, R1 ) 0.0991, wR2 ) 0.2580, goof ) 1.115 for
6889 reflections in the range 5.00° < 2θ < 45.06° with I >2σ(I0) refining
561 parameters at 293(2) K. Selected bond distances (Å) and angles
(deg): Pt(1)-Pt(2) 3.056(2) Pt(1)-Fe(1) 2.567(4) Pt(2)-Fe(1) 2.643(4)
Pt(1)-C(1) 2.08(3) Pt(2)-C(2) 1.98(2) Fe(1)-C(1) 2.10(3) Fe(1)-C(2)
2.04(3) C(1)-C(2) 1.42(4) Pt(1)-Pt(2)-C(2) 68.4(8) Pt(2)-Pt(1)-C(1)
63.7(8).
(29) (a) 6e was prepared as follows: To a C6H6 solution of 2 (0.26 g)
was added Fe(CO)5 (0.10 g). The solution was refluxed for 30 min,
cooled, and evaporated. The residue was separated by column chro-
matography (Al2O3) in CH2Cl2-hexane (1:1). An orange band was
collected and recrystallized from toluene to give reddish-orange crystals
(0.06 g, 21%/Pt atom). Anal. Found: C, 45.32; H, 3.09. Calc for
Figure 6. Crystal structures of (µ3-η1:η1:η2)-bonding alkyne
in triangular cluster: [FePt2(µ3-η1:η1:η2-PhCCPh)(CO)5-
(PPh3)2], iso-6d, and [FePt2(µ3-η1:η1:η2-CH3OCOCCCOO-
CH3)(CO)5(PPh3)2], 6e.
C
47H36O9P2FePt2: C, 45.06; H, 2.90. IR (Nujol mull): ν˜ (cm-1) 2045.6vs,
2010.2vs, 1967.5vs, 1939.8vs{ν(CO)}, 1713.2m 1693.7m{ν(CdO)}. 1H
NMR (CDCl3): δ (ppm) 2.86(CH3 of dmad). 13C(1H) NMR (CDCl3): δ
(ppm) resonances due to conformation A: 50.92 (s, CH3OCOCC-
COOCH3), 51.16(s, CH3OCOCCCOOCH3), 152.29 (s, CH3OCOC(Pt1)-
C(Pt2)-COOCH3), 174.45(s, CH3OCOC-(Pt1)-C(Pt2)COOCH3), 174.48-
(s, CH3OCO-C(Pt1)-C(Pt2)COOCH3), 193.46(s, Pt-CO), 215.24 {t,
Fe-CO, JP,C ) 5.95 Hz}. Resonances due to conformation B: 50.92(s,
CH3OCOCCCOOCH3), 51.16(s, CH3OCOCCCOOCH3), 152.32(s, CH3-
OCOC(Pt1)-C(Pt2)-COOCH3), 174.50(s, CH3OCOC(Pt1)-C(Pt2)-
COOCH3), 174.54(s, CH3OCOC(Pt1)-C(Pt2)-COOCH3), 193.54(s, Pt-
CO), 215.24{t, Fe-CO, JP,C ) 5.95 Hz}. (b) A single crystal of 6e was
obtained from toluene at 253 K. Crystal structure data for C47H36O9P2-
FePt2, 6e: M ) 1252.8, orange crystal, 0.35 × 0.3 × 0.2 mm,
monoclinic, space group P21/a, a ) 21.284(6) Å, b ) 18.822(6) Å, c )
1
consists of nuclear spin system A2MM′ with JA,M
)
1JPt,P ) 3640.9 and JA,M′ ) JPt,P ) 212.1 Hz at 17.37
ppm, rather than an AA′MM′26 spin system as observed
for [Pt2(µ2-η1:η1-C2(COOMe)(CO)2(PPh3)2).26 The 31P
NMR spectra for the other isomer, iso-6d, consists of
two independent resonances with equal intensities: one
2
2
due to an AMM′ spin system25 with JPt,P ) 3757.2 Hz
1
11.320(3) Å, â ) 104.61(2)°, V ) 4388.44 Å3, Z ) 4, Dc ) 1.896 g‚cm-3
,
µ(Cu KR) ) 156.07 mm-1, R ) 0.0455, wR ) 0.0665, goof(S) ) 1.1911
for 6354 refelections in the range 1° < θ < 25° with I > 2.00σ(I0)
refining 550 parameters. Selected bond distances (Å) and angles
(deg): Pt(1)-Pt(2) 2.981(1), Pt(1)-Fe(1) 2.579(3), Pt(2)-Fe(1) 2.567-
(3), Pt(1)-C(1) 2.014(17), Pt(2)-C(2) 2.021(17), Fe(1)-C(1) 2.069(17),
Fe(1)-C(2) 2.053(17), C(1)-C(2) 1.42(3), Pt(1)-Pt(2)-C(2) 67.7(5), Pt-
(2)-Pt(1)-C(1) 66.9(5).
2
and JPt,P ) 348.9 Hz appearing at 22.33(s) ppm; the
1
other an AM spin system with JPt,P ) 2415.3 Hz at
17.68(s) ppm. Therefore, 6d with the AMM′ spin sytem
may correspond to a symmetrical structure with two
phosphine ligands positioned mutually trans along the
Pt-Pt bond, while iso-6d is an unsymmetrical structure
in which one phosphine ligand with AM spin system is
positioned perpendicular to the Pt-Pt bond, for which
long-distance 2JPt,P could not be detected. A deep orange
single crystal of 6d was preferentially formed from C6H6
solution of these mixtures; however the other single
crystal of iso-6d28 was obtained from C6H6-acetone
solution. The crystal structure of iso-6d is shown in
Figure 6. The two phosphorus atoms in iso-6d are
(30) 6f was prepared as follows: To a C6H6 solution of 2 (0.20 g)
was added Ru3(CO)12 (0.11 g), and the solution was refluxed for 30
min, cooled, and evaporated. The residue was separated by TLC(SiO2).
An eluant of the yellow band gave orange microcrystals (0.08 g, 34%
yield/Pt atom). Anal. Found: C, 43.79; H, 3.04. Calc for C47H36O9P2-
Pt2Ru: C, 43.49; H, 2.80. IR (Nujol mull): ν˜ (cm-1) 2049.6vs, 2023.1vs,
2005.5vs, 1985.1vs, 1960.1vs{ν(CO)}, 1710.4s, 1695.7vs{ν(CdO)}. 1H
NMR (CDCl3): δ (ppm) 2.86(CH3 of dmadc). 13C NMR (CDCl3): δ (ppm)
50.98(s, CH3OCOCCCOOCH3), 51.18(s, CH3OCOCCCOOCH3), 152.3(s,
CH3OCOC(Pt1)dC(Pt2)-COOCH3), 174.13 (s, CH3OCOC(Pt1)dC(Pt2)-
COOCH3), 192.13{d, Pt-CO, JP,C ) 5.82 Hz, JPt,C not well resolved},
199.36 {t, Ru-CO, JP,C ) 4.52 Hz}.

Heterometallacycles of 1,3-Butadiyne
Organometallics, Vol. 24, No. 1, 2005 27
η2)-bonding alkyne do not significantly differ from those
of 6a,17 6d,28 and 6e.29
fluxional motion in a turnstyle manner as observed for
6a,12 which is in contrast to the stereochemical rigidity
of the corresponding group in 5a and 6b.
The structure of 6e in solution was consistent with
the crystal structure (Figure 6). Two 13C NMR reso-
nances due to the methylcarboxylate substituents were
distinct at around 51.0 and 152.3 ppm, respectively, at
293 K. These signals, however, collapsed to coalescence
at 308 K due to an allowance of free rotation of the
substituents. For 6e and 6f, 13C NMR resonances
arising from the M(CO)3 group (M ) Fe, Ru) were
unexpectedly observed as a single triplet pattern at
215.2 ppm (3JP,C ) 6 Hz) and 199.36 ppm (3JP,C ) 4.52
Hz), respectively, suggesting that the M(CO)3 group in
6e and 6f,30 in addition to 6d and iso-6d, may undergo
Acknowledgment. The authors thank JSPS and RS
for a fellowship (to S.Y.).
Supporting Information Available: Tables giving full
crystallographic details, positional and thermal parameters,
and bond distances and angles for 2, iso-3, 5a, iso-6d, and
6f. This material is available free of charge via the Internet
at http://pubs.acs.org.
OM0492754