Unusual reactions of cationic carbyne complexes of manganese and rhenium with the carbonylmetal anions [Ir(CO)4]- and [Ru(CO) 4]2-. Novel route to heteropolymetallic bridging carbyne complexes

Article abstract of DOI:10.1021/om058008a

The reaction of a cationic carbyne complex of manganese, [(η⁵-C₅H₅)(CO)₂Mn≡CC ₆H₅]BBr₄ (1), with [(Ph₃P) ₂N] [Ir(CO)₄] (3) in THF at low temperature gives a novel Mn₂-Ir₂ mixed-tetrametal bridging carbyne complex with μ and μ₃ bridging carbyne ligands, [Mn₂Ir ₂(μ-CC₆H₅)(μ₃-CC ₆H₅)(μ-CO)₃(CO)₃(n ⁵-C₅H₅)₂] (5), and a related Mn ₂-Ir₂ mixed-tetranuclear cluster with a μ bridging carbene ligand and a μ₃ bridging carbyne ligand, [Mn ₂Ir₂{μ-C(CO)-C₆H₅} (μ₃-CC₆H₅)(μ-CO)₃(CO) ₄(η⁵-C₅H₅)₂] (6). A cationic carbyne complex of rhenium, [(η⁵-C₅H ₅)(CO)₂Re≡CC₆H₅]BBr ₄ (2), reacts similarly with 3 to afford the corresponding Re ₂-Ir₂ mixed-tetrametal cluster [Re₂Ir ₂{μ-C(CO)C₆H₅}(μ3-CC₆H ₅)(μ-CO)₃(CO)₄(η⁵-C ₅H₅)₂] (8) and a novel Re-Ir₂ mixed-trimetal bridging carbyne complex with an allyl ligand, [ReIr ₂(μ-η¹:η²-C₃H ₅)(μ₃-CC₆H₅)(μ-CO) ₂(CO)₄(η⁵-C₅H₅)] (7). The cationic carbyne complex 1 also reacts with the anionic compound Na ₂[Ru(CO)₄] (4) to give a heterotrimetal bridging carbyne complex with a μ-H ligand, [MnRu₂-(μ-H)(μ-CO) ₂(μ₃-CC₆H₅)(CO) ₆(η⁵-C₅H₅)] (10), and the manganese aminocarbene complex [(η⁵-C₅H ₅)(CO)₂Mn=C(C₆H₅)NH₂] (11), while the analogous reaction of the cationic carbyne complex 2 with 4 produces a novel Re₂-Ru₂ mixed-tetrametal cluster with a μ₃-C(CC₆H₅)(μ-CC₆H ₅) bridging carbene ligand, [Re₂Ru₂{μ ₃-C(CC₆H₅)(μ-CC₆H ₅)}(μ-CO)(CO)₈(η⁵-C₅H ₅)₂] (13), in addition to the corresponding heterotrimetal bridging carbyne complex [ReRu₂(μ₃-CC ₆H₅)(μ-H)(μ-CO)₂(CO)₆(η ⁵-C₅H₅)] (12) and aminocarbene complex [η⁵-C₅H₅(CO)₂Re=C(C ₆H₅)NH₂] (14). The structures of complexes 6, 7, 11, 13, and 14 have been established by X-ray diffraction studies.

Full text of DOI:10.1021/om058008a

Organometallics 2005, 24, 5807-5816
5807
Unusual Reactions of Cationic Carbyne Complexes of
Manganese and Rhenium with the Carbonylmetal Anions
[Ir(CO)4]- and [Ru(CO)4]2-. Novel Route to
Heteropolymetallic Bridging Carbyne Complexes
Lei Zhang,† Nu Xiao,† Qiang Xu,*,‡ Jie Sun,† and Jiabi Chen*,†
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, China, and National
Institute of Advanced Industrial Science and Technology (AIST), 1-8-31, Midorigaoka, Ikeda,
Osaka 563-8577, Japan
Received February 11, 2005
The reaction of a cationic carbyne complex of manganese, [(η5-C5H5)(CO)2MntCC6H5]BBr4
(1), with [(Ph3P)2N][Ir(CO)4] (3) in THF at low temperature gives a novel Mn2-Ir2 mixed-
tetrametal bridging carbyne complex with µ and µ3 bridging carbyne ligands, [Mn2Ir2(µ-
CC6H5)(µ3-CC6H5)(µ-CO)3(CO)3(η5-C5H5)2] (5), and a related Mn2-Ir2 mixed-tetranuclear
cluster with a µ bridging carbene ligand and a µ3 bridging carbyne ligand, [Mn2Ir2{µ-C(CO)-
C6H5}(µ3-CC6H5)(µ-CO)3(CO)4(η5-C5H5)2] (6). A cationic carbyne complex of rhenium, [(η5-
C5H5)(CO)2RetCC6H5]BBr4 (2), reacts similarly with 3 to afford the corresponding Re2-Ir2
mixed-tetrametal cluster [Re2Ir2{µ-C(CO)C6H5}(µ3-CC6H5)(µ-CO)3(CO)4(η5-C5H5)2] (8) and a
novel Re-Ir2 mixed-trimetal bridging carbyne complex with an allyl ligand, [ReIr2(µ-η1:η2-
C3H5)(µ3-CC6H5)(µ-CO)2(CO)4(η5-C5H5)] (7). The cationic carbyne complex 1 also reacts with
the anionic compound Na2[Ru(CO)4] (4) to give a heterotrimetal bridging carbyne complex
with a µ-H ligand, [MnRu2(µ-H)(µ-CO)2(µ3-CC6H5)(CO)6(η5-C5H5)] (10), and the manganese
aminocarbene complex [(η5-C5H5)(CO)2MndC(C6H5)NH2] (11), while the analogous reaction
of the cationic carbyne complex 2 with 4 produces a novel Re2-Ru2 mixed-tetrametal cluster
with a µ3-C(CC6H5)(µ-CC6H5) bridging carbene ligand, [Re2Ru2{µ3-C(CC6H5)(µ-CC6H5)}(µ-
CO)(CO)8(η5-C5H5)2] (13), in addition to the corresponding heterotrimetal bridging carbyne
complex [ReRu2(µ3-CC6H5)(µ-H)(µ-CO)2(CO)6(η5-C5H5)] (12) and aminocarbene complex [η5-
C5H5(CO)2RedC(C6H5)NH2] (14). The structures of complexes 6, 7, 11, 13, and 14 have been
established by X-ray diffraction studies.
Introduction
trimetal bridging carbene and carbyne complexes, which
were carried out by the reactions of the cationic metal
carbyne complexes with metal carbonyl anions, have
been developed in our laboratory. One of the synthetic
methods for trimetal bridging carbyne complexes is to
conduct reactions4,5 of highly electrophilic cationic car-
byne complexes of manganese and rhenium, [(η5-C5H5)-
(CO)2MtCC6H5]BBr4 (1, M ) Mn; 2, M ) Re), with di-
or polymetal carbonyl anions of group VIII such as [Fe2-
(µ-CO)(µ-SeC4H9-n)(CO)6]-, [M3(CO)11]2- (M ) Ru, Os),
and [Fe4(CO)13]-. Recently, in a communication6 we
reported an unusual approach to polymetallic bridging
carbyne complexes: the reactions of cationic carbyne
complexes of manganese and rhenium, 1 and 2, with
the monoanionic metal carbonyl compound [(Ph3P)2N]-
[Rh(CO)4] gave novel heteronuclear polymetal clusters
It is well-known that mixed-metal-bonded cluster
complexes play important roles in a variety of homoge-
neous catalytic reactions.1 Since many dinuclear and
polynuclear metal bridging carbene and carbyne com-
plexes, where the metal atoms are directly bonded to
each other, are themselves metal clusters or are the
precursors of metal cluster complexes, the chemistry of
transition-metal bridging carbene and carbyne com-
plexes is an area of current interest. The first hetero-
bimetallic carbyne complexes were synthesized by Fis-
cher’s group2 in the 1970s, and a considerable number
of heteronuclear di- and trimetal bridging carbyne
complexes have been synthesized by Stone and co-
workers.3 In recent years, several new routes to di- and
† Shanghai Institute of Organic Chemistry.
(3) (a) Stone, F. G. A. Pure Appl. Chem. 1986, 58, 529. (b) Busetto,
L.; Green, M.; Howard, J. A. K.; Hessner, B.; Jeffery, J. C.; Mills, R.
M.; Stone, F. G. A.; Woodward, P. J. Chem. Soc., Chem. Commun. 1981,
1101. (c) Busetto, L.; Jeffery, J. C.; Mills, R. M.; Stone, F. G. A.; Went,
M. J.; Woodward, P. J. Chem. Soc., Dalton Trans. 1984, 101. (d) Jeffery,
J. C.; Lewis, D. B.; Lewis, G. E.; Stone, F. G. A. J. Chem. Soc., Dalton
Trans. 1985, 2001.
(4) Chen, J.-B.; Wang, R.-T. Coord. Chem. Rev. 2002, 231, 109.
(5) (a) Wang, R.-T.; Xu, Q.; Souma, Y.; Song, L.-C.; Sun, J.; Chen,
J.-B. Organometallics 2001, 20, 2226. (b) Xiao, N.; Xu, Q.; Tsubota,
S.; Sun, J.; Chen, J.-B. Organometallics 2002, 21, 2764.
(6) Zhang, L.; Zhu, B.-H.; Xiao, N.; Xu, Q.; Tsumori, N.; Sun, J.;
Yin, Y.-Q.; Chen, J.-B.; Organometallics 2003, 22, 4369.
‡ National Institute of Advanced Industrial Science and Technology.
(1) (a) Norton, J. H. In Fundamental Research in Homogeneous
Catalysis; Tsutsui, M., Ugo, R., Eds.; Plenum Press: New York, 1977;
Vol. 1, p 99. (b) Suess-Fink, G.; Meister, G. Adv. Organomet. Chem.
1993, 35, 41. (c) Gladfelter, W. L.; Roesselet, K. J. In The Chemistry
of Metal Cluster Complexes; Shriver, D. F., Kaesz, H. D., Adams, R.
D., Eds.; VCH: Weinheim, Germany, 1990; p 392. (d) Braunstein, P.;
Rose, J. In Comprehensive Organometallic Chemistry, 2nd ed.; Abel,
E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford,
U.K., 1995; Vol. 10, Chapter 7, pp 351-385.
(2) Fischer, E. O.; Lindner, T. L.; Kreissl, F. R.; Braunstein, P. Chem.
Ber. 1977, 110, 3139.
10.1021/om058008a CCC: $30.25 © 2005 American Chemical Society
Publication on Web 10/26/2005

5808 Organometallics, Vol. 24, No. 24, 2005
Zhang et al.
prepared in a manner similar to that for [(η5-C5H5)(CO)2Red
C(OC2H5)C6H4CF3-p]9 from [(η5-C5Me5)Re(CO)3]. The com-
pounds [(Ph3P)2N][Ir(CO)4] (3)10 and Na2[Ru(CO)4] (4)11 were
prepared by literature methods.
with µ and a µ3 bridging carbyne ligands, A and B, and
the related polymetal cluster compound C or D (eq 1).
The IR spectra were measured on a Perkin-Elmer 983G
spectrophotometer. All 1H NMR and 13C NMR spectra were
recorded in acetone-d6 at ambient temperature with TMS as
the internal reference using a Bruker AM-300 spectrometer.
However, the 13C NMR spectra for all of the compounds were
not obtained, due to their sensitivity to temperature and/or
poor solubility. Electron ionization mass spectra (EIMS) were
run on a Hewlett-Packard 5989A spectrometer. Melting points
obtained on samples in sealed nitrogen-filled capillaries are
uncorrected.
Reaction of [(η5-C5H5)(CO)2MntCC6H5]BBr4 (1) with
[(Ph3P)2N][Ir(CO)4] (3) To Give [Mn2Ir2(µ-CC6H5)(µ3-
CC6H5)(µ-CO)3(CO)3(η5-C5H5)2] (5) and [Mn2Ir2{µ-C(CO)-
C6H5}(µ3-CC6H5)(µ-CO)3(CO)4(η5-C5H5)2] (6). To 0.52 g (0.87
mmol) of freshly prepared compound 1 dissolved in 60 mL of
THF previously cooled to -100 °C was added 0.75 g (0.89
mmol) of [(Ph3P)2N][Ir(CO)4] (3). The solution turned im-
mediately from blackish brown to brown. The reaction mixture
was stirred at -100 to -50 °C for 4 h, during which time the
brown solution turned dark purple. The resulting mixture was
evaporated to dryness under high vacuum at -50 to -45 °C,
and the dark purple residue was chromatographed on an
alumina (neutral, 100-200 mesh) column (1.6 × 15-25 cm)
at -25 °C with petroleum ether/CH2Cl2 (2:1) as the eluant.
The blue-green band which eluted first was collected, and then
a blackish band was eluted with petroleum ether/CH2Cl2/Et2O
(2:1:0.5). The solvents were removed from the above two
eluates under vacuum at -20 °C, and the residues were
recrystallized from petroleum ether/CH2Cl2 solution at -80 °C.
From the first fraction, 0.20 g (22%, based on 1) of dark red
crystals of 6 was obtained: mp 133-135 °C dec; IR (CH2Cl2)
ν(CO) 2077 (vs), 2027 (s), 2014 (sh), 1977 (m), 1941 (vs, br),-
1889 (s, br), 1835 (m), 1759 (w) cm-1; 1H NMR (CD3COCD3) δ
7.74-7.60 (m, 3H, C6H5), 7.46-7.44 (m, 2H, C6H5), 7.24-7.18
(m, 3H, C6H5), 7.16-7.00 (m, 2H, C6H5), 5.53 (m, 1H, CH2-
Cl2), 4.98 (s, 2H, C5H5), 4.87 (d, 2H, C5H5), 4.71(d, 3H, C5H5),
4.50 (d, 3H, C5H5); MS m/e 595 [MnIr2(CC6H5)(C5H5)]+, 506
[MnIr2(C5H5)]+, 204 [Mn(CO)3(C5H5)]+, 176 [Mn(CO)2(C5H5)]+,
148 [Mn(CO)(C5H5)]+, 84 (CH2Cl2+). Anal. Calcd for C32H20O8-
Mn2Ir2‚0.5CH2Cl2: C, 36.50; H, 1.93. Found: C, 36.14; H, 2.16.
From the second fraction, 0.45 g (56%, based on 1) of blackish
green cryatalline 5 was obtained: mp >250 °C dec; IR (CH2-
On the other hand, it was found that the different
metal carbonyl anions involving those of the same group
exhibit a different reactivity toward the cationic metal
carbyne complexes and their reactions give different
products.4,7 To develop this new synthetic method for
the preparation of polymetallic bridging carbyne com-
plexes and further examine the reactivity of different
carbonylmetal anions of group VIII toward the cationic
carbyne complexes and their reaction products, we
investigated the reactions of cationic carbyne complexes
1 and 2 with the monoanionic carbonyliridium com-
pound [(Ph3P)2N][Ir(CO)4] and the dianionic carbonyl-
ruthenium compound Na2[Ru(CO)4]. These reactions
yield a number of novel heteronuclear polymetallic
bridging carbyne complexes and related polymetallic
clusters or bridging carbene complexes. In this paper,
we report these unusual reactions and the structures
of the resulting products.
Cl2) ν(CO) 2041 (vs), 1994 (vs, br), 1803 (s, br), 1759 (m) cm-1
;
1H NMR (CD3COCD3) δ 7.62-7.59 (m, 2H, C6H5), 7.47-7.42
(m, 3H, C6H5), 7.21-7.16 (m, 3H, C6H5), 7.03-6.99 (m, 2H,
C6H5), 5.65 (m, 1H, CH2Cl2), 5.33 (s, 2H, C5H5), 5.24 (d, 2H,
C5H5), 4.67 (d, 3H, C5H5), 4.62 (d, 3H, C5H5); MS m/e 595
[MnIr2(CC6H5)(C5H5)]+, 571 [MnIr2(C5H5)2]+, 204 [Mn(CO)3-
(C5H5)]+, 176 [Mn(CO)2(C5H5)]+, 84 (CH2Cl2+). Anal. Calcd for
C30H20O6Mn2Ir2‚0.5CH2Cl2: C, 37.73; H, 2.18. Found: C, 37.70;
H, 2.39.
Experimental Section
All reactions were performed under a dry, oxygen-free N2
atmosphere using standard Schlenk techniques. All solvents
employed were of reagent grade and were dried by refluxing
over appropriate drying agents and stored over 4 Å molecular
sieves under N2. Tetrahydrofuran and diethyl ether were
distilled from sodium benzophenone ketyl, while petroleum
ether (30-60 °C) and CH2Cl2 were distilled from CaH2. Neutral
alumina (Al2O3) was deoxygenated under high vacuum for 16
h, deactivated with 5% w/w N2-saturated water, and stored
under N2. The compounds [(η5-C5Me5)Re(CO)3] and NaNH2
were purchased from Aldrich Chemical Co. The complexes [(η5-
C5H5)(CO)2MntCC6H5]BBr4 (1)8a and [(η5-C5H5)(CO)2Ret
CC6H5]BBr4 (2)8b were prepared as previously described.
The complex [(η5-C5Me5)(CO)2RetCC6H5]BBr4 (2-Cp*) was
prepared8 in a manner similar to that for complexes 1 and 2
from [(η5-C5Me5)(CO)2RedC(OC2H5)C6H5], which itself was
Reaction of [(η5-C5H5)(CO)2Re≡CC6H5]BBr4 (2) with 3
To Give [ReIr2(µ-η1:η2-C3H5)(µ3-CC6H5)(µ-CO)2(CO)4(η5-
C5H5)] (7) and [Re2Ir2{µ-C(CO)C6H5}(µ3CC6H5)(µ-CO)3-
(CO)4(η5-C5H5)2] (8). Similar to the procedures used in the
reaction of 1 with 3, freshly prepared compound 2 (0.63 g, 0.86
mmol) was treated with 3 (0.83 g, 0.98 mmol) at -100 to -50
°C for 4 h, during which time the dark green solution turned
brown. After removal of the solvent in vacuo at -50 to -45
°C, the dark brown residue was chromatographed on Al2O3 at
-25 °C with petroleum ether/CH2Cl2 (5:1) as the eluant. A
(9) Fischer, E. O.; Chen, J.-B.; Scherzer, K. J. Organomet. Chem.
1983, 253, 231.
(7) Tang, Y.-Y.; Sun, J.; Chen, J.-B. Organometallics 2000, 19, 72.
(8) (a) Fischer, E. O.; Meineke, E. W.; Kreissl, F. R. Chem. Ber. 1977,
110, 1140. (b) Fischer, E. O.; Chen, J.-B.; Scherzer, K. J. Organomet.
Chem. 1983, 253, 231.
(10) Garlaschelli, L.; Chini, P.; Martinengo, S. Gazz. Chim. Ital.
1982, 112, 285.
(11) Cotton, J. D.; Bruce, M. I.; Stone, F. G. A. J. Chem. Soc. A 1968,
2162.

Heteropolymetallic Bridging Carbyne Complexes
Organometallics, Vol. 24, No. 24, 2005 5809
yellow-green band was eluted first; then a blackish band was
eluted with petroleum ether/CH2Cl2 (4:1). The solvents were
removed from the above two eluates under vacuum, and the
residues were recrystallized from petroleum ether/CH2Cl2 at
-80 °C. From the first fraction, 0.055 g (22%, based on 2) of 7
as dark yellow crystals was obtained: mp 136-138 °C dec; IR
(CH2Cl2) ν(CO) 2046 (s), 2021 (s), 1985 (s), 1875 (m), 1829 (m)
cm-1; 1H NMR (CD3COCD3) δ 7.20 (m, 5H, C6H5), 5.54 (m, 1H,
CH2Cl2), 5.33 (s, 5H, C5H5), 4.75 (m, 1H, dCH), 3.07 (m, 2H,
dCH2), 1.66-1.61 (m, 2H, -CH2); MS m/e 849 [M+ - 4CO],
821 [M+ - 5CO], 793 [M+ - 6CO], 336 [Re(CO)3(C5H5)]+, 308
[Re(CO)2(C5H5)]+, 280 [Re(CO)(C5H5)]+, 252 [Re(C5H5)]+, 84
(CH2Cl2+), 41 (C3H5+). Anal. Calcd for C21H14O6ReIr2‚CH2Cl2:
C, 25.96; H, 1.58. Found: C, 25.97; H, 1.61. From the second
fraction, 0.251 g (41%, based on 2) of blackish red crystals of
8 was obtained: mp 135-138 °C dec; IR (CH2Cl2) ν(CO) 2068
(vs), 2029 (vs), 2016 (vs), 1996 (m), 1932 (m), 1863 (m), 1794
From the second fraction, 0.065 g (15%, based on 1) of orange-
yellow crystals of 11 was obtained: mp 84-86°C dec; IR (CH2-
1
Cl2) ν(CO) 1930 (vs), 1857 (vs) cm-1; H NMR (CD3COCD3) δ
9.43 (s, 1H, NH2), 8.88 (s, 1H, NH2), 7.34-7.06 (m, 5H, C6H5),
4.49 (s, 5H, C5H5); MS m/e, 281 (M+), 225 [M+ - 2CO]. Anal.
Calcd for C14H12O2NMn: C, 59.80; H, 4.30; N, 4.98. Found:
C, 60.06; H, 4.18; N, 4.89.
Reaction of 2 with 4 To Give [ReRu2(µ3-CC6H5)-
(µ-H)(µ-CO)2(CO)6(η5-C5H5)] (12), [Re2Ru2{µ3-C(CC6H5)-
(µ-CC6H5)}(µ-CO)(CO)8(η5-C5H5)2] (13), and [(η5-C5H5)-
(CO)2RedC(C6H5)NH2] (14). To freshly prepared 2 (0.94 g,
1.29 mmol) dissolved in 60 mL of THF at -100 °C was added
0.026 g (1.00 mmol) of 4. The reaction mixture was stirred at
-100 to -50 °C for 4 h, during which time the yellow solution
turned brown-red. The resulting mixture was evaporated to
dryness under vacuum at -45 to -40 °C, and the dark brown
residue was chromatographed on Al2O3 at -25 °C with
petroleum ether/CH2Cl2 (10:1) as the eluant. An orange-red
band which eluted first was collected, and then a red band
was eluted with petroleum ether/CH2Cl2 (5:1), A third orange-
yellow band was eluted with petroleum ether/CH2Cl2/Et2O (5:
1:0.5). The solvents were removed from the above three eluates
in vacuo at -20 °C, and the residues were recrystallized from
petroleum ether or petroleum ether/CH2Cl2 solution at -80
°C. From the first fraction, 0.154 g (40%, based on 2) of brown-
red crystals of 125b was obtained: mp 105-107 °C dec; IR (CH2-
Cl2) ν(CO) 2087 (m), 2065 (vs), 2023 (vs), 2000 (s), 1926 (m),
1
(w) cm-1; H NMR (CD3COCD3) δ 7.73-7.068 (m, 5H, C6H5),
5.54 (s, 5H, C5H5), 5.424 (s, 5H, C5H5); MS m/e 727 [ReIr2-
(CC6H5)(C5H5)]+, 638 [ReIr2(C5H5)]+, 336 [Re(CO)3(C5H5)]+, 308
[Re(CO)2(C5H5)]+, 280 [Re(CO)(C5H5)]+. Anal. Calcd for C30H20O6-
Re2Ir2: C, 29.81; H, 1.56. Found: C, 30.11; H, 1.35.
Reaction of [(η5-C5Me5)(CO)2Re≡CC6H5]BBr4 (2-Cp*)
with 3 To Give [Re2Ir2(µ-CC6H5)(µ3-CC6H5)(µ-CO)3(CO)3-
(η5-C5Me5)2] (9). To 0.59 g (0.75 mmol) of the complex [(η5-
C5Me5)(CO)2RetCC6H5]BBr4, freshly prepared (in situ) by the
reaction of [(η5-C5Me5)(CO)2RedC(OC2H5)C6H5] (0.40 g, 0.78
mmol) with BBr3 at -70 °C, dissolved in 60 mL of THF
previously cooled to -100 °C was added 0.63 g (0.75 mmol) of
3. The green-yellow solution was stirred at -100 to -90 °C
for 1 h; during this time no color change was observed. The
reaction mixture was warmed to -80 °C and stirred at -80 to
-50 °C for 4 h, during which time the green solution gradually
turned dark brown. The resulting mixture was evaporated to
dryness under high vacuum at -50 to -45 °C, and the dark
purple residue was chromatographed on Al2O3 at -25 °C with
petroleum ether/CH2Cl2 (5:1) as the eluant. A brown band was
eluted and collected. The solvent was removed, and the residue
was recrystallized from petroleum ether/CH2Cl2 solution at
-80 °C to give 0.53 g (52%, based on 2-Cp*) of blackish
cryatalline 9: mp 108-110 °C dec; IR (CH2Cl2) ν(CO) 2021
1870 (m) cm-1 1H NMR (CD3COCD3) δ 7.66-7.08 (m, 5H,
;
C6H5), 5.39 (s, 5H, C5H5), -17.47 (s, 1H, µ-H); MS m/e 336
[Re(CO)3(C5H5)]+, 308 [Re(CO)2(C5H5)]+, 280 [Re(CO)(C5H5)]+.
Anal. Calcd for C20H11O8ReRu2: C, 31.30; H, 1.45. Found: C,
31.41; H, 1.56. From the second fraction, 0.120 g (20%, based
on 2) of blackish red crystals of 13 was obtained: mp 80-82
°C dec; IR (CH2Cl2) ν(CO) 2076 (m), 2065 (m), 2021 (vs), 2009
(vs), 1983 (vs), 1949 (vs), 1928 (s), 1889 (m), 1872 (m) cm-1
;
1H NMR (CD3COCD3) δ 7.49-7.19 (m, 10H, 2C6H5), 5.39 (s,
10H, 2C5H5), 1.29-1.09 (m, 8H, CH3(CH2)4CH3), 0.86 (m, 6H,
CH3(CH2)4CH3); MS m/e 336 [Re(CO)3(C5H5)]+, 308 [Re(CO)2-
(C5H5)]+, 280 [Re(CO)(C5H5)]+, 86 (C6H14+). Anal. Calcd for
C34H20O9Re2Ru2‚C6H14: C, 38.96; H, 2.78. Found: C, 38.63;
H, 2.48. From the third fraction, 0.061 g (13%, based on 2) of
orange crystalline 14 was obtained: mp 128-130 °C dec; IR
(CH2Cl2) ν(CO) 1928 (vs), 1848 (vs) cm-1; 1H NMR (CD3COCD3)
δ 9.121 (m, 2H, NH2), 7.35-7.13 (m, 5H, C6H5), 5.11 (s, 5H,
C5H5); MS m/e 412 (M+), 384 [M+ - CO], 356 [M+ - 2CO].
Anal. Calcd for C14H12O2NRe: C, 40.77; H, 2.93; N, 3.40.
Found: C, 40.15; H, 3.02; N, 2.90.
1
(s), 2027 (s), 1972 (vs), 1765 (s), 1732 (m, br) cm-1; H NMR
(CD3COCD3) δ 7.40-7.03 (m, 10H, 2C6H5), 1.99 (s, 15H, C5-
Me5), 1.85 (m, 15H, C5Me5); MS m/e 406 [Re(CO)3(C5Me5)]+,
378 [Re(CO)2(C5Me5)]+, 350 [Re(CO)(C5Me5)]+. Anal. Calcd for
C40H40O6Re2Ir2: C, 34.96; H, 2.94. Found: C, 34.92; H, 3.26.
Reaction of 1 with Na2[Ru(CO)4] (4) To Give [MnRu2-
(µ3-CC6H5)(µ-H)(µ-CO)2(CO)6(η5-C5H5)] (10) and [(η5-C5H5)-
(CO)2MndC(C6H5)NH2] (11). To 0.90 g (1.51 mmol) of freshly
prepared compound 1 dissolved in 60 mL of THF previously
cooled to -100 °C was added 0.38 g (1.50 mmol) of Na2[Ru-
(CO)4] (4). The solution immediately turned from yellow-brown
to brown-red. The reaction mixture was stirred at -100 to -50
°C for 4 h, during which time the brown-red solution turned
dark brown. The resulting mixture was evaporated to dryness
under vacuum at -45 to -40 °C, and the dark brown residue
was chromatographed on alumina at -25 °C with petroleum
ether/CH2Cl2 (5:1) as the eluant. An orange-red band which
eluted first was collected, and then a yellow band was eluted
with petroleum ether/CH2Cl2/Et2O (5:1:0.5). The solvents were
removed from the above two eluates under vacuum at -25 °C,
and the residues were recrystallized from petroleum ether/
CH2Cl2 solution at -80 °C. From the first fraction, 0.27 g (47%,
based on 1) of brown-red cryatalline 105b was obtained: mp
144-146 °C dec; IR (CH2Cl2) ν(CO) 2092 (vs), 2071 (vs), 2031
(vs), 2004 (s), 1932 (m), 1839 (m) cm-1; 1H NMR (CD3COCD3)
δ 7.84-7.21 (m, 5H, C6H5), 4.68 (s, 5H, C5H5), -18.06 (s, 1H,
µ-H); MS m/e 492 [MnRu2(CO)6(C5H5)]+, 464 [MnRu2(CO)5-
(C5H5)]+, 436 [MnRu2(CO)4(C5H5)]+, 204 [Mn(CO)3(C5H5)]+, 176
[Mn(CO)2(C5H5)]+, 148 [Mn(CO)(C5H5)]+. Anal. Calcd for
C20H11O8MnRu2: C, 37.75; H, 1.74. Found: C, 37.31; H, 1.78.
Reaction of 1 with NaNH2 To Give 11. To 0.52 g (0.86
mmol) of freshly prepared 1 dissolved in 60 mL of THF
previously cooled to -100 °C was added 0.035 g (0.90 mmol)
of NaNH2. The solution turned immediately from yellow-brown
to red. The mixture was stirred at -100 to -50 °C for 5 h,
during which time the red solution turned dark red. The
resulting mixture was evaporated to dryness under vacuum
at -45 to -40 °C, and the dark residue was chromatographed
on Al2O3 at -25 °C with petroleum ether/CH2Cl2 (2:1) as the
eluant. An yellow band was eluted and collected. The solvent
was removed under vacuum, and the residue was recrystal-
lized from petroleum ether/CH2Cl2 solution at -80 °C to give
0.175 g (72%, based on 1) of yellow crystals of 11, which was
1
identified by its IR and H NMR spectra.
Reaction of 2 with NaNH2 To Give 14. To 0.39 g (0.54
mmol) of freshly prepared 2 dissolved in 60 mL of THF
previously cooled to -100 °C was added 0.023 g (0.59 mmol)
of NaNH2. The solution turned immediately from yellow to red.
The reaction mixture was stirred at -100 to -50 °C for 5 h,
during which time the red solution turned dark red. The
resulting mixture was evaporated to dryness under vacuum
at -45 to -40 °C, and the dark residue was chromatographed
on Al2O3 at -25 °C with petroleum ether/CH2Cl2 (2:1) as the
eluant. An orange-yellow band was eluted and collected. The
solvent was removed under vacuum, and the residue was

5810 Organometallics, Vol. 24, No. 24, 2005
Zhang et al.
carbyne complex of rhenium, [(η5-C5H5)(CO)2RetCC6H5]-
BBr4 (2), reacts similarly with the anionic carbonyliri-
dium compound 3 to afford the corresponding Re2-Ir2
mixed-tetrametal cluster [Re2Ir2{µ-C(CO)C6H5}(µ3-
CC6H5)(µ-CO)3(CO)4(η5-C5H5)2] (8) and a novel Re-Ir2
mixed-trimetal bridging carbyne complex with an allyl
ligand, [ReIr2(µ-η1:η2-C3H5)(µ3-CC6H5)(µ-CO)2(CO)4(η5-
C5H5)] (7), in 41 and 22% yields, respectively (eq 3),
among which the structure of 7 has been confirmed by
the X-ray diffraction study.
recrystallized from petroleum ether/CH2Cl2 solution at -80 °C
to give 0.172 g (78%, based on 2) of 14 as orange crystals, which
1
was identified by its IR and H NMR spectra.
X-ray Crystal Structure Determinations of Complexes
6, 7, 9, 11, 13, and 14. The single crystals of complexes 6, 7,
9, 11, 13, and 14 suitable for X-ray diffraction study were
obtained by recrystallization from petroleum ether, petroleum
ether/CH2Cl2, or petroleum ether/Et2O at -80 °C. Single
crystals were mounted on a glass fiber and sealed with epoxy
glue or placed in a sealed N2-filled capillary. The X-ray
diffraction intensity data of 6, 7, 9, 11, 13, and 14 were
collected with a Bruker Smart diffractometer at 20 °C using
Mo KR radiation with an ω-2θ scan mode.
The structures of 6, 7, 9, 11, 13, and 14 were solved by direct
methods and expanded using Fourier techniques. For the six
complexes, the non-hydrogen atoms were refined anisotropi-
cally and the hydrogen atoms were included but not refined.
The absorption corrections were applied using SADABS. The
final cycle of full-matrix least-squares refinement was based
on the observed reflections and the variable parameters and
converged with unweighted and weighted agreement to give
agreement factors of R ) 0.0665 and Rw ) 0.1430 for 6, R )
0.0796 and Rw ) 0.1976 for 7, R )0.0682 and Rw ) 0.1790 for
9, R ) 0.0516 and Rw ) 0.1238 for 11, R ) 0.0404 and Rw
0.0613 for 13, and R ) 0.0574 and Rw ) 0.1282 for 14.
)
Crystallographic data and details of the procedures used for
data collection and reduction information for 6, 7, 11, 13, and
14 are given in Table 1. Selected bond lengths and angles are
listed in Table 2 for 6, 7, and 13 and in Table 3 for 11 and 14.
The molecular structures of 6, 7, 11, 13, and 14 are given in
Complexes 5-8 are only soluble in polar organic
solvents such as CH2Cl2 and THF. They are very
sensitive to air and temperature in solution but rela-
tively stable in the solid state. Elemental analyses and
spectroscopic data are consistent with their composi-
tions and assigned structures. The infrared studies of
complexes 5-8 showed the presence of terminal and
bridging carbonyl groups, and the 1H NMR spectroscopic
data indicated the absence of hydride protons for
Figures 1-5, respectively. The atomic coordinates and Biso
/
Beq values, anisotropic displacement parameters, all bond
lengths and angles, and least-squares planes for 6, 7, 9, 11,
13, and 14 are given in the Supporting Information. Crystal-
lographic data and details of the procedures used for data
collection and reduction information for 9 (Table 4) and the
molecular structure of 9 (Figure 6) are also given in the
Supporting Information.
1
complexes 5-8. For complex 7, the H NMR spectrum
Results and Discussion
showed three unique resonances for the allyl ligand at
δ 4.75 (m, 1H, dCH-), 3.07 (m, 2H, dCH2), and 1.66-
1.61 (m, 2H, -CH2), in addition to the resonances for
the phenyl and cyclopentadienyl protons.
A cationic carbyne complex of manganese, [(η5-
C5H5)(CO)2MntCC6H5]BBr4 (1), was reacted with an
equimolecular amount of the anionic carbonyliridium
ionic compound [(Ph3P)2N][Ir(CO)4] (3) in THF at low
temperature (-100 to -50 °C) for 4-5 h. After removal
of the solvent under high vacuum, the residue was
chromatographed on an alumina column at -25 °C and
the crude products were recrystallized from petroleum
ether/CH2Cl2 at -80 °C to give a novel Mn2-Ir2 mixed-
tetrametal bridging carbyne complex with µ and a µ3
bridging carbyne ligands, [Mn2Ir2(µ-CC6H5)(µ3-CC6H5)-
(µ-CO)3(CO)3(η5-C5H5)2] (5), and a related Mn2-Ir2
mixed-tetranuclear cluster with a µ bridging carbene
ligand and a µ3 bridging carbyne ligand, [Mn2Ir2{µ-
C(CO)C6H5}(µ3-CC6H5)(µ-CO)3(CO)4(η5-C5H5)2] (6), in 56
and 22% isolated yields, respectively (eq 2). A cationic
The formulas of complexes 5 and 6 shown in eq 2 were
based on the elemental analyses and spectral data, and
the structure of 5 was established by comparison of its
IR, 1H NMR, and mass spectra with those of analogous
complexes A and B (eq 1), while the structure of 6 has
been further confirmed by a single-crystal X-ray dif-
fraction study. The results of the X-ray diffraction work
are summarized in Table 1, selected bond distances and
angles are given in Table 2, and the molecular structure
is shown in Figure 1.
The molecular structure of 6 revealed that the cluster
compound contains the bridging carbyne unit (µ3-
CC6H5)Mn(1)Ir(1)Ir(2) and the bridging carbene unit {µ-
C(CO)C6H5}Mn(2)Ir(2), in which the four metal atoms
of the tetrametal framework lie in different coordination
environments. In this cluster, the interactions between
ligands and metals and between metals and metals
provide different electron environments for the four
metal atoms. In the (µ3-CC6H5)Mn(1)Ir(1)Ir(2) portion,
the three metal atoms construct an approximately
isosceles triangle (Mn(1)-Ir(1) ) 2.694(3) Å, Mn(1)-Ir-
(2) ) 2.626(3) Å, Ir(1)-Ir(2) ) 2.7121(13) Å). The
µ-C(7)-Mn(1), µ-C(7)-Ir(1), and µ-C(7)-Ir(2) distances
are 1.996(19), 2.028(16), and 1.97(2) Å, respectively. In
the (µ-CC6H5)Mn(2)Ir(2) portion, the Mn(2)-Ir(2) bond

Heteropolymetallic Bridging Carbyne Complexes
Organometallics, Vol. 24, No. 24, 2005 5811
Table 1. Crystal Data and Experimental Details for Complexes 6, 7, 11, 13, and 14
6‚1.5CH2Cl2
7
11
13‚CH2Cl2
14
formula
formula wt
space group
a (Å)
C
33.5H23O8Cl3Mn2Ir2
C
21H15O6Ir2Re
C14H12O2NMn
281.19
C35H22O9Cl2Re2Ru2
1231.97
C
14H12O2NRe
1154.15
P21/n (No. 14)
11.336(2)
13.548(3)
23.138(5)
93.839(4)
3545.4(13)
4
933.93
412.45
P21/n (No. 14)
8.7448(8)
20.6234(19)
12.0056(11)
93.867(2)
2160.3(3)
4
Pn (No. 7)
6.0443(9)
10.6127(15)
9.8443(14)
98.527(3)
624.50(16)
2
P21/n (No.14)
9.2216(7)
33.276(3)
11.4992(9)
96.302(2)
3507.3(5)
4
P21/n (No. 14)
7.6652(8)
14.3918(15)
11.7411(12)
102.083(2)
1266.5(2)
4
b (Å)
c (Å)
â (deg)
V (Å3 )
Z
Dcalcd (g /cm3)
F(000)
2.162
2.872
1.495
2.333
2.163
2172
1672
288
2304
776
µ(Mo KR) (cm-1
radiation
diffractometer
temp (°C)
)
84.54
179.14
10.48
79.31
95.86
Mo KR (monochromated in incident beam; λ ) 0.710 73 Å)
Bruker Smart
20
20
20
20
20
orientation rflns:
4.636-55.575
5.069-47.153
5.679-39.048
4.609-46.146
4.538-46.088
range (2θ) (deg)
scan method
ω-2θ
3.48-51.00
6593
3137
412
ω-2θ
3.94-51.00
4027
2909
272
ω-2θ
3.84-55.00
2244
1623
163
ω-2θ
4.32-54.00
7628
4769
446
ω-2θ
data collecn range, 2θ (deg)
no. of unique data, total
no. of data with I >2.00σ(I)
no. of params refined
4.54-55.00
2860
2090
172
correction factors, max-min 0.71710-1.00000
0.37403-1.00000 0.66288-1.00000 0.38028-1.00000
0.51098-1.00000
0.0574
0.1282
0.912
Ra
Rw
0.0665
0.1430
0.866
0.0796
0.1976
0.971
0.0516
0.1238
0.979
0.0404
0.0613
0.728
b
quality of fit indicatorc
max shift/esd, final cycle
largest peak, e/Å3
0.031
0.042
0.000
0.001
0.082
2.123
5.029
0.489
1.301
3.051
smalles peak, e/Å3
-1.587
-2.960
-0.272
-0.974
-1.972
2
a R )∑||Fo| - |Fc||/∑|Fo|. b Rw ) [∑w(|Fo| - |Fc|)2/∑w|Fo| ]1/2; w ) 1/σ2(|Fo|). c Quality of fit ) [∑w(|Fo| - |Fc|)2/(Nobservns - Nparams)]1/2
.
is bridged by a C(CO)C6H5 ligand, giving a dimetalla-
cyclopropane ring with the following dimensions: Mn-
(2)-Ir(2) ) 2.565(3) Å, µ-C(10)-Mn(2) ) 2.07(2) Å, and
µ-C(10)-Ir(2) ) 2.06(2) Å. In this portion, a unique
feature of the structure is the presence of the C(26)O-
(8) group bonded to C(10) with a C(26)-O(8) distance
of 1.30(3) Å and a C(26)-C(10) distance of 1.32(3) Å.
The former distance might correspond either to a CdO
or to a CtO bond, and the latter distance suggests Cd
C double-bond character. Thus, the C(CO)C6H5 group
in 6 might be also regarded as a ketenyl ligand, C6H5Cd
CdO, across the metal-metal bond.12 Analogous struc-
tures were found in the complexes [MCo{µ-C(CO)C6H5}-
(CO)5(η5-C5H5)] (M ) Mn, Re),13 [MW{µ-C(CO)C6H5}-
(CO)4(η5-C5H5)2] (M ) Mn, Re),7 and [MCo{µ-C(CO)-
C6H5}(CO)4(η5-C5H5)2] (M ) Mn, Re).7 Evidently, as
shown by X-ray crystallography, complex 6 is a novel
cluster with a µ3 bridging carbyne unit and a bridging
carbene unit (or ketene species).
The structure of complex 8 was established by el-
emental analysis and by comparison of its IR, 1H NMR,
and mass spectra with those of the analogous product
6, while the structure of complex 7 was confirmed by a
single-crystal X-ray diffraction study, in addition to
elemental analysis and spectral analysis. The X-ray
results confirm the novel structure of 7 (Figure 2), which
has a triangular ReIr2 arrangement with a capping µ3-
CC6H5 ligand and an allyl ligand coordinated to the two
Ir atoms through the three carbon atoms. The three
metal atoms ReIr2 construct an approximate isosceles
triangle (Re(1)-Ir(1) ) 2.7906(11) Å, Re(1)-Ir(2) )
2.8062(11) Å, and Ir(1)-Ir(2) ) 2.6798(12) Å). Although
an analogous bridging carbyne complex with a trimet-
allatetrahedrane CReFe2 core, [ReFe2(µ-H)(µ-CO)2(µ3-
CC6H5)(CO)6(η5-C5H5)], has been prepared5b from cat-
ionic 2 and [(Ph3P)2N]2[Fe4(CO)13], no analogous bridging
carbyne complex with a CReIr2 core has been reported.
Only a W-Ir3 mixed-tetrametal cluster with a bridging
carbyne ligand, [WIr3(µ3-CPh){µ3-η4-C(Ph)C(Ph)C(Ph)C-
(Ph)}(µ-CPh)(CO)5(η5-C5H4Me)], is known.14 Complex 7
appears to be the first example of a species with Re-
Ir2 and Ir-Ir bonds studied by X-ray crystallography,
and hence, comparison of the Re-Ir and Ir-Ir bond
distances with others involving these elements is not
possible. The two Re-Ir bond lengths, 2.7906(11) and
2.8062(11) Å, respectively, are nearly the same. The Ir-
Ir bond length of 2.6798(22) Å in 7 is somewhat shorter
than that in the W-Ir3 mixed-tetrametal bridging
carbyne complex [WIr3(µ3-CPh){µ3-η4-C(Ph)C(Ph)C(Ph-
)C(Ph)}(µ-CPh)(CO)5(η5-C5H4Me)] (average 2.724 Å)14
but is significantly shorter than that in the related
triiridium cluster compound [NMe3(CH2Ph)][Ir3(µ-S)2-
(CO)6] (average 3.085 Å).15 The µ-C(7)-Re, µ-C(7)-Ir-
(1), and µ-C(7)-Ir(2) distances are 2.15(2), 2.09(2), and
2.064(19) Å, respectively, of which the µ-C(7)-Re bond
distance is close to that found in the related complexes
[ReFeCo(µ3-CC6H5)(µ-CO)2(CO)6(η5-C5H5)] (2.052(8) Å)13
and [ReFe2(µ-H)(µ-CO)2(µ3-CC6H5)(CO)5(PPh3)(η5-C5H5)]
2.092(7) Å),5b and the two µ-C(7)-Ir bond lengths are
nearly the same, both being shorter than those found
in [WIr3(µ3-CPh){µ3-η4-C(Ph)C(Ph)C(Ph)C(Ph)}(µ-CPh)-
(CO)5(η5-C5H4Me)] (µ-C(40)-Ir(1) ) µ-C(40)-Ir(2) )
2.15(1) Å).14
In complex 7, as anticipated from the 1H NMR
spectrum, an allyl group is coordinated to the Ir(1) and
Ir(2) atoms through the three carbon atoms, where the
C(19) and C(20) atoms are bonded to the Ir(1) atom in
(14) Notaras, E. G. A.; Lucas, N. T.; Blitz, J. P.; Humphrey, M. G.
J. Organomet. Chem. 2001, 631, 143.
(15) Pergola, R. D.; Garlaschelli, L. J. Chem. Soc., Dalton Trans.
1986, 2463.
(12) Martin-Gil, J.; Howard, J. A. K.; Navarro, R.; Stone, F. G. A.
J. Chem. Soc., Chem. Commun. 1979, 1168.
(13) Tang, Y.-J.; Sun, J.; Chen, J.-B. Organometallics 1998, 17, 2945.

5812 Organometallics, Vol. 24, No. 24, 2005
Zhang et al.
Table 2. Selected Bond Lengths (Å)a and Angles
(deg)a for Complexes 6, 7, and 13
6 (M ) Mn,
M′ ) Ir)
7 (M ) Re,
M′ ) Ir)
13 (M ) Re,
M′ ) Ru)
M(1)-M′(1)
M(1)-M′(2)
M′(1)-M′(2)
M(2)-M′(1)
M(2)-M′(2)
M(1)-C(1)
2.694(3)
2.626(3)
2.7121(13)
2.7906(11)
2.8062(11)
2.6798(12)
2.9115(8)
2.7705(8)
2.9157(7)
2.8305(7)
1.871(10)
1.889(10)
2.030(8)
2.115(6)
2.041(7)
2.310(7)
2.064(7)
2.203(7)
2.565(3)
1.80(2)
1.91(2)
1.88(2)
M(1)-C(2)
1.795(17)
1.92(2)
M(2)-C(4)
M(2)-C(10)
M(1)-C(7)
2.07(2)
1.996(19)
2.028(16)
1.97(2)
2.15(2)
M′(1)-C(7)
M′(2)-C(7)
M′(1)-C(10)
M′(2)-C(10)
M′(2)-C(4)
M′(1)-C(1)
M′(2)-C(2)
M′(1)-C(19)
M′(1)-C(20)
M′(2)-C(21)
C(26)-O(8)
C(7)-C(8)
2.09(2)
2.064(19)
2.06(2)
2.05(2)
2.046(8)
2.60(2)
2.50(2)
2.19(2)
2.51(3)
2.16(2)
Figure 1. Molecular structure of 6, showing the atom-
numbering scheme with 45% thermal ellipsoids. CH2Cl2
has been omitted for clarity.
1.30(3)
1.51(3)
1.47(3)
C(7)-C(11)
C(10)-C(11)
C(10)-C(29)
C(11)-C(23)
C(19)-C(20)
C(20)-C(21)
C(26)-C(10)
1.420(9)
1.410(9)
1.525(9)
1.500(9)
1.389(13)
1.328(13)
1.32(3)
1.48(3)
1.31(6)
1.51(5)
1.348(19)
M(1)-M′(1)-M′(2)
M(1)-M′(2)-M′(1)
M′(1)-M(1)-M′(2)
M(1)-M′(2)-M(2)
M(2)-M′(1)-M′(2)
M′(1)-M(2)-M′(2)
M(2)-M′(2)-M′(1)
M(1)-M′(1)-C(7)
M(1)-M′(2)-C(7)
M′(1)-M(1)-C(7)
M′(2)-M(1)-C(7)
M(1)-C(7)-M′(1)
M(1)-C(7)-M′(2)
M′(1)--M′(2)-C(7)
M′(2)-M′(1)-C(7)
M(2)-M′(1)-C(10)
M(2)-M′(2)-C(10)
M′(1)-M(2)-C(10)
M′(2)-M(2)-C(10)
M(2)-C(10)-M′(1)
M(2)-C(10)-M′(2)
M(2)-M′(2)-C(4)
M′(2)-M(2)-C(4)
M(2)-C(4)-M′(2)
M′(1)-C(7)-M′(2)
M(1)-C(1)-O(1)
M′(1)-C(1)-O(1)
M′(2)-C(1)-O(1)
M(1)-C(2)-O(2)
M′(2)-C(2)-O(2)
M(1)-C(7)-C(11)
C(7)-M′(1)-C(11)
M(2)-C(10)-C(11)
M′(1)-C(19)-C(20)
M′(1)-C(20)-C(19)
M′(1)-C(20)-C(21)
M′(2)-C(21)-C(20)
C(7)-C(11)-C(10)
C(19)-C(20)-C(21)
58.12(7)
60.60(7)
61.69(3)
61.10(3)
57.21(3)
91.77(2)
61.28(7)
143.51(10)
124.02(2)
59.64(2)
57.628(18)
62.730(19)
155.72(8)
47.5(5)
48.9(5)
48.5(5)
48.3(6)
84.1(6)
82.8(8)
48.2(5)
46.5(6)
49.7(6)
49.5(6)
47.9(5)
47.0(5)
82.4(7)
83.5(7)
50.2(5)
49.4(5)
44.52(19)
45.15(19)
139.3(3)
90.3(3)
54.75(19)
46.87(17)
46.26(17)
51.8(7)
51.3(7)
48.82(19)
153.9(3)
84.9(2)
76.8(8)
47.4(6)
52.1(6)
80.5(9)
85.3(7)
149(2)
Figure 2. Molecular structure of 7, showing the atom-
45.8(2)
46.3(2)
88.0(3)
78.4(2)
176.3(8)
numbering scheme with 45% thermal ellipsoids.
80.4(7)
165(2)
119(2)
an analogous diiridium complex with an η1:η3-allyl
group, [(η5-C5Me5)(PMe3)Ir(η1:η3-C3H4)Ir(η5-C5Me5)] (Ir-
(1)-C(1) ) 2.046(7) Å, Ir(2)-C(1) ) 2.139(6) Å, Ir(2)-
C(2) ) 2.107(7) Å, Ir(2)-C(3) ) 2.112(7) Å).16 The two
C-C bond lengths of the allyl ligand in 7 are very
different. C(20)-C(21) has a bond length of 1.51(5) Å,
which is a normal C-C single-bond distance and is
much longer than the corresponding C-C distance
found in the analogous diiridium complex [(η5-C5Me5)-
(PMe3)Ir(η1:η3-C3H4)Ir(η5-C5Me5)] (C(1)-C(2) ) 1.421-
(11) Å).16 The other is C(19)-C(20), with a bond length
of 1.31(6) Å, which is between the CdC and CtC
distances and is somewhat shorter than the correspond-
ing C-C distance in [(η5-C5Me5)(PMe3)Ir(η1:η3-C3H4)Ir(η5-
C5Me5)] (C(2)-C(3) ) 1.453(11) Å).16 The bond angle
C(19)-C(20)-C(21) ) 128(3)° in 7 is also much larger
123.9(17)
157.5(18)
162.6(18)
118.8(14)
174.6(8)
139.6(5)
36.2(2)
122.9(5)
88(2)
60.5(13)
106(2)
95.9(19)
118.1(6)
128(3)
a Estimated standard deviations in the least significant figure
are given in parentheses.
an η2 bonding mode and the C(21) atom is η1-bound to
the Ir(2) atom with bond lengths Ir(1)-C(19) ) 2.19(2)
Å, Ir(1)-C(20) ) 2.51(3) Å, and Ir(2)-C(21) ) 2.16(2)
Å, which are significantly longer than those found in
(16) McGhee, M. D.; Hollander, F. J.; Bergmann, R. G. J. Am. Chem.
Soc. 1988, 110, 8428.

Heteropolymetallic Bridging Carbyne Complexes
Organometallics, Vol. 24, No. 24, 2005 5813
Scheme 1
ligand in cationic 2, the pentamethylcyclopentadienyl
cationic carbyne complex [(η5-C5Me5)(CO)2RetCC6H5]-
BBr4 (2-Cp*) was prepared from [(η5-C5Me5)(CO)2Red
C(OC2H5)C6H5] and BBr3 and used for the reaction with
anion 3. Unfortunately, the reaction of cationic 2-Cp*
gave only a Re2-Ir2 mixed-tetrametal bridging carbyne
complex with µ and a µ3 bridging carbyne ligands, [Re2-
Ir2(µ-CC6H5)(µ3-CC6H5)(µ-CO)3(CO)3(η5-C5Me5)2] (9), a
pentamethylcyclopentadienyl analogue of complexes B
and 5, in 52% isolated yield (eq 4), instead of the
than the corresponding angle in [(η5-C5Me5)(PMe3)Ir-
(η1:η3-C3H4)Ir(η5-C5Me5)] (C(1)-C(2)-C(3) ) 117.5-
(7)°).16 These data indicate that the allyl ligand in 7 is
an η1:η2-C3H5 ligand rather than an η1:η3-C3H5 ligand.
The two Ir atoms each carry two terminal CO groups,
and the Re atom carries two CO groups, being semibridg-
ing to the two Ir atoms, respectively (Re(1)-C(1)-O(1)
) 165(2)°, Re(1)-C(1) ) 1.91(2) Å; Re(1)-C(2)-O(2) )
162.6(18)°, Re(1)-C(2) ) 1.88(2) Å). The semibridging
CO ligands reveal themselves in the IR spectrum with
expected Re-Ir2 mixed-trimetal bridging carbyne com-
plex with a trimethyl-substituted allyl ligand (C3H2Me3)
and the analogue of the Re2-Ir2 mixed-tetrametal
cluster 8. This might arise from the lower reactivity of
pentamethylcyclopentadienyl cationic carbyne complex
2-Cp*, as compared with that of cationic 2, due to the
electron-pushing action and steric hindrance of the
pentamethylcyclopentadienyl group in 2-Cp* leading to
a decrease in the electrophilicity of cationic 2-Cp*,
which is indeed the case. The reaction of cationic 2 with
anionic 3 can occur even below -100 °C, while the
reaction of cationic 2-Cp* occurred only over -80 °C (see
Experimental Section). Although the reaction (eq 4) does
not provide evidence for splitting of the pentamethyl-
cyclopentadienyl ligand in 2-Cp* to form a trimethyl-
substituted allyl ligand to result in the expected C3H2-
Me3-coordinated mixed-trimetal bridging carbyne com-
plex, an analogue of 7, it cannot exclude the possibility
of the cleavage of the cyclopentadienyl ligand in cationic
2 to form an allyl group in the reaction (eq 3), since
cationic 2 has higher reactivity toward anionic 3 than
does cationic 2-Cp*.
Since the cyclopentadienyl ligand (C5H5) in 2 does not
contains enough H atoms to account for a splitting
reaction to produce C2H2 and C3H5 units, the allyl group
(C3H5) in product 7 is hypothesized to be derived by
abstracting two H atoms from solvent THF. To prove
this hypothesis, CH2Cl2, instead of THF, was used as
the solvent for the reaction of cationic 2 with anionic 3
under the same conditions as those in THF, and no
product 7 was obtained. This provided evidence that the
two added H atoms of the allyl ligand in 7 could be from
the solvent THF. A 1H NMR tube reaction of cationic 2
with anionic 3 in THF-d8 was also attempted. Unfor-
tunately, no deuterium atoms of the allyl ligand in
product 7 can be recognized from the complex 1H NMR
spectrum, since the reaction products were a mixture
and the deuterated product 7, a minor product, was
hardly formed. Thus, there is not sufficient evidence to
establish the origin of the two H- of the C3H5 ligand in
product 7 at present.
a strong and a broad band at 1875 and 1829 cm-1
.
Compound 7 is a 48-CVE (cluster valence electron)
complex, where the Re (1), Ir(1), and Ir(2) atoms
formally have 19, 18, and 17 electrons, respectively,
which probably accounts for the presence of the
semibridging carbonyls and a bridging allyl group.
Analogous 48-valence-electron structures were found in
the complexes [MW2(µ3-C2R2)(CO)7(η5-C5H5)] (M ) Ru,
Os),17 [ReFeCo(µ3-CC6H5)(CO)8(η5-C5H5)],13 [MnFe2(µ-
H)(µ-CO)2(µ3-CC6H5)(CO)6(η5-C5H5)],5a and [MnRu2(µ-
H)(µ-CO)2(µ3-CC6H5)(CO)6(η5-C5H5)].5b
The formation of product 7 is unexpected. The origin
of the allyl group (C3H5) in this product could be the
cyclopentadienyl ligand (C5H5) of the cationic carbyne
complex 2. During the reaction of 2 with carbonylmetal
anion 3, two carbon-carbon bonds of the cyclopentadi-
enyl ligand were cleaved and torn into two pieces, a two-
carbon unit (C2H2) and a three-carbon unit (C3H3). The
three CH moieties were trapped by cationic 2 and/or
anionic 3 accompanied by the abstraction of two hydro-
gens from solvent THF to form an allyl ligand bonded
to the Ir(1) and Ir(2) atoms in η2 and η1 modes,
respectively, to construct the trimetal bridging carbyne
complex 7. Indeed, the transfer of a three-carbon unit
from a cyclopentadienyl ligand to a complex has been
documented: the reaction of titanacyclopentadiene (I)
with 2 equiv of PhCN in THF at reflux for 1 h resulted
in the formation of 1,2,3,4-tetraethylbenzene (II) and
2,6-diphenylpyridine (III), which were formed by re-
spectively trapping a two-carbon unit and a three-
carbon unit generated from cleavage of the two C-C
bonds of a cyclopentadienyl ligand (Scheme 1).18
To explore the possibility of the allyl group (C3H5) in
product 7 forming on cleavage of the cyclopentadienyl
(17) Busetto, L.; Green, M.; Howard, J. A. K.; Hessner, B.; Jeffery,
J. C.; Mills, R. M.; Stone, F. G. A.; Woodward, P. J. Chem. Soc., Chem.
Commun. 1981, 1101.
(18) Xi, Z.-F.; Sato, K.; Gao, Ye.; Lu, J.-M.; Takahashi, T. J. Am.
Chem. Soc. 2003, 125, 9568.

5814 Organometallics, Vol. 24, No. 24, 2005
Zhang et al.
Table 3. Selected Bond Lengths (Å)a and Angles
(deg)a for Complexes 11 and 14
Although several di- and polynuclear metal complexes
with an η1:η3-allyl ligand have been reported,16,19 only
a dinuclear metal compound with an η1:η2-allyl ligand,
[(η5-C5Me5)Ir(η1:η2-C3H5)(η2:η1-C2H3)Ir(η5-C5Me5)], is
known.16 Evidently, compound 7 is the first example of
a polymetallic bridging carbyne complex with an allyl
ligand.
In contrast to the reaction of the carbonyliridium
anion 3 to give the mixed-tetrametal bridging carbyne
complexes or mixed-trimetal bridging carbyne com-
plexes with an allyl ligand, the reaction of the dianionic
carbonylruthenium compound Na2[Ru(CO)4] (4) with
cationic 1 under the same conditions as for 3 yields a
mixed-trimetal bridging carbyne complex with a µ-H
ligand, [MnRu2(µ-H)(µ-CO)2(µ3-CC6H5)(CO)6(η5-C5H5)]
(10), and a manganese aminocarbene complex, [η5-
C5H5(CO)2MndC(C6H5)NH2] (11) (eq 5), in 47 and 15%
11 (M ) Mn)
14 (M ) Re)
M-C(1)
1.729(8)
1.735(9)
1.938(8)
1.312(9)
1.465(9)
2.146
1.880(11)
1.896(11)
2.042(10)
1.313(14)
1.509(14)
2.307
M-C(2)
M-C(8)
C(8)-N(1)
C(8)-C(9)
M-C(Cp) (av)
C(1)-O(1)
C(2)-O(2)
1.183(9)
1.184(11)
1.171(13)
1.162(12)
M-C(8)-N(1)
M-C(8)-C(9)
N(1)-C(8)-C(9)
M-C(1)-O(1)
M-C(2)-O(2)
125.4(5)
122.6(5)
112.0(6)
176.0(8)
175.5(8)
127.9(9)
121.3(7)
110.2(9)
178.2(9)
177.1(9)
a Estimated standard deviations in the least significant figure
are given in parentheses.
yields, respectively. The analogous reaction of 4 with
cationic 2 produces the analogous trimetal bridging
carbyne complex [ReRu2(µ3-CC6H5)(µ-H)(µ-CO)2(CO)6-
(η5-C5H5)] (12) and aminocarbene complex [(η5-C5H5)-
(CO)2RedC(C6H5)NH2] (14) and a novel Re2-Ru2 mixed-
tetrametal cluster with a µ3-C(CC6H5)(µ-CC6H5) carbene
ligand, [Re2Ru2{µ3-C(CC6H5)(µ-CC6H5)}(µ-CO)(CO)8(η5-
C5H5)2] (13), in 40, 13, and 20% yields, respectively (eq
6).
Figure 3. Molecular structure of 11, showing the atom-
numbering scheme with 40% thermal ellipsoids.
Products 10 and 12 are known compounds, which
have been obtained from the reactions of [(PPh3)2N][Ru3-
(CO)11] with the cationic carbine complexes 1 and 2,
respectively, among which product 10 has been struc-
turally characterized by X-ray crystallography.5b The
formulas of products 11, 13, and 14 were established
by microanalytical data and IR, 1H NMR, and mass
spectra (Experimental Section), as well as X-ray crystal-
lography.
Although several Fischer-type carbene complexes of
chromium with an amino NH2 group on the carbene
carbon have been synthesized by Fischer et al.,20 none
of them have been studied by X-ray diffraction, and no
aminocarbene complex of manganese or rhenium has
ever been reported. Therefore, single-crystal X-ray dif-
fraction studies were carried out on complexes 11 and
14 for comparison with analogous aminocarbene com-
plexes. The results are given in Tables 1 and 3, and the
molecules are illustrated in Figures 3 and 4, respec-
tively.
The complexes 11 and 14 have the same molecular
configurations as shown in Figures 3 and 4, respectively,
and have many common features. In molecules 11 and
14, the M-C(8)carbene distances are 1.938(8) and 2.042-
(10) Å, respectively, which are shorter than those found
in the analogous aminocarbene complexes [(CO)5Crd
C(OC2H5)N(CH3)2] (2.133(4) Å)21 and [(CO)5CrdC(CH3)N-
(19) (a) McGhee, M. D.; Bergmann, R. G. J. Am. Chem. Soc. 1986,
108, 5621. (b) Michaell, B.; Michaell, W. J. Organomet. Chem. 1985,
288, C55. (c) Housecroft, C. E.; Johnson, B. F. G.; Lewis, J.; Lunniss,
J. A.; Owen, S. M.; Raithby, P. R. J. Organomet. Chem. 1991, 409,
271. (d) Chihara, T.; Yamazaki, H. J. Organomet. Chem. 1992, 428,
169. (e) Chihara, T.; Yamazaki, H. J. Chem. Soc., Dalton Trans. 1995,
1369. (f) Chihara, T.; Kubota, H.; Fukumoto, M.; Orgawa, H.; Yama-
moto, Y.; Wakatsuki, Y. Inorg. Chem. 1997, 36, 5488.
(20) (a) Fischer, E. O.; Kollmeier, H. J. Chem. Ber. 1971, 104, 1339.
(b) Knauss, L.; Fischer, E. O. J. Organomet. Chem. 1971, 31, C68.

Heteropolymetallic Bridging Carbyne Complexes
Organometallics, Vol. 24, No. 24, 2005 5815
Figure 4. Molecular structure of 14, showing the atom-
numbering scheme with 40% thermal ellipsoids.
Figure 5. Molecular structure of 13, showing the atom-
numbering scheme with 45% thermal ellipsoids. CH2Cl2
has been omitted for clarity.
(C2H5)2] (2.16(1) Å).22 The C(8)-N(1) bond lengths of 11
(1.312(9) Å) and 14 (1.313(19) Å) are the same within
experimental error, which are somewhat shorter than
the corresponding distance in [(CO)5CrdC(OC2H5)N-
(CH3)2] (1.328(4) Å).21 The M-C(8)-N(1) bond angles
of 125.4(5)° for 11 and of 127.9(9)° for 14 are much
smaller than the corresponding angle (129.4(1)°)22 in
[(CO)5CrdC(CH3)N(C2H5)2]. The carbene carbon atom
(C(8)) is coplanar with the benzene ring in both com-
plexes. The M, C(8), N(1), and C(9) atoms in 11 and 14
lie approximately in one plane, and the dihedral angles
between this plane and the benzene ring plane in 11
and 14 are 67.62 and 57.92°, respectively. The plane of
the cyclopentadienyl ring is inclined at an angle of
16.53° for 11 and of 17.98° for 14 to the plane of the
benzene ring.
Of special interest is the structure of product 13. The
crystallographic investigation of 13 reveals a highly
unusual structure (Figure 5), which contains a butterfly-
like Re2Ru2 arrangement with a capping µ3-C(CC6H5)-
(µ-CC6H5) ligand. The µ3-C(7) atom is at a distance of
2.041(7) Å from the Re(1) atom, at distances of 2.310(7)
and 2.064(7) Å from the Ru(1) and Ru(2) atoms, respec-
tively, and at a distance of 1.420(9) Å from the C(11)
atom. The structural features of the (µ-CC6H5)Re(2)Ru-
(1) portion in 13 are very similar to those of the same
unit in 6, except the µ-carbene carbon is linked to a
carbon (C(11)) atom in the former but to a bridging CO
group in the latter. In the (µ-CC6H5)Re(2)Ru(1) portion,
the Re(2)-Ru(1) bond is bridged by a µ-C(C6H5)(µ3-
CCC6H5) ligand with the dimensions Re(2)-Ru(1) )
2.9157(7) Å, µ-C(10)-Re(2) ) 2.115(6) Å, and µ-C(10)-
Ru(1) ) 2.203(7) Å. In this portion, a more interesting
feature is the bonding of the µ-carbene carbon (C(10))
to a carbon atom (C(11)) of the µ3-C(CC6H5) moiety with
a C(10)-C(11) distance of 1.410(9) Å. The shorter
C(10)-C(11) and C(7)-C(11) bond distances in the µ3-
C(CC6H5)(µ-CC6H5) moiety indicate that there is some
double-bond character for both C-C bonds and that the
C(7), C(11), and C(10) three carbon atoms are η3-bound
to the Ru(1) atom.
Complexes 10 and 12 could be produced via a
[Ru2(CO)6H]- species generated from a dimerization of
the dianion [Ru(CO)4]2-. The formed [Ru2(CO)6H]-
anion then becomes bonded to the carbyne carbon of
cationic 1 or 2 through the two Ru atoms with bonding
of the Mn or Re atom to the two Ru atoms to give com-
plex 10 or 12. This reaction pathway is rather analogous
to that of the reactions5 of [M′3(CO)11]2- (M′ ) Ru, Os)
and [Fe2(µ-CO)(µ-SeC4H9-n)(CO)6]- anions with com-
plex 1 or 2. Those reactions were assumed to proceed
via a [M′2(CO)6H]- (M′ ) Ru, Os) and [Fe2(CO)6H]-
species, respectively, which attacked at the carbyne
carbon of cationic 1 or 2 to afford the bridging carbyne
complexes [MM′2(µ-H)(µ-CO)2(µ3-CC6H5)(CO)6(η5-C5H5)]
(M ) Mn, Re; M′ ) Ru, Os)5b and [MFe2(µ-H)(µ-CO)2-
(µ3-CC6H5)(CO)6(η5-C5H5)] (M ) Mn),5a respectively.
Since [Ru(CO)4]2- is a dianion, its protonation could give
the [Ru(CO)4H]- anion in the presence of water, which
is a trace contaminant in the solvent THF or from
glassware. The formed [Ru(CO)4H]- anion could be the
species responsible for the origin of H- in these reac-
tions. Thus, the heteronuclear trimetal bridging carbyne
complexes [MRu2(µ-H)(µ-CO)2(µ3-CC6H5)(CO)6(η5-C5H5)]
(M ) Mn, Re) can be obtained not only from the
trimetallic carbonylruthenium anion5b but also from the
monometallic carbonylruthenium anion by reactions
with cationic carbyne complexes 1 and 2.
The route for the formation of product 13 is not clear.
We speculate that it could proceed via a [Ru2(CO)6]2-
species, derived by dimerization of the [Ru(CO)4]2-
dianion, which might become bonded to the carbyne
carbons of two molecules of cationic 2 through the two
Ru atoms to form the unstable dicarbene intermediate
[{(η5-C5H5)(CO)2RedCC6H5}2{Ru2(CO)6}]. Then the link-
age of the two Ru atoms to the two Re atoms, ac-
companied by an insertion of a CO ligand of a Ru(CO)3
moiety into the Re-µ-C bridging carbene bond (Re(1)-
µ-C(11)), occurred to the intermediate owing to its
lability. Subsequently, the reduction-elimination of the
oxygen atom from the inserted CdO group with the
bonding of the Ru(1) atom of another Ru(CO)3 moiety
to the carbonyl carbon (C(7)) and the µ-carbene carbon
(21) Fischer, E. O.; Winkler, E.; Kreiter, C. G.; Huttner, G.; Krieg,
B. Angew. Chem. 1971, 83, 1021; Engl. Ed. 1971, 10, 922.
(22) Connor, J. A.; Mills, O. S. J. Chem. Soc. A 1969, 334.

5816 Organometallics, Vol. 24, No. 24, 2005
Zhang et al.
(C(10)) to the C(11) atom could occur to eventually
produce product 13. However, the reaction pathway to
aminocarbene complexes 11 and 14, which are undes-
[Ir(CO)4]-, the products were novel polymetallic bridging
carbyne complexes with µ and µ3 bridging carbyne
ligands, with a µ3 bridging carbyne ligand and a µ
bridging carbene ligand, or with a µ3 bridging carbyne
ligand and an allyl ligand, while in the case of
[Ru(CO)4]2-, the major products were the trimetal
carbyne complexes with a µ-H ligand or a novel Re2-
Ru2 mixed-tetrametal cluster with a µ3-C(CC6H5)(µ-
CC6H5) bridging carbene ligand. These results demon-
strate the variety of the reactions of the cationic carbyne
complexes with carbonylmetal anions. The title reaction
may offer a convenient and useful method for the
preparation of heteronuclear polymetallic bridging car-
byne complexes.
-
ired byproducts, could be via a direct attack of NH2
anion at the carbyne carbon of cationic 1 or 2. The
-
source of the NH2 anion would be NaNH2, which is a
contaminant in the starting Na2[Ru(CO)4] obtained11
from Ru3(CO)12 and NaNH2 prepared (in situ) by the
reaction of ammonia and sodium and is difficult to
remove from the starting Na2[Ru(CO)4]. This has been
confirmed by the experimental fact that when NaNH2
was reacted with cationic carbyne complexes 1 and 2
under the same conditions as those of 4, the products
11 and 14 were obtained (eq 7) in 72 and 78% yields,
respectively.
Acknowledgment. We thank the National Natural
Science Foundation of China, the Science Foundation
of the Chinese Academy of Sciences, and the JSPS of
Japan for financial support of this research.
Supporting Information Available: Tables of the posi-
tional parameters and Biso/Beq values, H atom coordinates,
anisotropic displacement parameters, complete bond lengths
and angles, and least-squares planes for 6, 7, 9, 11, 13, and
14 and a figure giving the molecular structure for 9 (Figure
6). This material is available free of charge via the Internet
at http://pubs.acs.org.
In conclusion, we have discovered the remarkable
reactions of cationic carbyne complexes 1 and 2 with
the carbonyliridium monoanion [Ir(CO)4]- and carbon-
ylruthenium dianion [Ru(CO)4]2-. In the reactions of
OM058008A