Novel reactions of cationic carbyne complexes of manganese and rhenium with polymetal carbonyl anions. An approach to trimetal bridging carbyne complexes

Article abstract of DOI:10.1021/om0201359

The reaction of a cationic carbyne complex of manganese, [(η-C₅H₅)(CO)₂Mn≡CC₆H ₅]BBr₄ (1), with [(Ph₃P)₂N]₂[Ru₃(CO)₁₁] (3) in THF at low temperature gave the heteronuclear trimetal bridging carbyne complex [MnRu₂(μ-H)(μ-CO)₂(μ₃-CC₆H ₅)(CO)₆(η-C₅H₅)] (7). A cationic carbyne complex of rhenium, [(η-C₅H₅)(CO)₂Re≡CC₆H ₅]BBr₄ (2), reacts similarly with 3, affording the corresponding bridging carbyne complex [ReRu₂(μ-H)(μ-CO)₂(μ₃-CC₆H ₅)(CO)₆(η-C₅H₅)] (8) and neutral Re-carbyne dimer [Re(CO)₂(η-C₅H₅)(μ-CC₆H₅ )]₂ (9). The compound [(Ph₃P)₂N]₂[Os₃(CO)₁₁] (4) only reacts with 1 to give the trimetal bridging carbyne complex [MnOs₂(μ-H)(μ-CO)₂(μ₃-CC₆H ₅)(CO)₆(η-C₅H₅)] (10) and neutral Mn-carbyne dimer [Mn(CO)₂(η-C₅H₅)(μ-CC₆H₅ )]₂ (11). [(Ph₃P)₂N]₂[Fe₄(CO)₁₃] (5) also reacts with cationic carbyne complexes 1 and 2 to give the trimetal bridging carbyne complexes [MnFe₂(μ-H)(μ-CO)₂(μ₃CC₆H ₅)(CO)₆(η-C₅H₅)] (12) and [ReFe₂(μ-H)(μ-CO)₂(μ₃-CC₆H ₅)(CO)₆(η-C₅H₅)] (13), respectively. Product 13, when treated with an excess of PPh₃, gave the PPh₃-substituted bridging carbyne complex [ReFe₂(μ-H)(μ-CO)₂(μ₃-CC₆H ₅)(CO)₅(PPh₃)(η-C₅H₅) ] (14). In contrast to carbonylmetal anions 3-5, [Mo(η-C₅H₅)₂(H)CO][Mn₃(CO)₉ (μ-SC₆H₅)₄] (6) reacts with 1 to produce not the analogous bridging carbyne complexes but rather the mercapto-carbene complex [(ηC₅H₅)(CO)₂Mn=C(SC₆H₅ )C₆H₅] (15) and the thiolato-bridged Mo-Mn carbonyl complex [Mo(η-C₅H₅)(CO)₂(μ-SC₆H₅ )₂Mn(CO)₃] (16), while the analogous reaction of 2 with 6 yields the mercaptocarbene complex [(η-C₅H₅)(CO)₂Re=C(SC₆H₅ )C₆H₅] (17) and phenylcarbene complex [(η-C₅H₅)(CO)₂Re=C(H)C₆H₅ ] (18). The structures of 7, 9, 13, 14, and 16 have been established by X-ray diffraction studies.

Full text of DOI:10.1021/om0201359

2764
Organometallics 2002, 21, 2764-2772
Novel Rea ction s of Ca tion ic Ca r byn e Com p lexes of
Ma n ga n ese a n d Rh en iu m w ith P olym eta l Ca r bon yl
An ion s. An Ap p r oa ch to Tr im eta l Br id gin g Ca r byn e
Com p lexes†
Nu Xiao,‡ Qiang Xu,*,§ Susumu Tsubota,§ J ie Sun,‡ and J iabi 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, J apan
Received February 19, 2002
The reaction of a cationic carbyne complex of manganese, [(η-C5H5)(CO)2MntCC6H5]BBr4
(1), with [(Ph3P)2N]2[Ru3(CO)11] (3) in THF at low temperature gave the heteronuclear
trimetal bridging carbyne complex [MnRu2(µ-H)(µ-CO)2(µ3-CC6H5)(CO)6(η-C5H5)] (7). A
cationic carbyne complex of rhenium, [(η-C5H5)(CO)2RetCC6H5]BBr4 (2), reacts similarly
with 3, affording the corresponding bridging carbyne complex [ReRu2(µ-H)(µ-CO)2(µ3-CC6H5)-
(CO)6(η-C5H5)] (8) and neutral Re-carbyne dimer [Re(CO)2(η-C5H5)(µ-CC6H5)]2 (9). The
compound [(Ph3P)2N]2[Os3(CO)11] (4) only reacts with 1 to give the trimetal bridging carbyne
complex [MnOs2(µ-H)(µ-CO)2(µ3-CC6H5)(CO)6(η-C5H5)] (10) and neutral Mn-carbyne dimer
[Mn(CO)2(η-C5H5)(µ-CC6H5)]2 (11). [(Ph3P)2N]2[Fe4(CO)13] (5) also reacts with cationic carbyne
complexes 1 and 2 to give the trimetal bridging carbyne complexes [MnFe2(µ-H)(µ-CO)2(µ3-
CC6H5)(CO)6(η-C5H5)] (12) and [ReFe2(µ-H)(µ-CO)2(µ3-CC6H5)(CO)6(η-C5H5)] (13), respectively.
Product 13, when treated with an excess of PPh3, gave the PPh3-substituted bridging carbyne
complex [ReFe2(µ-H)(µ-CO)2(µ3-CC6H5)(CO)5(PPh3)(η-C5H5)] (14). In contrast to carbonylmetal
anions 3-5, [Mo(η-C5H5)2(H)CO][Mn3(CO)9(µ-SC6H5)4] (6) reacts with 1 to produce not the
analogous bridging carbyne complexes but rather the mercapto-carbene complex [(η-
C5H5)(CO)2MndC(SC6H5)C6H5] (15) and the thiolato-bridged Mo-Mn carbonyl complex [Mo-
(η-C5H5)(CO)2(µ-SC6H5)2Mn(CO)3] (16), while the analogous reaction of 2 with 6 yields the
mercaptocarbene complex [(η-C5H5)(CO)2RedC(SC6H5)C6H5] (17) and phenylcarbene complex
[(η-C5H5)(CO)2RedC(H)C6H5] (18). The structures of 7, 9, 13, 14, and 16 have been established
by X-ray diffraction studies.
In tr od u ction
Stone and co-workers4,5 by reactions of carbene or
carbyne complexes with low-valent metal species or by
reactions of neutral or anionic carbyne complexes with
metal hydrides or cationic metal compounds, and sev-
eral trimetal bridging carbyne complexes have also been
synthesized4,5 by Stone et al. by reactions of alkylidyne
complexes, such as [W(tCC6H4Me-4)(CO)2(η-C5H5)],
with low-valent metal species. Recently, we have shown
a convenient method for the preparation of the bridging
carbene and carbyne complexes: the reactions6,7 of
highly electrophilic cationic carbyne complexes of man-
ganese and rhenium, [(η-C5H5)(CO)2MtCC6H5]BBr4 (M
Our interest in the synthesis, structure, and chem-
istry of di- and polymetal bridging carbene and bridging
carbyne complexes stems from the fact that metal-
metal-bonded cluster complexes are well known to play
an important role in many catalytic reactions1-3 and
that many di- and polynuclear metal bridging carbene
and bridging carbyne complexes are themselves metal
clusters or the precursors of metal cluster complexes.
A considerable number of dimetal bridging carbene and
bridging carbyne complexes have been synthesized by
† Dedicated to Professor Robert J . Angelici on the occasion of his
65th birthday and in recognition of his brilliant contributions to
organometallic chemistry.
(4) Stone, F. G. A. In Advances in Metal Carbene Chemistry;
Schubert, U., Ed.; Kluwer Academic: Dordrecht, The Netherlands,
1989; p 11.
‡ Shanghai Institute of Organic Chemistry.
§ National Institute of Advanced Industrial Science and Technology.
(1) Su¨ss-Fink, G.; Meister, G. Adv. Organomet. Chem. 1993, 35, 41.
(2) (a) 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. (b) Maire, G. In Metal
Clusters in Catalysis; Gates, B. C., Guczi, L., Knoezinger, H., Eds.;
Elsevier: Amsterdam, The Netherlands, 1986; p 509. (c) Dickson, R.
S.; Greaves, B. C. Organometallics 1993, 12, 3249.
(5) Stone, F. G. A. Pure Appl. Chem. 1986, 58, 529.
(6) (a) Chen, J .-B.; Yu, Y.; Liu, K.; Wu, G.; Zheng, P.-J . Organome-
tallics 1993, 12, 1213. (b) Yu, Y.; Chen, J .-B.; Chen, J .; Zheng, P.-J . J .
Chem. Soc., Dalton Trans. 1996, 1443.
(7) (a) Tang, Y.-J .; Sun, J .; Chen, J .-B. Organometallics 1999, 18,
4337. (b) Tang, Y.-J .; Sun, J .; Chen, J .-B. J . Chem. Soc., Dalton Trans.
1998, 931. (c) Tang, Y.-J .; Sun, J .; Chen, J .-B. J . Chem. Soc., Dalton
Trans. 1998, 4003. (d) Tang, Y.-J .; Sun, J .; Chen, J .-B. Organometallics
1998, 17, 2945. (e) Tang, Y.-J .; Sun, J .; Chen, J .-B. Organometallics
2000, 19, 72. (f) Tang, Y.-J .; Sun, J .; Chen, J .-B. Organometallics 1999,
18, 2459.
(3) Sneeden, R. P. A. In Comprehensive Organometallic Chemistry;
Wilkinson, S. G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon Press:
Oxford, U.K., 1982; Vol. 8, p 50.
10.1021/om0201359 CCC: $22.00 © 2002 American Chemical Society
Publication on Web 05/25/2002

Cationic Carbyne Complexes of Mn and Re
Organometallics, Vol. 21, No. 13, 2002 2765
µ-H); MS m/e 294 [M+ - Ru2(CO)5] 204 [Mn(CO)3(C5H5)]+, 176
) Mn, Re), with mono- or dimetal carbonyl anions or
mixed-dimetal carbonyl anions.
[Mn(CO)2(C5H5)]+, 148 [Mn(CO)(C5H5)]+. Anal. Calcd for
C
20H11O8MnRu2: C, 37.75; H, 1.74. Found: C, 37.59; H, 2.00.
In a continuation of our interest in developing the
methodologies of the synthesis of transition-metal bridg-
ing carbene and carbyne complexes, we are now inter-
ested in developing a more convenient method for the
preparation of trimetal bridging carbyne complexes.
Thus, we carried out the study of the reactivity of tri-
and polymetalcarbonyl anions with highly electrophilic
cationic carbyne complexes of manganese and rhenium,
[(η-C5H5)(CO)2MtCC6H5]BBr4 (1, M ) Mn; 2, M ) Re).
These reactions have produced a series of new hetero-
nuclear trimetal bridging carbyne complexes. Herein we
describe these unusual reactions and the structures of
the resulting products.
Rea ction of [(η-C5H5)(CO)2RetCC6H5]BBr 4 (2) w ith 3
To Give [ReRu 2(µ-H)(µ-CO)2(µ3-CC6H5)(CO)6(η-C5H5)] (8)
a n d [Re(CO)2(η-C5H5)(µ-CC6H5)]2 (9). Similar to the proce-
dures used in the reaction of 1 with 3, freshly prepared
compound 2 (0.80 g, 1.10 mmol) was treated with 3 at -100
to -50 °C for 4 h, during which time the brown solution turned
dark brown-red. After removal of the solvent under vacuum
at -50 to -45 °C, the dark brown-red residue was chromato-
graphed on Al2O3 at -25 °C with petroleum ether/CH2Cl2 (5:
2) as the eluant. The brown-red band which eluted first was
collected, and then a deep red band was eluted with petroleum
ether/CH2Cl2 (2:1). The solvents were removed from the above
two eluates under vacuum, and the residues were recrystal-
lized from petroleum ether/CH2Cl2 at -80 °C. From the first
fraction, 0.201 g (48%, based on 2) of 8 as brown-red crystals
were obtained: mp 106-108 °C dec; IR (CH2Cl2) ν(CO) 2086
Exp er im en ta l Section
(m), 2062 (vs), 2022 (vs, br), 1999 (w), 1928 (m), 1868 (m) cm-1
;
All reactions were performed under a dry, oxygen-free N2
atmosphere using standard Schlenk techniques. All solvents
employed were of reagent grade and 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 complexes [(η-C5H5)(CO)2MntCC6H5]BBr4 (1)8 and [(η-
C5H5)(CO)2RetCC6H5]BBr4 (2)9 were prepared as previously
described.Thecompounds[(Ph3P)2N]2[Ru3(CO)11](3),10 [(Ph3P)2N]2-
[Os3(CO)11] (4),10 [(Ph3P)2N]2[Fe4(CO)13] (5),11 and [Mo(η-C5H5)2-
(H)CO][Mn3(CO)9(µ-SC6H5)4] (6)12 were all prepared by litera-
ture methods.
1H NMR (CD3COCD3) δ 7.62 (m, 2H, C6H5), 7.33 (m, 2H, C6H5),
7.08 (m, 1H, C6H5), 5.36 (s, 5H, C5H5), -17.52 (s, 1H, µ-H);
MS m/e 686 (M+ - 3CO), 500 [M+ - Ru(CO)3], 342 [M+ - Ru2-
(CO)5], 252 [Re(CO)(C5H5)]+. Anal. Calcd for C20H11O8ReRu2:
C, 31.30; H, 1.45. Found: C, 31.24; H, 1.66. From the second
fraction, 0.090 g (21%, based on 2) of blackish red crystalline
9 was obtained: mp 100-102 °C dec; IR (CH2Cl2) ν(CO) 1975
(s), 1943 (s) cm-1; 1H NMR (CD3COCD3) δ 7.79-7.32 (m, 10H,
C6H5), 5.09 (s, 10H, C5H5); MS m/e 794 (M+), 766 [M+ - CO],
682 [M+ - 4CO], 486 [M+ - 2CO - C5H5Re], 430 [M+ - 4CO
- C5H5Re], 336 [Re(CO)3(C5H5)]+, 252 [Re(CO)(C5H5)]+. Anal.
Calcd for C28H20O4Re2: C, 42.42; H, 2.54. Found: C, 42.08; H,
2.80.
Rea ction of 1 w ith [(P h 3P )2N]2[Os3(CO)11] (4) To Give
[Mn Os2(µ-H)(µ-CO)2(µ3-CC6H5)(CO)6(η-C5H5)] (10) an d [Mn -
(CO)2(η-C5H5)(µ-CC6H5)]2 (11). Compound 1 (0.60 g, 1.01
mmol) was treated, in a manner similar to that described above
for the reaction of 1 with 3, with [(Ph3P)2N]2[Os3(CO)11] (4; 1.02
g, 0.52 mmol) at -100 to -50 °C for 4 h, during which time
the brown-red solution turned brown-green. Further treatment
of the brown-green resulting solution similar to that described
in the reaction of 2 with 3 afforded 0.190 g (47%, based on 1)
of brown-red crystals of 10 and 0.064 g (24%, based on 1) of
11 as blackish red crystals. 10: mp 138-140 °C dec; IR (CH2-
Cl2) ν(CO) 2088 (s), 2061 (vs), 2022 (vs), 1990 (s), 1921 (m),
The IR spectra were measured on a Perkin-Elmer 983G
spectrophotometer. All 1H NMR spectra were recorded at
ambient temperature in acetone-d6 with TMS as the internal
reference using a Bruker AM-300 spectrometer. 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.
Rea ction of [(η-C5H5)(CO)2Mn tCC6H5]BBr 4 (1) w ith
[(P h 3P )2N]2[Ru 3(CO)11] (3) To Give [Mn Ru 2(µ-H)(µ-CO)2-
(µ3-CC6H5)(CO)6(η-C5H5)] (7). To 0.59 g (1.0 mmol) of freshly
prepared (in situ) compound 1 dissolved in 60 mL of THF
previously cooled to -100 °C was added 1.01 g (0.52 mmol) of
[(Ph3P)2N]2[Ru3(CO)11] (3). The solution turned immediately
from brown-red to dark brown. The reaction mixture was
stirred at -100 to -50 °C for 4 h, during which time the dark
brown solution turned dark brown-red. The resulting mixture
was evaporated to dryness under vacuum at -50 to -45 °C,
and the dark brown-red residue was chromatographed on an
alumina (neutral, 100-200 mesh) column (1.6 × 15-25 cm)
at -25 °C with petroleum ether/CH2Cl2 (5:2) as the eluant.
The brown-red band was eluted and collected. The solvent was
removed under vacuum at -20 °C, and the residue was
recrystallized from petroleum ether/CH2Cl2 at -80 °C to give
0.161 g (51%, based on 1) of brown-red crystals of 7: mp 146-
148 °C dec; IR (CH2Cl2) ν(CO) 2091 (s), 2071 (vs), 2030 (vs),
1850 (m) cm-1 1H NMR (CD3COCD3) δ 7.67-6.98 (m, 5H,
;
C6H5), 4.54 (s, 5H, C5H5), -17.95 (s, 1H, µ-H); MS m/e 790
(M+ - CO), 762 (M+ - 2CO), 706 (M+ - 4CO), 176 [Mn(CO)2-
(C5H5)]+. Anal. Calcd for C20H11O8MnOs2: C, 29.49; H, 1.36.
Found: C, 29.65; H, 1.43. 11: mp 121-123 °C dec; IR (CH2-
Cl2) ν(CO) 1978 (s), 1939 (s) cm-1 1H NMR (CD3COCD3) δ
;
7.64-7.28 (m, 10H, C6H5), 4.96 (s, 10H, C5H5); MS m/e 530
(M+), 502 [M+ - CO], 418 [M+ - 4CO], 298 [M+ - 4CO -
MnC5H5], 204 [Mn(CO)3(C5H5)]+. Anal. Calcd for C28H20O4-
Mn2: C, 63.41; H, 3.80. Found: C, 63.45; H, 4.02.
Rea ction of 1 w ith [(P h 3P )2N]2[F e4(CO)13] (5) To Give
[Mn Fe2(µ-H)(µ-CO)2(µ3-CC6H5)(CO)6(η-C5H5)] (12). The pro-
cedure used in the reaction of 1 (0.85 g, 1.42 mmol) with
[(Ph3P)2N]2[Fe4(CO)13] (5; 1.11 g, 0.67 mmol) was the same as
that for the reaction of 1 with 3 at -100 to -50 °C for 5-6 h,
during which time the blackish solution gradually turned
purple red. The resulting mixture was evaporated to dryness
under vacuum at -50 to -45 °C, and the dark purple-red
residue was chromatographed on Al2O3 at -25 °C with
petroleum ether/CH2Cl2 (5:2) as the eluant. The purple-red
band was eluted and collected. The solvent was removed under
vacuum, and the residue was recrystallized from petroleum
ether/CH2Cl2 (10:1) at -80 °C to give 0.33 g (85%, based on 1)
1
1999 (s), 1929 (m), 1835 (s, br) cm-1; H NMR (CD3COCD3) δ
7.86-7.21 (m, 5H, C6H5), 4.64 (s, 5H, C5H5), -18.08 (s, 1H,
(8) Fischer, E. O.; Meineke, E. W.; Kreissl, F. R. Chem. Ber. 1977,
110, 1140.
(9) Fischer, E. O.; Chen, J .-B.; Scherzer, K. J . Organomet. Chem.
1983, 253, 231.
(10) Karet, G. B.; Voss, E. J .; Sailor, M. J .; Shriver, D. F. Inorg.
Synth. 1998, 32, 277.
(11) Whitmire, K. H.; Ross, J .; Cooper, C. B., III; Shriver, D. F. Inorg.
Synth. 1982, 21, 66.
(12) Dias, A. R.; Galvao, A.; Garcia, M. H.; Villa de Brito, M. J . J .
Organomet. Chem. 2001, 620, 276.

2766 Organometallics, Vol. 21, No. 13, 2002
Xiao et al.
of 1213 as deep purple-red crystals: mp 106 °C dec; IR (CH2-
Cl2) ν(CO) 2077 (s), 2048 (vs), 2014 (s), 1989 (s), 1868 (s, br),
(CD3COCD3) δ 7.55-7.52 (m, 5H, C6H5), 7.28-7.22 (m, 5H,
C6H5), 6.27 (s, 5H, C5H5); MS m/e 492 [M+ - 3CO], 464 [M+
-
1831 (w) cm-1
;
1H NMR (CD3COCD3) δ 8.01 (m, 2H, C6H5),
4CO], 436 [M+ - 5CO]. Anal. Calcd for C22H15O5S2MoMn: C,
46.01; H, 2.63. Found: C, 45.71; H, 2.90.
7.55 (m, 2H, C6H5), 7.33 (m, 1H, C6H5), 4.80 (s, 5H, C5H5),
-23.80 (s, 1H, µ-H); MS m/e 546 (M+), 518 [M+ - CO], 490
Rea ction of 2 w ith 6 To Give [(η-C5H5)(CO)2RedC-
(SC6H5)C6H5] (17) a n d [(η-C5H5)(CO)2RedC(H)C6H5] (18).
Compound 2 (0.49 g, 0.67 mmol) was treated, as used in the
reaction of 1 with 3, with 6 (0.74 g, 0.67 mmol) at -100 to
-45 °C for 5 h, during which time the orange-red solution
gradually turned brown-red. Further treatment in a manner
similar to that described in the reaction of 1 with 6 gave 0.160
g (47%, based on 2) of gold-yellow crystals of 1714 and 0.070 g
(26%, based on 2) of red crystals of 18.6a,15 17: mp 118-120
[M+ - 2CO], 462 [M+ - 3CO], 434 [M+ - 4CO], 406 [M+
-
5CO], 378 [M+ - 6CO], 350 [M+ - 7CO], 322 [M+ - 8CO].
266 [M+ - Fe2(CO)6]. Anal. Calcd for C20H11O8MnFe2: C, 44.00;
H, 2.03. Found: C, 43.86; H, 2.08.
Rea ction of 2 w ith 5 To Give [ReF e2(µ-H)(µ-CO)2(µ3-
CC6H5)(CO)6(η-C5H5)] (13). Using the same procedures for
the reaction of 1 with 5, compound 2 (0.73 g, 1.00 mmol) was
treated with 5 (0.828 g, 0.50 mmol) to give 0.300 g (88%, based
on 2) of deep purple-red crystals of 13: mp 140 °C dec; IR (CH2-
Cl2) ν(CO) 2072 (s), 2041 (vs), 2004 (s), 1982 (s), 1894 (s, br),
°C dec; IR (CH2Cl2) ν(CO) 1961 (vs), 186 (s) cm-1 1H NMR
;
(CD3COCD3) δ 7.14-6.74 (m, 10H, C6H5), 5.51 (s, 5H, C5H5);
MS m/e 506 (M+), 478 [M+ - CO], 450 [M+ - 2CO], 373 [M+
- 2CO - C6H5], 341 [M+ - 2CO - SC6H5]. Anal. Calcd for
1851 (w) cm-1 1H NMR (CD3COCD3) δ 7.68 (m, 2H, C6H5),
;
7.36 (m, 2H, C6H5), 7.10 (m, 1H, C6H5), 5.40 (s, 5H, C5H5),
-23.09 (s, 1H, µ-H); MS m/e 678 (M+), 650 [M+ - CO], 622
C
20H15O2SRe: C, 47.51; H, 2.99. Found: C, 47.45; H, 3.11. 18:
1
mp 70 °C dec; IR (CH2Cl2) ν(CO) 1965 (s), 1885 (s) cm-1; H
[M+ - 2CO], 594 [M+ - 3CO], 566 [M+ - 4CO], 538 [M+
-
5CO], 510 [M+ - 6CO], 482 [M+ - 7CO], 454 [M+ - 8CO].
398 [M+ - Fe2(CO)6]. Anal. Calcd for C20H11O8ReFe2: C, 35.47;
H, 1.64. Found: C, 35.27; H, 1.73.
NMR (CD3COCD3) δ 16.53 (s, 1H, Ccarbene-H), 7.91-7.39 (m,
5H, C6H5), 6.02 (s, 5H, C5H5); MS m/e 398 (M+), 370 [M+
-
CO], 342 [M+ - 2CO]. Anal. Calcd for C14H11O2Re: C, 42.31;
H, 2.79. Found: C, 42.19; H, 2.81.
Rea ction of 13 w ith P P h 3 To Give [ReF e2(µ-H)(µ-CO)2-
(µ3-CC6H5)(CO)5(P P h 3)(η-C5H5)] (14). To 0.010 g (0.015
mmol) of 13 dissolved in 30 mL of THF at -20 °C was added
0.015 g (0.057 mmol) of PPh3. The mixture was stirred at -20
to 5 °C for 24 h, during which time the dark purple-red solution
turned purple-red. After the solution was evaporated at 0 °C
under vacuum to dryness, the residue was chromatographed
on Al2O3 at 0 °C with petroleum ether/CH2Cl2 (5:1) as the
eluant. The purple-red band was eluted and collected. The
solvent was removed in vacuo, and the crude product was
recrystallized from petroleum ether/CH2Cl2 at -80 °C to give
0.012 g (91%, based on 13) of purple-red crystals of 14: mp
166 °C dec; IR (CH2Cl2) ν(CO) 2048 (s), 1993 (vs), 1977 (sh),
X-r a y Cr ysta l Str u ctu r e Deter m in a tion s of Com p lexes
7, 9, 13, 14, a n d 16. Single crystals of complexes 7, 9, 13, 14,
and 16 suitable for X-ray diffraction study were obtained by
recrystallization from petroleum ether/CH2Cl2 or petroleum
ether/Et2O at -80 °C. Single crystals were mounted on a glass
fiber and sealed with epoxy glue. The X-ray diffraction
intensity data for 2525, 3996, 9476, and 1518 independent
reflections, of which 1809, 3372, 5396, and 1080 with I > 2.00σ-
(I) for 7, 13, 14, and 16 and 3617 with I > 3.00σ(I) for 9 were
observable, were collected with a Rigaku AFC7R and Brock
Smart diffractometer at 20 °C using Mo KR radiation with an
ω-2θ scan mode.
The structures of 7, 9, 13, and 14 were solved by direct
methods and expanded using Fourier techniques, while the
structure of 16 was solved by heavy-atom Patterson methods
and expanded using Fourier techniques. For complexes 7, 13,
and 14, the non-hydrogen atoms were refined anisotropically.
For 9 and 16, some non-hydrogen atoms were refined aniso-
tropically, while the rest were refined isotropically. For all five
complexes, the hydrogen atoms were included but not refined.
The final cycle of full-matrix least-squares refinement was
respectively based on 1809, 3617, 3372, 5396, and 1080
observed reflections and 278, 314, 284, 445, and 248 variable
parameters and converged with unweighted and weighted
agreement factors of R ) 0.049 and Rw ) 0.051 for 7, R ) 0.043
and Rw ) 0.049 for 9, R ) 0.0583 and Rw ) 0.1628 for 13, R )
0.0501 and Rw ) 0.1115 for 14, and R ) 0.043 and Rw ) 0.046
for 16, respectively.
1
1940 (s), 1867 (s, br), 1810 (m) cm-1; H NMR (CD3COCD3) δ
7.39-7.36 (m, 20H, C6H5), 5.38 (m, 2H, CH2Cl2), 5.25 (s, 5H,
C5H5), -22.06 (d, 1H, µ-H); MS m/e 568 (M+ - PPh3 - 3CO),
512 [M+ - PPh3 - 5CO], 398 [M+ - PPh3 - Fe2(CO)5], 84 (CH2-
Cl2+). Anal. Calcd for C37H26O7PReFe2‚CH2Cl2: C, 45.81; H,
2.83. Found: C, 45.40; H, 3.22.
Rea ction of 1 w ith [Mo(η-C5H5)2(H)CO][Mn 3(CO)9(µ-
SC6H5)4] (6) To Give [(η-C5H5)(CO)2Mn dC(SC6H5)C6H5]
(15) a n d [Mo(η-C5H5)(CO)2(µ-SC6H5)2Mn (CO)3] (16). Com-
pound 1 (0.57 g, 0.96 mmol) was treated, in a manner similar
to that in the reaction of 1 with 3, with [Mo(η-C5H5)2(H)CO]-
[Mn3(CO)9(µ-SC6H5)4] (6) (1.06 g, 0.96 mmol) in THF at -100
to -50 °C for 5 h, during which time the brown-yellow solution
turned brown-green. After the solution was evaporated at -50
to -45 °C under vacuum to dryness, the residue was chro-
matographed on Al2O3 at -25 °C with petroleum ether/CH2-
Cl2 (5:1) as the eluant. The brown-yellow band was eluted with
petroleum ether/CH2Cl2 (5:2) and collected, and then the
brown-red band was eluted with petroleum ether/CH2Cl2 (2:
1). The solvents were removed from the above two eluates
under vacuum, and the two residues were recrystallized from
petroleum ether/CH2Cl2 or petroleum ether/THF solution at
-80 °C. From the first fraction, 0.180 g (50%, based on 1) of
1514 as orange-red crystals was obtained: mp 116-118 °C dec;
The details of the crystallographic data and the procedures
used for data collection and reduction information for 7, 9, 13,
14, and 16 are given in Table 1. Selected bond lengths and
angles are listed in Tables 2 and 3, respectively. The atomic
coordinates and
Biso/Beq values, anisotropic displacement
parameters, all bond lengths and angles, and least-squares
planes for 7, 9, 13, 14, and 16 are given in the Supporting
Information. The molecular structures of 7, 9, 13, 14, and 16
are given in Figures 1-5, respectively.
IR (CH2Cl2) ν(CO) 1965 (s), 1902 (s) cm-1
COCD3) δ 7.13-6.62 (m, 10H, C6H5), 4.92 (s, 5H, C5H5); MS
m/e 374 (M+), 346 [M+ - CO], 318 [M+ - 2CO], 241 [M+
2CO - C6H5], 209 [M+ - 2CO - SC6H5]. Anal. Calcd for
20H15O2SMn: C, 64.17; H, 4.04. Found: C, 64.02; H, 4.21.
;
1H NMR (CD3-
-
Resu lts a n d Discu ssion
C
Two equivalents of a cationic carbyne complex of
manganese, [(η-C5H5)(CO)2MntCC6H5]BBr4 (1), reacts
with 1 equiv of [(Ph3P)2N]2[Ru3(CO)11] (3) in THF at low
temperature (-100 to -50 °C) for 4-5 h. After workup
as described in the Experimental Section, the Mn-Ru
From the second fraction, 0.165 g (30%, based on 6) of 16 as
brown-red crystals was obtained: mp 150 °C dec; IR (CH2Cl2)
ν(CO) 2023 (vs), 1982 (s), 1947 (s), 1913 (m) cm-1 1H NMR
;
(13) Wang, R.-T.; Xu, Q. Souma, Y.; Song, L.-C.; Sun, J .; Chen,
J .-B. Organometallics 2001, 20, 2226.
(14) Qiu, Z.-L.; Sun, J . Chen, J .-B. Organometallics 1998, 17, 600.
(15) Fischer, E. O.; Frank, A. Chem. Ber. 1978, 111, 3740.

Cationic Carbyne Complexes of Mn and Re
Organometallics, Vol. 21, No. 13, 2002 2767
Ta ble 1. Cr ysta l Da ta a n d Exp er im en ta l Deta ils for Com p lexes 7, 9, 13, 14, a n d 16
7
9
13
14‚CH2Cl2
16‚CH2Cl2
formula
fw
C20H11O8MnRu2
636.38
C32H28O5Re2
864.98
C20H11O8ReFe2
677.19
C38H28O7PRe Fe2
996.37
C23H17O5Cl2S2MoMn
659.29
space group
a (Å)
b (Å)
Cc (No. 9)
18.494(6)
8.541(2)
P21/n (No. 14)
10.925(3)
15.318(2)
17.434(2)
P21/c (No. 14)
8.2317(9)
9.0035(9)
P21/n (No. 14)
14.4098(13)
12.5868(11)
22.727(2)
P212121 (No. 19)
10.967(3)
23.803(4)
9.691(4)
90
90
90
2529(1)
4
1.731
1312.00
14.08
Mo KR (λ )
0.71069 Å)
Rigaku AFC7R
20
c (Å)
16.124(4)
27.757(3)
R (deg)
â (deg)
γ (deg)
V (Å3)
125.25(1)
103.12(1)
90.517(2)
97.451(2)
2079(1)
4
2.032
1232.00
20.77
Mo KR (λ )
0.71069 Å)
Rigaku AFC7R
20
2841.4(9)
4
2.022
1640.00
85.56
Mo KR (λ )
0.71069 Å)
Rigaku AFC7R
20
2057.1(4)
4
2.187
1288
73.07
Mo KR (λ )
0.71073 Å)
Brock Smart
20
4087.3(6)
4
1.619
1952
38.68
Mo KR (λ )
0.71073 Å)
Brock Smart
20
Z
Dcalcd (g/cm3)
F(000)
µ(Mo KR) (cm-1
radiationa
)
diffractometer
temp (°C)
orientation rflns:
no.; range (2θ) (deg)
scan method
data collecn range, 2θ (deg)
unique data
22; 14.0-21.4
23; 13.7-21.7
2.38-27.25
4.54-47.72
19; 14.1-16.4
ω-2θ
5-55.0
ω-2θ
5-51.0
ω-2θ
2.94-52.0
ω-2θ
3.18-56.66
ω-2θ
5-51.0
total no.
2525
5504
3996
9476
1518
no. with I > 2.00σ(I)
no. of params refined
correcn factors: max-min
Rb
1809
278
0.9082-1.0000
0.049
0.051
1.30
0.01
1.24
-1.14
3617 (I > 3.00σ(I))
3372
284
0.5992-1.0000
0.0583
0.1628
1.110
0.006
2.857
-1.706
5396
445
1080
248
0.7994-1.0000
0.043
0.046
1.34
0.01
0.49
-0.69
314
0.4014-1.0000
0.043
0.049
1.57
0.02
2.27
-1.11
0.7590-1.0000
0.0501
0.1115
0.909
0.00000(5)
2.491
c
Rw
quality of fit indicatord
max shift/esd, final cycle
largest peak (e/Å3)
min peak (e/Å3)
-1.165
a
b
2
d
Monochromated in incident beam. R ) ∑||Fo| - |Fc||/∑|Fo|. c Rw ) [∑w(|Fo| - |Fc|)2/∑w|Fo| ]1/2; w ) 1/σ2(|Fo|). Quality of fit ) [∑w(|Fo|
- |Fc|)2/(Nobservns - Nparams)]1/2
.
[Re(CO)2(η-C5H5)(µ-CC6H5)]2 (9) in 48% and 21% yields,
respectively (eq 2).
F igu r e 1. Molecular structure of 7, showing the atom-
numbering scheme. Thermal ellipsoids are shown at 45%
probability.
heteronuclear trimetal bridging carbyne complex [MnRu2-
(µ-H)(µ-CO)2(µ3-CC6H5)(CO)6(η-C5H5)] (7) (eq 1)was ob-
tained in 51% isolated yield. A cationic carbyne complex
of rhenium, [(η-C5H5)(CO)2RetCC6H5]BBr4 (2), reacts
similarly with 3 to afford the corresponding trimetal
bridging carbyne complex [ReRu2(µ-H)(µ-CO)2(µ3-CC6H5)-
(CO)6(η-C5H5)] (8) and the neutral Re-carbyne dimer
Unlike the ruthenium anionic compound 3, the os-
mium anionic compound [(Ph3P)2N]2[Os3(CO)11] (4) re-

2768 Organometallics, Vol. 21, No. 13, 2002
Xiao et al.
Ta ble 2. Selected Bon d Len gth s (Å)a a n d An gles
(d eg)a for Com p lexes 7, 13, a n d 14
Ta ble 3. Selected Bon d Len gth s (Å)a a n d An gles
(d eg)a for Com p lexes 9 a n d 16
7 (M ) Mn, 13 (M ) Re,
14 (M ) Re,
M′ ) Fe)
Complex 9
M′ ) Ru)
M′ ) Fe)
Re(1)-C(15)
Re(1)-C(16)
Re(2)-C(15)
Re(2)-C(16)
C(15)-C(16)
C(15)-C(17)
C(16)-C(23)
2.23(1)
2.30(1)
2.29(1)
2.25(1)
1.36(2)
1.46(2)
1.47(2)
Re(1)-C(1)
1.90(1)
1.91(1)
1.91(1)
1.86(1)
2.288
Re(1)-C(2)
M-M′(1)
M- M′(2)
2.703(3)
2.708(2)
2.860(2)
1.81(2)
1.81(2)
1.99(1)
2.07(2)
2.08(1)
1.92
2.709(2)
2.715(2)
2.626(3)
1.923(18)
1.926(16)
2.062(12)
1.966(12)
1.973(11)
1.792
2.7209(11)
2.7282(9)
2.6420(14)
1.904(9)
1.940(8)
2.092(7)
1.952(7)
1.965(7)
1.787
Re(2)-C(3)
Re(2)-C(4)
Re(1)-C(Cp) (av)
Re(2)-C(Cp) (av)
M′(1)-M′(2)
M-C(1)
2.278
M-C(2)
M-C(6)
M′(1)-C(6)
Re(1)-C(15)-Re(2) 113.3(5) Re(1)-C(15)-C(17)
Re(1)-C(16)-Re(2) 112.2(5) Re(1)-C(16)-C(23)
125.0(9)
120.0(8)
118.9(8)
124.4(8)
137(1)
M′(2)-C(6)
M′(1)-C(CO) (av)
M′(2)-C(CO) (av)
M′(1)-C(1)
C(15)-Re(1)-C(16)
C(15)-Re(2)-C(16)
Re(1)-C(15)-C(16)
Re(1)-C(16)-C(15)
Re(2)-C(15)-C(16)
Re(2)-C(16)-C(15)
35.0(4) Re(2)-C(15)-C(17)
34.9(4) Re(2)-C(16)-C(23)
75.2(7) C(17)-C(15)-C(16)
69.8(6) C(15)-C(16)-C(23)
71.0(7) Re(1)-C-O(CO) (av) 174.5
74.1(7) Re(2)-C-O(CO) (av) 174.5
1.93
1.794
1.755
2.36(2)
2.34(2)
2.526(15)
2.476(19)
2.587(10)
2.383(7)
2.290(2)
1.485(10)
1.80(2)
M′(2)-C(2)
M′(2)-P
140(1)
C(6)-C(7)
1.51(2)
1.60
1.478(19)
1.68(2)
1.68(2)
2.242
M′(1)-H(11)
M′(2)-H(11)
M-C(Cp) (av)
M-M′(1)-M′(2)
M-M′(2)-M′(1)
M′(1)-M-M′(2)
M-M′(1)-C(6)
M-M′(2)-C(6)
M′(1)-M-C(6)
M′(2)-M-C(6)
M-C(6)-M′(1)
M-C(6)-M′(2)
M′(1)-M′(2)-C(6)
M′(2)-M′(1)-C(6)
M′(1)-C(6)-M′(2)
M-C(6)-C(7)
M′(1)-C(6)-C(7)
M′(2)-C(6)-C(7)
M-M′(2)-P
1.70
1.80(2)
2.274
2.136
Complex 16
58.17(6)
58.02(6)
63.82(6)
46.9(4)
46.8(4)
49.5(4)
49.6(4)
83.6(5)
83.6(5)
46.2(4)
46.4(4)
87.3(6)
129(1)
128(1)
128(1)
61.16(6)
60.92(6)
57.92(6)
49.3(3)
49.1(3)
46.2(3)
46.3(3)
84.5(5)
84.6(4)
48.1(3)
48.3(3)
83.6(5)
131.6(9)
128.4(8)
127.7(9)
61.14(3)
60.86(3)
58.00(3)
49.9(2)
Mo-Mn
2.786(3)
Mn-C(3)
1.76(2)
1.79(2)
1.77(2)
1.76(2)
1.81(2)
2.32
Mo-S(1)
Mo-S(2)
Mn-S(1)
Mn-S(2)
Mo-C(1)
Mo-C(2)
2.491(4)
2.507(5)
2.349(5)
2.344(5)
1.98(2)
Mn-C(4)
Mn-C(5)
S(1)-C(11)
S(2)-C(17)
Mo-C(Cp) (av)
49.7(2)
45.58(19)
45.79(18)
84.5(3)
84.5(3)
47.4(2)
47.78(19)
84.8(3)
127.3(5)
131.2(5)
128.5(5)
124.83(6)
166.6(7)
157.6(6)
1.98(2)
Mo-Mn-S(1)
Mo-Mn-S(2)
Mn-Mo-S(1)
Mn-Mo-S(2)
Mo-S(1)-Mn
Mo-S(2)-Mn
S(1)-Mo-S(2)
57.3(1)
57.7(1)
52.5(1)
77.6(5)
70.2(1)
70.0(1)
68.8(2)
S(1)-Mn-S(2)
74.0(2)
117.9(5)
113.6(5)
112.9(5)
115.1(6)
175.5
Mo-S(1)-C(11)
Mo-S(2)-C(17)
Mn-S(1)-C(11)
Mn-S(2)-C(17)
Mo-C-O(CO) (av)
Mn-C-O(CO) (av)
176.3
M-C(1)-O(1)
M-C(2)-O(2)
155(1)
152(1)
162.8(16)
161.9(17)
a
Estimated standard deviations in the least significant figure
are given in parentheses.
a
Estimated standard deviations in the least significant figure
are given in parentheses.
initially revealed by their 1H NMR spectra, which
showed high-field resonances at -18.08, -17.52, and
-17.95 ppm, respectively, characteristic for a M-H-M
species.
acts only with cationic carbyne complex 1 under the
same conditions to form the heterotrimetal bridging
carbyne complex [MnOs2(µ-H)(µ-CO)2(µ3-CC6H5)(CO)6-
(η-C5H5)] (10) and the neutral Mn-carbyne dimer [Mn-
(CO)2(η-C5H5)(µ-CC6H5)]2 (11) in 47% and 24% isolated
yields (eq 3), respectively.
The structures of complexes 7 and 9 have been further
confirmed by X-ray crystallography. The results of the
X-ray diffraction work are summarized in Table 1, and
their molecular structures are shown in Figures 1 and
2, respectively. In 7, the triangular MnRuRu arrange-
ment with a capping µ3-CC6H5 ligand is confirmed. The
three MnRuRu metal atoms construct an approximate
isosceles triangle (Mn-Ru(1) ) 2.703(3) Å, Mn-Ru(2)
) 2.708(2) Å, and Ru(1)-Ru(2) ) 2.860(2) Å). Although
an analogous bridging carbyne complex with a trimet-
allatetrahedrane CMnFe2 core, [MnFe2(µ3-CCH3)(µ-CO)-
(CO)3(η-C5H5)2], has been prepared by reaction16 of
[Mn3(µ3-H)3(CO)12] with trans-[Fe2(µ-CdCH2)(µ-CO)-
(CO)2(η-C5H5)2], no analogous CMn-Ru2 bridging car-
byne complex has been reported. Only the triruthenium
bridging carbyne complex [Ru3(µ3-COMe)(µ-H)3(CO)9] is
known.17 Complex 7 appears to be the first example of
a species with Mn-Ru2 and Ru-Ru bonds studied by
X-ray crystallography, and hence, comparison of the
Mn-Ru and Ru-Ru bond distances with others involv-
ing these elements is not possible. The two Mn-Ru bond
lengths, 2.703(3) and 2.708(2) Å, respectively, are nearly
the same. The Ru-Ru bond length of 2.860(2) Å in 7 is
somewhat longer than that found in the triruthenium
Complexes 7-11 are readily soluble in polar organic
solvents but slightly soluble in nonpolar solvents. They
are air-sensitive in solution but relatively stable as the
solid. Products 7, 8, and 10 are formulated as hetero-
nuclear trimetal bridging carbyne complexes possessing
a µ-H bridged to the two Ru or Os atoms, while products
9 and 11 are formulated as neutral carbyne dimer
complexes. The structures of complexes 7, 8, and 10 and
complexes 9 and 11 have been established by their IR,
1H NMR, and mass spectra. The existence of the
bridging hydrogen in complexes 7, 8, and 10 was
(16) Brun, P.; Dawkins, G. M.; Green, M.; Mills, R. M.; Salaun, J .
Y.; Stone, F. G. A.; Woodward, P. J . Chem. Soc., Dalton Trans. 1983,
1357.
(17) Keister, J . B.; Payne, M. W.; Muscatella, M. J . Organometallics
1983, 2, 219.

Cationic Carbyne Complexes of Mn and Re
Organometallics, Vol. 21, No. 13, 2002 2769
F igu r e 4. Molecular structure of 14, showing the atom-
numbering scheme. Thermal ellipsoids are shown at 45%
probability. CH2Cl2 has been omitted for clarity.
F igu r e 2. Molecular structure of 9, showing the atom-
numbering scheme. Thermal ellipsoids are shown at 45%
probability.
F igu r e 3. Molecular structure of 13, showing the atom-
numbering scheme. Thermal ellipsoids are shown at 40%
probability.
F igu r e 5. Molecular structure of 16, showing the atom-
numbering scheme. Thermal ellipsoids are shown at 45%
probability. CH2Cl2 has been omitted for clarity.
bridging carbyne complex [Ru3(µ-CNMe2)(µ-H)(CO)10]
(average 2.818 Å).18 The µ-C(6)-Mn, µ-C(6)-Ru(1), and
µ-C(6)-Ru(2) distances are 1.99(1), 2.07(2), and 2.08-
(1) Å, respectively, of which the µ-C(6)-Mn bond
distance is closely related to that found in the complexes
[MnFeCo(µ3-CC6H5)(µ-CO)(CO)7(η-C5H5)] (1.94(1) Å)7d
and [MnFe2(µ-H)(µ-CO)2(µ3-CC6H5)(CO)6(η-C5H5)] (2.00-
(1) Å),13 and the two µ-C(6)-Ru bond lengths are
essentially the same.
In complex 7 the Ru(1) and Ru(2) atoms are asym-
metrically bridged by a hydrogen, the Ru(1)-H and Ru-
(2)-H distances being 1.60 and 1.70 Å, respectively. The
two Ru atoms each carry three terminal CO groups, and
the Mn atom carries two CO groups, being semibridging
to the two Ru atoms, respectively (Mn-C(1)-O(1) )
155(1)°, Mn-C(1) ) 1.81(2) Å; Mn-C(2)-O(2) ) 152-
(1)°, Mn-C(2) ) 1.81(2) Å). The semibridging CO
ligands reveal themselves in the IR spectrum with a
strong and broad band at 1835 cm-1. Compound 7 is a
48-CVE (cluster valence electron) complex, where the
Mn and Ru atoms formally have 19 and 17 electrons,
respectively, which probably accounts for the presence
of the semibridging carbonyl and bridging hydrogen.
Several di- and polynuclear ruthenium complexes with
semibridging carbonyl and bridging hydrogen ligands
have been reported.19-22 The analogous 48-valence-
(18) Churchill, M. R.; Deboer, B. G.; Rotella, F. J .; Abel, E. W.;
Rowly, R. J . J . Am. Chem. Soc. 1975, 97, 7158.
(19) (a) Yawney, D. B. W.; Stone, F. G. A. J . Chem. Soc. A 1969,
502. (b) Gilmore, C. J .; Woodward, P. J . Chem. Soc. A 1971, 3453.

2770 Organometallics, Vol. 21, No. 13, 2002
Xiao et al.
electron structure was found in the complexes [MW2-
(µ3-C2R2)(CO)7(η-C5H5)] (M ) Ru, Os),23 [ReFeCo(µ3-
CC6H5)(CO)8(η-C5H5)],7d and [MnFe2(µ-H)(µ-CO)2(µ3-
CC6H5)(CO)6(η-C5H5)].13
knowledge, no such dimerization of carbyne species in
reactions of transition-metal carbyne complexes has
been reported.
Not all trimetal carbonyl anions can react with
cationic carbyne complexes 1 and 2 to give trimetal
bridging carbyne complexes, since the triiron carbonyl
anion [Fe3(CO)11]2- reacted only with complex 2 to give
not the trimetal bridging carbyne complex but rather
the dimetal bridging carbene complex [ReFe{µ-C(H)-
C6H5}(CO)6(η-C5H5)], the same product6a as that of the
The complex 9 was shown by X-ray crystallography
to have a µ-C2Re2 core arranged as a “butterfly” (inter-
planar angle 121.58°), with the two Re atoms each
occupying one of the “wingtips” and carrying a cyclo-
pentadienyl ligand. The molecular structure of 9 (Figure
2) shows that the two Re atoms bridged by the two PhC
groups are not directly bonded to each other. The two
Re atoms each carry two terminal CO groups, in
addition, to bond a cyclopentadienyl group and the two
µ-carbons of the PhC groups, thus giving each Re atom
18 valence electrons. In 9, the two phenyl groups are
on the opposite side of the two Re atoms. The C(15)-
C(16) distance between the two bridging carbons is 1.36-
(2) Å, which is between normal C-C double- and triple-
bond distances, indicating that the two bridging carbons
have strong interactions. The µ-C-Re distance (average
2.27 Å) is very close to that found in the analogous
dirhenium complex [Re2(µ-H){µ-C(SiPh3)CO}(CO)8] (av-
erage 2.28 Å), reported by Fischer et al.24
reaction of 2 with [Fe(CO)4]2- or [Fe2(CO)8]2-
.
Like the trimetal carbonyl anions 3 and 4, the
tetrametal carbonyl anionic compound [(PPh3)2N]2[Fe4-
(CO)13] (5) can also react with cationic carbyne com-
plexes 1 and 2 under the same conditions to afford the
analogous trimetal bridging carbyne complexes [MnFe2-
(µ-H)(µ-CO)2(µ3-CC6H5)(CO)6(η-C5H5)] (12) and [ReFe2-
(µ-H)(µ-CO)2(µ3-CC6H5)CO)6(η-C5H5)] (13) (eq 4) in high
The dihedral angle between the plane defined by Re-
(1), C(15), and C(16) and the plane comprised of Re(2),
C(15), and C(16) is 121.58°. The angles between the two
cyclopentadienyl ring planes and the two benzene ring
planes are 49.31 and 43.97°, respectively.
Complexes 7, 8, and 10 might be produced by loss of
a M′(CO)5 (M ) Ru, Os) moiety from the [M′3(CO)11]2-
(M′ ) Ru, Os) anion or by cleavage of the formed carbene
intermediate [(η-C5H5)(CO)2MdC(C6H5)M′3(CO)11] (M )
Mn, Re, M′ ) Ru, Os) to generate a [M′2(CO)6H]-
species, which then becomes bonded to the carbyne or
carbene carbon through the two Ru or Os atoms with
bonding of the Mn or Re atom to the two Ru or Os atoms
to give complexes 7 or 8 and 10. This reaction pathway
to complexes 7, 8, and 10 is rather analogous to that of
the reaction13 of reactive [Fe2(µ-CO)(µ-SeC4H9-n)(CO)6]-
anion with complex 1. The latter was assumed to
proceed via a [Fe2(CO)6H]- species, which attacks the
carbyne carbon of cationic 1 to afford the bridging
carbyne complex [MnFe2(µ-H)(µ-CO)2(µ3-CC6H5)(CO)6-
(η-C5H5)]. The origin of the H- in these reactions could
be THF solvent or water, which is a trace contaminant
in the solvent THF or from glassware.
yields (>85%), respectively, among which product 12 is
a known compound obtained from the reaction of 1 with
reactive [Fe2(µ-CO)(µ-SeC4H9-n)(CO)6]- anion and has
been characterized by X-ray crystallography.13
The formation pathway of complexes 12 and 13 could
proceed via a [Fe2(CO)6H]- species derived from cleav-
age of the [Fe4(CO)13]2- anion, analogous to that of
ruthenium and osmium complexes 7, 8, and 10, which
was assumed to be via an [M′2(CO)6H]- (M′ ) Ru, Os)
species.
A number of trimetal bridging carbyne complexes
have been prepared by Stone et al. and by us, as
mentioned in the Introduction. However, complexes 7,
8, 10, 12, and 13, as heteronuclear trimetal bridging
carbyne complexes, were synthesized first by the reac-
tion of the cationic carbyne complexes with the poly-
metal carbonyl anions in one step. Undoubtedly, this is
a new and convenient method for preparation of such
trimetal bridging carbyne complexes.
It is equally interesting that complex 13, when treated
with an excess of PPh3 in THF at 0 to 5 °C for 24 h,
gave the PPh3-substituted bridging carbyne complex
[ReFe2(µ-H)(µ-CO)2(µ3-CC6H5)(CO)5(PPh3)(η-C5H5)] (14)
(eq 5) in 91% yield.
Unexpectedly, the Mn-Fe2 trimetal bridging carbyne
complex 12 does not react with PPh3 under the same
conditions to afford the analogous PPh3-substituted
complex, even at room temperature for 48 h.
The reaction pathway to complexes 9 and 11 is
presumed to be via the neutral carbyne intermediate
[(η-C5H5)(CO)2MtCC6H5] (M ) Mn, Re), arising from
the reduction of the carbyne cation 1 or 2. Two [(η-C5H5)-
(CO)2MtCC6H5] fragments could form the neutral car-
byne dimer 9 or 11 by their dimerization. To our
(20) Takusagawa, F.; Fumagalli, A.; Koetzle, T. F.; Steinmetz, G.
R.; Rosen, R. P.; Gladfelter, W. L.; Geoffroy, G. L.; Bruck, M. A.; Bau,
R. Inorg. Chem. 1981, 20, 3823.
(21) (a) Haines, R. J . In Comprehensive Organometallic Chemistry
II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press:
Oxford, U.K., 1995; Vol. 7, p 633. (b) Field, J . S.; Haines, R. J .; Stewart,
M. W.; Woollam, S. F. S. Afr. J . Chem. 1993, 46, 45.
(22) (a) Field, J . S.; Haines, R. J .; Sundermeyer, J .; Woollam, S. F.
J . Chem. Soc., Chem. Commun. 1991, 1382. (b) Field, J . S.; Haines, R.
J .; Stewart, M. W.; Sundermeyer, J .; Woollam, S. F. J . Chem. Soc.,
Dalton Trans. 1993, 947.
(23) Busetto, L.; Green, M.; Howard, J . A. K.; Hessner, B.; J effery,
J . C.; Mills, R.M.; Stone, F. G. A.; Woodward, P. J . Chem. Soc., Chem.
Commun. 1981, 1101.
(24) Fischer, E. O.; Rustemeyer, P.; Orama, O.; Neugebauer, D.;
Schubert, U. J . Organomet. Chem. 1983, 247, 7.
The formulas of complexes 12-14 were also supported
by microanalytical and spectroscopic data (Experimental

Cationic Carbyne Complexes of Mn and Re
Organometallics, Vol. 21, No. 13, 2002 2771
workup as described in the Experimental Section, no
expected trimetal bridging carbyne complex but the
(phenylthio)carbene complex [(η-C5H5)(CO)2MndC-
(SC6H5)C6H5] (15) and thiolato-bridged Mo-Mn carbo-
nyl complex [Mo(η-C5H5)(CO)2(µ-SC6H5)2Mn(CO)3] (16)
(eq 6) were obtained in 50% and 30% yields, respec-
tively, of which product 15 is a known compound and
was characterized by an X-ray diffraction analysis.14
Section). Their 1H NMR spectra had resonances at
-23.80, -23.09, and -22.06 ppm, respectively. These
resonances have undergone remarkable upfield shifts,
as compared with those of the analogous bridging
carbyne complexes 7, 8, and 10. Their structures were
further confirmed by X-ray diffraction determinations
of 13 and 14.
The structure of 13 shown in Figure 3 is very similar
to that of the analogous bridging carbyne complex
[MnFe2(µ-H)(µ-CO)2(µ3-CC6H5)(CO)6(η-C5H5)],13 except
that the Re atom in 13 is displaced by the Mn atom in
the latter. The Re-Fe distances (Re-Fe(1) ) 2.709(2)
Å, Re-Fe(2) ) 2.715(2) Å) are somewhat longer than
the corresponding distances in [MnFe2(µ-H)(µ-CO)2(µ3-
CC6H5)(CO)6(η-C5H5)] (Mn-Fe(1) ) 2.606(3) Å, Mn-Fe-
(2) ) 2.612(3) Å).13 The µ-C(6)-Re distance of 2.062(12)
Å and the average µ-C(6)-Fe distance of 1.970 Å are
both slightly longer than those found in [MnFe2(µ-H)-
(µ-CO)2(µ3-CC6H5)(CO)6(η-C5H5)] (µ-C(6)-Mn ) 2.00(1)
Å, average µ-C(6)-Fe ) 1.94 Å),13 while the average
Fe-H bond length (1.68 Å) is somewhat shorter than
that in [MnFe2(µ-H)(µ-CO)2(µ3-CC6H5)(CO)6(η-C5H5)]
(1.77 Å).13
Like 1, cationic carbyne complex 2 also reacts with
anion 6; however, the products are different. The
reaction of 2 with 6 under the same conditions as those
for 1 yields only the known mercaptocarbene complex
[(η-C5H5)(CO)2RedC(SC6H5)C6H5] (17)14 and phenyl-
carbene complex [(η-C5H5)(CO)2RedC(H)C6H5] (18)6a,15
(eq 7) in 47% and 26% yields, respectively. The forma-
The X-ray structure study of complex 14 (Figure 4)
confirmed the presence of the PPh3 ligand in 14. Its
structure resembles that of 13, except that a terminal
CO ligand in the latter is displaced by PPh3 in 14. Many
structural features of the principal [ReFe2(µ-H)(µ-CO)2-
(µ3-CC6H5)(CO)6(η-C5H5)] moiety in 14 are nearly the
same as those of 13: the two Re-Fe distances, the Fe-
Fe distance, the µ-C-Re distance, the two µ-C-Fe
distances, and the average Re-C(Cp) distance. An
apparent difference in the structures of 14 and 13 is
the longer Fe-H bond length in 14 (average 1.80(2) Å),
as compared to 13 (average 1.68(2) Å), and the larger
angles between the benzene ring plane defined by C(7)
through C(12) and the cyclopentadienyl ring plane in
14 (28.89°) as compared to 13 (23.15°), arising from the
steric hindrance of the bulky PPh3 group on the Fe(2)
atom.
tion of products 15-18 is unexpected, and we do not
know the chemistry involved.
The structure of complex 16 (Figure 5) was estab-
lished by single-crystal X-ray diffraction. The Mo-Mn
distance of 2.786(3) Å is somewhat longer than that
found in the analogous compound [MoMn(CO)(η-C5H5)-
{µ-(η5:η1-C5H4)}] (2.7605(8) Å).25 The Mo-µ-S(1) and
Mo-µ-S(2) bond lengths are 2.491(4) and 2.507(5) Å,
respectively, which are nearly the same as those in the
thiolato-bridged molybdenum compound [Et3NH]2-
[Mo2(NNHPh)(NNPh)(SCH2CH2S)3(SCH2CH2SH)] (av-
Of particular interest are the reactions of the novel
trimanganese tetrathiolated incomplete cubane [Mo(η-
C5H5)2(H)CO][Mn3(CO)9(µ-SC6H5)4] (6), reported most
recently by Dias et al.12 The freshly prepared 6 was
treated with an equimolar quantity of cationic 1 in THF
at low temperature (-100 to -50 °C) for 4-5 h. After
(25) Hoxmeier, R. J .; Knobler, C. B.; Kaesz, H. D. Inorg. Chem. 1979,
18, 3462.

2772 Organometallics, Vol. 21, No. 13, 2002
Xiao et al.
erage Mo-µ-S ) 2.501(6) Å),26 while the distances of
Mn-µ-S(1) and Mn-µ-S(2), 2.349(5) and 2.344(5) Å,
respectively, are significantly longer than the corre-
sponding bonds in the analogous thiolato-bridged man-
ganese carbonyl complex [MnCr2(µ-SCMe3)(µ3-S)2(CO)3]
(Mn-S(1) ) 2.272(2) Å, Mn-S(2) ) 2.297(2) Å).27
The dihedral angle between the plane defined by Mo,
Mn, and S(1) and the plane comprised of Mo, Mn, and
S(2) is 91.04°. The angle between the two benzene ring
planes is 140.47°. The benzene ring plane defined as
C(11) through C(16) is respectively oriented 120.39 and
35.45° with respect to the MoMnS(1) plane and MoMnS-
(2) plane, while the benzene ring C(17)C(18)C(19)C-
(20)C(21)C(22) plane is oriented 33.35 and 121.71°,
respectively, with respect to the MoMnS(1) and MoMnS-
(2) planes.
complexes of manganese and rhenium, 1 and 2, to give
a series of heteronuclear trimetal bridging carbyne
complexes. The reaction results indicate that the dif-
ferent center metals in the cationic carbyne complexes
and the different carbonylmetal anions exert great
influence on the reactivity of the cationic carbyne
complexes and the resulting products. The title reaction
may offer a convenient and useful method for prepara-
tion of trimetal bridging carbyne complexes.
Ack n ow led gm en t. Financial support from the Na-
tional Natural Science Foundation of China and the
Science Foundation of the Chinese Academy of Sciences
is gratefully acknowledged.
Su p p or tin g In for m a tion Ava ila ble: Tables of the posi-
tional parameters and Biso/Beq values, H atom coordinates,
anisotropic displacement parameters, all bond lengths and
angles, and least-squares planes for 7, 9, 13, 14, and 16. This
material is available free of charge via the Internet at
http://pubs.acs.org.
The title reaction shows the novel reactions of the tri-
and tetrametal carbonyl anions with cationic carbyne
(26) Hsieh, T.-C.; Gebreyes, K.; Zubieta, J . J . Chem. Soc., Chem.
Commun. 1984, 1172.
(27) Pasynkii, A. A.; Eremenko, I. L.; Orezsakhatov, B.; Casanov,
G. S. J . Organomet. Chem. 1984, 270, 53.
OM0201359