Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with Carbonylmetal Anions Containing Cyclopentadienyl, PPh3, and NO Ligands. a Route to Dimetal Bridging Carbyne Complexes

Article abstract of DOI:10.1021/om9906262

The reactions of cationic carbyne complexes of manganese and rhenium, [η-C₅H₅(CO)₂M≡ CC₆H₅]BBr₄ (1, M = Mn; 2, M = Re), with Na[η-C₅H₅Mo(CO)₃] (3) in THF at low temperature afford η¹,η²-ketene complexes [MnMo{C(CO)C₆H₅}(CO)₄(η-C₅H ₅)₂] (8) and [ReMo{C(CO)-C₆H₅}(CO)₄(η-C ₅H₅)₂] (9), respectively. Analogous reactions of Na[η-C₅H₅W(CO)₃] (4) with 1 and 2 give the corresponding ketene complexes [MnW{C(CO)C₆H₅}(CO)₄(η-C₅H ₅)₂] (10) and [ReW{C(CO)C₆H₅}(CO)₄(η-C₅H ₅)₂] (11). Na[Co(CO)₃PPh₃] (5) also reacts with 1 and 2 to yield ketenyl-bridged complexes [MnCo{C(CO)C₆H₅}(CO)₄(PPh ₃)(η-C₅H₅)] (12) and [ReCo{C(CO)-C₆H₅}(CO)₄(PPh ₃)(η-C₅H₅)] (13), respectively. However, compound Na[η-C₅H₅Fe(CO)₂] (6) reacts only with 2 to form a η¹,η₂-ketene complex [ReFe{C(CO)C₆H₅}(CO)₃(η-C₅H ₅)₂] (14), while the reactions of (Ph₃P)₂N[Fe(CO)₃NO] (7) with 1 and 2 produce dimetal bridging carbyne complexes [MnFe(μ-CC₆H₅)(CO)₄(NO)(η-C ₅H₅)] (15) and [ReFe(μ-CC₆H₅)(CO)₄(NO)-(η-C ₅H₅)] (16), respectively. Compound 15 treated with an excess of Fe₂(CO)₉ gives a trimetallic bridging carbyne complex, [MnFe₂(μ₃-CC₆H₅)(CO) ₇(NO)(η-C₅H₅)] (17). Complexes 12 and 13 also react with Fe₂(CO)₉, leading to loss of the PPh₃ ligand to afford trimetallic bridging carbyne complexes [MnFeCo(μ₃-CC₆H₅)(CO) ₈(η-C₅H₅)] (18) and [ReFeCo(μ₃-CC₆H₅)-(CO) ₈(η-C₅H₅)] (19), respectively. The structures of 10, 13, and 15 have been established by X-ray diffraction studies.

Full text of DOI:10.1021/om9906262

72
Organometallics 2000, 19, 72-80
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 Ca r bon ylm eta l An ion s Con ta in in g
Cyclop en ta d ien yl, P P h 3, a n d NO Liga n d s. A Rou te to
Dim eta l Br id gin g Ca r byn e Com p lexes
Yongjun Tang, J ie Sun, and J iabi Chen*
Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, People’s Republic of China
Received August 5, 1999
The reactions of cationic carbyne complexes of manganese and rhenium, [η-C5H5(CO)2Mt
CC6H5]BBr4 (1, M ) Mn; 2, M ) Re), with Na[η-C5H5Mo(CO)3] (3) in THF at low temperature
afford η1,η2-ketene complexes [MnMo{C(CO)C6H5}(CO)4(η-C5H5)2] (8) and [ReMo{C(CO)-
C6H5}(CO)4(η-C5H5)2] (9), respectively. Analogous reactions of Na[η-C5H5W(CO)3] (4) with 1
and 2 give the corresponding ketene complexes [MnW{C(CO)C6H5}(CO)4(η-C5H5)2] (10) and
[ReW{C(CO)C6H5}(CO)4(η-C5H5)2] (11). Na[Co(CO)3PPh3] (5) also reacts with 1 and 2 to yield
ketenyl-bridged complexes [MnCo{C(CO)C6H5}(CO)4(PPh3)(η-C5H5)] (12) and [ReCo{C(CO)-
C6H5}(CO)4(PPh3)(η-C5H5)] (13), respectively. However, compound Na[η-C5H5Fe(CO)2] (6)
reacts only with 2 to form a η1,η2-ketene complex [ReFe{C(CO)C6H5}(CO)3(η-C5H5)2] (14),
while the reactions of (Ph3P)2N[Fe(CO)3NO] (7) with 1 and 2 produce dimetal bridging
carbyne complexes [MnFe(µ-CC6H5)(CO)4(NO)(η-C5H5)] (15) and [ReFe(µ-CC6H5)(CO)4(NO)-
(η-C5H5)] (16), respectively. Compound 15 treated with an excess of Fe2(CO)9 gives a
trimetallic bridging carbyne complex, [MnFe2(µ3-CC6H5)(CO)7(NO)(η-C5H5)] (17). Complexes
12 and 13 also react with Fe2(CO)9, leading to loss of the PPh3 ligand to afford trimetallic
bridging carbyne complexes [MnFeCo(µ3-CC6H5)(CO)8(η-C5H5)] (18) and [ReFeCo(µ3-CC6H5)-
(CO)8(η-C5H5)] (19), respectively. The structures of 10, 13, and 15 have been established by
X-ray diffraction studies.
In tr od u ction
with low-valent metal species or by reactions7-9 of
neutral or anionic carbyne complexes with metal hy-
drides or cationic metal compounds. In our laboratory,
one of the synthetic methods of bridging carbene and
carbyne complexes is to conduct reactions of the highly
electrophilic cationic carbyne complexes of manganese
and rhenium, [η-C5H5(CO)2MntCC6H5]BBr4 (1) and
[η-C5H5(CO)2RetCC6H5]BBr4 (2), with carbonylmetal
anion compounds such as Na2[Fe(CO)4], (Et4N)2[Fe2-
(CO)8], (Me4N)[HFe(CO)4], Na2[W(CO)5], and (Ph3P)2N-
[FeCo(CO)8] or (Ph3P)2N[WCo(CO)9] to form the hetero-
nuclear dimetal bridging carbene or bridging carbyne
complexes.10-14 This represents a new route to dimetal
The current considerable interest in the synthesis and
study of a variety of metal-metal-bonded cluster com-
plexes is largely due to their important role in many
catalytic processes.1-3 Since many transition metal
bridging carbene and carbyne complexes are the metal
clusters themselves or are the precursors of metal
cluster complexes, the chemistry of transition metal
bridging carbene and carbyne complexes are areas of
current interest. In this regard, we are interested in
developing the methodology of the synthesis of transi-
tion metal bridging carbene and carbyne complexes. The
transition metal bridging carbene and carbyne com-
plexes have been examined extensively by Stone and
co-workers. A great number of dimetal bridging carbene
and carbyne complexes have been synthesized by them
by the reactions4-6 of carbene or alkylidyne complexes
(5) (a) Ashworth, T. V.; Howard, J . A.; Laguna, K. M.; Stone, F. G.
A. J . Chem. Soc., Dalton Trans. 1980, 1593. (b) Berry, M.; Howard, J .
A. K.; Stone, F. G. A. J . Chem. Soc., Dalton Trans. 1980, 1601. (c)
Carriedo, G. A.; Howard, J . A. K.; Stone, F. G. A. J . Chem. Soc., Dalton
Trans. 1984, 1555.
(6) (a) Garcia, M. E.; J effery, J . C.; Sherwood, P.; Stone, F. G. A. J .
Chem. Soc., Dalton Trans. 1987, 1209. (b) Evans, D. G.; Howard, J .
A.. K.; J effery, J . C.; Lewis, D. B.; Lewis, G. E.; Grosse-Ophoff, M. J .;
Parrott, M. J .; Stone, F. G. A. J . Chem. Soc., Dalton Trans. 1986, 1723.
(c) Busetto, L.; J effery, J . C.; Mills, R. M.; Stone, F. G. A.; Went, M. J .;
Woodward, P. J . Chem. Soc., Dalton Trans. 1983, 101.
(7) Hodgson, D.; Howard, J . A. K.; Stone, F. G. A.; Went, M. J . J .
Chem. Soc., Dalton Trans. 1985, 331.
(8) Pilotti, M. U.; Stone, F. G. A.; Topaloglu, L. J . Chem. Soc., Dalton
Trans. 1991, 1621.
(9) Howard, J . A. K.; Mead, K. A.; Moss, J . R.; Navarro, R.; Stone,
F. G. A.; Woodward, P. J . Chem. Soc., Dalton Trans. 1981, 743.
(10) (a) Chen, J .-B.; Yu, Y.; Liu, K.; Wu, G.; Zheng, P.-J . Organo-
metallics 1993, 12, 1213. (b) Yu, Y.; Chen, J .-B.; Chen, J .; Zheng, P.-
J .; J . Chem. Soc., Dalton Trans. 1996, 1443.
(1) Stone, F. G. A.; West, R. 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) Gates, B. C.
In Metal-Metal Bonds and Clusters in Chemistry and Catalysis;
Fackler, J . P., J r., Ed.; Plenum: New York, 1990; p 127.
(3) (a) Poilblance, R. Inorg. Chim. Acta 1982, 62, 75. (b) Green, M.
L. H.; McGowan, C.; Morise, X. Polyhedron 1994, 13, 2971. (c) Dickson,
R. S.; C.Greaves, B. Organometallics 1993, 12, 3249.
(4) Stone, F. G. A. In Advances in Metal Carbene Chemistry;
Schubert, U., Ed.; Kluwer Academic Publishers: Dordrecht, The
Netherlands, 1989; p 11.
10.1021/om9906262 CCC: $19.00 © 2000 American Chemical Society
Publication on Web 12/11/1999

Reactions of Cationic Carbyne Complexes
Organometallics, Vol. 19, No. 1, 2000 73
bridging carbene and bridging carbyne complexes. We
found that the reactivity and resulting products depend
not only on the central metal10,15 of the cationic carbyne
complexes but also on the carbonylmetal anions. For
instance, the carbonyliron anion compound (Me4N)[HFe-
(CO)4] reacted with cationic carbyne complex 1 to give
a novel Mn-Fe dimetal bridging carbene complex (eq
1), in which a hydride migrated from the Fe atom of
the HFe(CO)4 moiety to the bridging carbene carbon
with the bonding of the Fe atom to the Mn atom to
construct a dimetalclopropane ring,12 whereas the reac-
similar bridging carbene complexes but phenyl(penta-
carbonylcyanotungsten)carbenemanganese and -rhe-
nium complexes [η-C5H5(CO)2MdC(C6H5)NCW(CO)5]
(M ) Mn or Re) (eq 5).15 Unexpectedly, the reaction of
the isothiocyano-substituted carbonyltungsten anion
compound (Ph3P)2N[W(CO)5SCN] with 1 led to loss of
the sulfur atom to give a novel phenyl(pentacarbonyl-
isocyanotungsten)carbenemanganese complex [η-C5H5-
(CO)2MndC(C6H5)CNW(CO)5] (eq 6),15 but the analo-
gous reaction with 2 yielded an (isothiocyanato)phenyl-
carbenerhenium complex [η-C5H5(CO)2RedC(C6H5)-
SCN].15
tions of the cyano-substituted carbonyliron anion com-
pound Na[Fe(CO)4CN] with cationic carbyne complexes
1 and 2 gave phenyl(tetracarbonylcyanoiron)carbene-
manganese and -rhenium complexes [η-C5H5(CO)2Md
C(C6H5)NCFe(CO)4] (M ) Mn, Re) (eq 2),11 respectively.
In contrast to monometal carbonyl anion, the mixed-
dimetal carbonyl anion compounds such as (PPh3)2N-
[FeCo(CO)8] reacted with complex 1 and 2 to yield
heteronuclear dimetal bridging carbyne complexes [MCo-
(µ-CC6H5)(CO)5(η-C5H5)] (M ) Mn, Re) and bridging
carbene complexes [MCo(µ-C(CO)C6H5)(CO)5(η-C5H5)]
(M ) Mn, Re) (eq 3).14
To investigate the scope of this new synthetic method
for dimetal bridging carbene and carbyne complexes and
further examine the effect of different metalcarbonyl
anions containing a bulky subsitituent of cyclopentadi-
enyl and PPh3 or a three-electron ligand of NO on the
reactivity of the cationic carbyne complexes and reaction
products, we chose metalcarbonyl anion compounds of
group VIB, such as Na[η-C5H5Mo(CO)3] (3) and Na[η-
C5H5W(CO)3] (4), and of group VIII, such as Na[Co-
(CO)3PPh3] (5), Na[η-C5H5Fe(CO)2] (6), and (Ph3P)2N[Fe-
(CO)3NO] (7), as nucleophiles for the reactions with
cationic carbyne complexes of manganese and rhenium,
1 and 2. In this paper we describe these unusual
(11) Tang, Y.-J .; Sun, J .; Chen, J .-B. Organometallics 1999, 18, 4337.
(12) Tang, Y.-J .; Sun, J .; Chen, J .-B. J . Chem. Soc., Dalton Trans.
1998, 931.
(13) Tang, Y.-J .; Sun, J .; Chen, J .-B. J . Chem. Soc., Dalton Trans.
1998, 4003.
(14) Tang, Y.-J .; Sun, J .; Chen, J .-B. Organometallics 1998, 17, 2945.
(15) Tang, Y.-J .; Sun, J .; Chen, J .-B. Organometallics 1999, 18, 2459.
In addition, compound Na2[W(CO)5] also reacted with
1 and 2 to yield Mn-W and Re-W dimetal bridging
carbene complexes [MW{µ-C(H)C6H5}(CO)7(η-C5H5)] (M
) Mn or Re) (eq 4),13 respectively, whereas Na-
[W(CO)5CN] reacted with complex 1 and 2 to afford no

74 Organometallics, Vol. 19, No. 1, 2000
Tang et al.
above with 0.153 g (0.21 mmol) of 2 at -90 to -45 °C for 6 h.
Further treatment of the resulting solution as described in the
reaction of 1 with 3 afforded 0.14 g (90%, based on 2) of 9 as
brown-red crystals: mp 81-82 °C dec; IR (CH2Cl2) ν CO 2054
reactions and the structural characterizations of the
resulting products.
Exp er im en ta l Section
(m), 2023 (sh), 1984 (s), 1945 (vs, br), 1911 (s),1886 (w) cm-1
;
1H NMR (CD3COCD3) δ 7.37 (m, 2H, C6H5), 7.28 (m, 2H, C6H5),
All reactions were performed under a dry, oxygen-free N2
atmosphere by using standard Schlenk techniques. All solvents
employed were reagent grade and dried by refluxing over
appropriate drying agents and stored over 4 Å molecular sieves
under N2. The tetrahydrofuran (THF) and diethyl ether (Et2O)
were distilled from sodium benzophenone ketyl, while petro-
leum ether (30-60 °C) and CH2Cl2 were distilled from CaH2.
The neutral SiO2 (Scientific Adsorbents Incorporated, 40
microns Flash) used for chromatography was deoxygenated at
room temperature under high vacuum for 12 h, and the neutral
alumina (Al2O3) was deoxygenated under high vacuum for 16
h, deactivated with 5% w/w N2-saturated water, and stored
under N2. Complexes [η-C5H5(CO)2MntC C6H5]BBr4 (1)16 and
[η-C5H5(CO)2RetCC6H5]BBr4 (2)17 were prepared as previously
described. Compounds Na[η-C5H5Mo(CO)3] (3),18 Na[η-C5H5W-
(CO)3] (4),18 Na[Co(CO)3PPh3] (5),19 Na[η-C5H5Fe(CO)2] (6),20,21
and (Ph3P)2N[Fe(CO)3NO] (7)22 were prepared by literature
methods.
7.25 (m, 1H, C6H5), 5.63 (s, 5H, C5H5), 5.39 (s, 5H, C5H5); MS
m/e 642 (M+), 558 (M+ - 3CO), 530 (M+ - 4CO), 502 (M+
-
5CO), 336 [C5H5Re(CO)3+], 308 [C5H5Re(CO)2+], 280 [C5H5Re-
(CO)+]. Anal. Calcd for C22H15O5ReMo: C, 41.19; H, 2.36.
Found: C, 41.40; H, 2.14.
Rea ction of 1 w ith Na [η-C5H5W(CO)3] (4) To Give
[Mn W{C(CO)C6H5}(CO)4(η-C5H5)2] (10). To 5 mL of 0.8%
Na/Hg in 50 mL of THF was added 0.268 g (0.40 mmol) of
[η-C5H5W(CO)3]2. The mixture was stirred at room tempera-
ture for 2 h. The resulting light yellow solution of Na[η-C5H5W-
(CO)3]18 was cooled to -90 °C, then poured rapidly on to 0.432
g (0.73 mmol) of 1 previously cooled to -90 °C. Immediately
the orange-red solution turned deep red. The mixture was
stirred at -90 to -45 °C for 5 h, during which time the solution
gradually turned dark red. Further treatment of the resulting
solution as described in the reaction of 1 with 3 gave 0.22 g
(92%, based on 1) of reddish-brown crystalline 10: mp 109-
111 °C dec; IR (CH2Cl2) ν CO 2054 (w), 2008 (sh), 1985 (s),
1940 (vs,br), 1916 (s), 1886 (w) cm-1; 1H NMR (CD3COCD3) δ
7.46 (m, 2H, C6H5), 7.34 (m, 2H, C6H5), 7.13 (m, 1H, C6H5),
5.62 (s, 5H, C5H5), 4.71 (s, 5H, C5H5); MS m/e 598 (M+), 570
(M+ - CO), 542 (M+ - 2CO), 514 (M+ - 3CO), 204 [C5H5Mn-
(CO)3+]. Anal. Calcd for C22H15O5MnW: C, 44.18; H, 2.53.
Found: C, 44.18; H, 2.58.
The IR spectra were measured on a Shimadzu-IR-440
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 Na -
[η-C5H5Mo(CO)3] (3) To Give [Mn Mo{C(CO)C6H5}(CO)4-
(η-C5H5)2] (8). To a 5 mL of 0.8% Na/Hg in 50 mL of THF
was added 0.107 g (0.22 mmol) of [η-C5H5Mo(CO)3]2. The
mixture was stirred at room temperature for 2 h. The resulting
light yellow solution of Na[η-C5H5Mo(CO)3]18 was cooled to -90
°C, then poured rapidly on to 0.259 g (0.43 mmol) of 1
previously cooled to -90 °C. Immediately the orange-red
solution turned deep red. The mixture was stirred at -90 to
-45 °C for 7 h, during which time the solution gradually
turned dark red. The resulting solution was evaporated under
high vacuum at -45 to -40 °C to dryness. The residue was
chromatographed on an alumina column (1.6 × 15 cm) at -25
°C with petroleum ether as the eluant. After elution of a small
pink band which contained unreacted [η-C5H5Mo(CO)3]2 from
the column, the brown-red band was eluted with petroleum
ether/CH2Cl2/Et2O (10:1:1) and collected. The solvent was
removed under vacuum, and the residue was recrystallized
from petroleum ether/CH2Cl2 solution at -80 °C to give 0.22
g (93%, based on 1) of brown-red crystals of 8: mp 73-74 °C
dec; IR (CH2Cl2) ν CO 2051 (s), 2022 (m), 1988 (s), 1934 (vs,
br), 1888 (sh) cm-1; 1H NMR (CD3COCD3) δ 7.44 (m, 2H, C6H5),
7.33 (m, 2H, C6H5), 7.16 (m, 1H, C6H5), 5.45 (s, 5H, C5H5), 4.73
Rea ction of 2 w ith 4 To Give [ReW{C(CO)C6H5}(CO)4-
(η-C5H5)2] (11). Similar to that described for the reaction of 1
with 4, compound 2 (0.153 g, 0.21 mmol) was treated with a
fresh Na[η-C5H5Mo(CO)3] solution prepared by reaction of
[η-C5H5W(CO)3]2 (0.070 g, 0.11 mmol) with 1.5 mL of 0.8% Na/
Hg in 40 mL of THF at -90 to -45 °C for 6 h. Further
treatment of the resulting solution as described in the reaction
of 1 with 3 afforded 0.14 g (90%, based on 2) of reddish-brown
crystals of 11: mp 81-82 °C dec; IR (CH2Cl2) ν CO 2048 (m),
1985 (s), 1942 (vs,br), 1908 (s), 1860 (w) cm-1 1H NMR
;
(CD3COCD3) δ 7.36 (m, 2H, C6H5), 7.30 (m, 2H, C6H5), 7.05
(m, 1, C6H5), 5.63 (s, 5H, C5H5), 5.38 (s, 5H, C5H5); MS m/e
729 (M+), 701 (M+ - CO), 673 (M+ - 2CO), 645 (M+ - 3CO),
617 (M+ - 4CO), 589 (M+ - 5CO), 336 [C5H5Re(CO)3+], 308
[C5H5Mn(CO)2+]. Anal. Calcd for C22H15O5ReW: C, 36.23; H,
2.07. Found: C, 36.36; H, 2.11.
Rea ction of 1 w ith Na [Co(CO)3P P h 3] (5) To Give
[Mn Co{C(CO)C6H5}(CO)4(P P h 3)(η-C5H5)] (12). To 6 mL of
0.8% Na/Hg in 50 mL of THF was added 0.391 g (0.48 mmol)
of [Co(CO)3PPh3]2. The mixture was stirred at room temper-
ature for 2 h. The resulting yellow solution of Na[Co-
(CO)3PPh3]19 was cooled to -90 °C, then poured rapidly onto
0.518 g (0.87 mmol) of 1 previously cooled to -90 °C. The red
solution turned immediately dark red. The mixture was stirred
at -90 to -45 °C for 5 h, during which time the solution
gradually turned blackish red. The resulting solution was
evaporated under vacuum at -50 to -40 °C to dryness, and
the residue was chromatographed on silica gel at -25 °C with
petroleum ether followed by petroleum ether/CH2Cl2 (5:1) as
the eluant. A blackish-green band was eluted and collected.
After removal of the solvent in vacuo, the dark green residue
was recrystallized from petroleum ether/CH2Cl2 solution at
-80 °C to give 0.62 g (89%, based on 1) of blackish-green
crystals of 12: mp 80-81 °C dec; IR (CH2Cl2) ν CO 2054 (m),
2018 (s), 1957 (vs, br), 1905 (w), 1863 (sh), 1766 (m) cm-1; 1H
NMR (CD3COCD3) δ 7.52 (m, 5H, C6H5), 7.36 (m, 10H, C6H5),
7.10 (m, 5H, C6H5), 5.62 (s, 5H, C5H5); MS m/e 670 (M+), 614
(M+ - 2CO), 586 (M+ - 3CO), 204 [C5H5Mn(CO)3+], 176 [C5H5-
Mn(CO)2+]. Anal. Calcd for C35H25O5PMnCo‚CH2Cl2: C, 57.24;
H, 3.60. Found: C, 57.29; H, 3.80.
(s, 5H, C5H5); MS m/e 510 (M+), 482 (M+ - CO), 426(M+
-
3CO), 398 (M+ - 4CO), 370 (M+ - 5CO), 204 [C5H5Mn(CO)3+],
176 [C5H5Mn(CO)2+]. Anal. Calcd for C22H15O5MnMo: C, 51.79;
H, 2.96. Found: C, 51.73; H, 3.03.
Rea ction of [η-C5H5(CO)2RetCC6H5]BBr 4 (2) w ith 3 To
Give [ReMo{C(CO)C6H5}(CO)4(η-C5H5)2] (9). A fresh Na-
[η-C5H5Mo(CO)3] solution prepared by reaction of [η-C5H5Mo-
(CO)3]2 (0.051 g, 0.10 mmol) with 2.5 mL of 0.8% Na/Hg in 50
mL of THF was reacted in a manner similar to that described
(16) Fischer, E. O.; Meineke, E. W.; Kreissl, F. R. Chem. Ber. 1977,
110, 1140.
(17) Fischer, E. O.; Chen, J .-B.; Scherzer, K. J . Organomet. Chem.
1983, 253, 231.
(18) Ellis, J . E.; Flom, E. A. J . Organomet. Chem. 1975, 99, 263.
(19) Hieber, W.; Ekkehard, H. Chem. Ber. 1961, 94, 1417.
(20) King, R. B. J . Inorg. Nucl. Chem. 1963, 25, 1296.
(21) Angelici, R. J . Inorg. Synth. Vol. 28, 208.
(22) Connelly, N. G.; Gardner, C. J . Chem. Soc., Dalton Trans. 1976,
1525.

Reactions of Cationic Carbyne Complexes
Organometallics, Vol. 19, No. 1, 2000 75
Rea ction of 2 w ith 5 To Give [ReCo{C(CO)C6H5}(CO)4-
(P P h 3)(η-C5H5)] (13). Compound 2 (0.460 g, 0.63 mmol) was
treated, in a manner similar to that in the reaction of 1 with
5, with a fresh solution of Na[Co(CO)3PPh3] prepared by the
reaction of [Co(CO)3PPh3]2 (0.283 g, 0.35 mmol) with 4.5 mL
of 0.8% Na/Hg in 50 mL of THF at -90 to -45 °C for 6 h. The
resulting mixture was treated as described for the reaction of
1 with 5 to give 0.29 g (81%, based on 2) of 13 as blackish-
green crystals: mp 77-78 °C dec; IR (CH2Cl2) ν CO 2054 (w),
gradually turned dark red. After the solution was evaporated
at 0 °C under vacuum to dryness, the dark red residue was
chromatographed on SiO2 at -20 °C with petroleum ether/
CH2Cl2 (10:1) as the eluant. The purple-red band was eluted
and collected. The solvent was removed from the red eluate
in vacuo, and the crude product was recrystallized from
petroleum ether/CH2Cl2 at -80 °C to give 0.026 g (76%, based
on 15) of purple-red crystals of 17: mp 81-82 °C dec; IR
(CH2Cl2) ν CO 2065 (s), 2023 (vs), 2012 (sh), 1985 (w), 1963
2018 (vs), 1956 (vs, br), 1894 (vs), 1852 (sh), 1750 (m) cm-1
;
(m), 1925 (w), 1840 (m) cm-1 1H NMR (CD3COCD3) δ 7.92
;
1H NMR (CD3COCD3) δ 7.41 (m, 5H, C6H5), 7.29 (m, 10H,
C6H5), 7.06 (m, 5H, C6H5), 5.49 (s, 5H, C5H5); MS m/e 802 (M+),
774 (M+ - 2CO), 662 (M+ - 5CO), 336 [C5H5Re(CO)3+], 308
[C5H5Re(CO)2+]. Anal. Calcd for C35H25O5PReCo‚CH2Cl2: C,
48.77; H, 3.07. Found: C, 48.49; H, 3.06.
(m, 2H, C6H5), 7.62 (m, 2H, C6H5), 7.36 (m, 1H, C6H5), 4.96 (s,
5H, C5H5); MS m/e 547 (M+), 491 (M+ - 2CO), 351 (M+ - 7CO),
321 (M+ - 7CO - NO). Anal. Calcd for C19H10O8NMnFe2: C,
41.73; H, 1.84; N, 2.56. Found: C, 41.48; H, 1.91; N, 2.37.
Rea ction of 12 w ith F e2(CO)9 To Give [Mn F eCo(µ3-
CC6H5)(CO)8(η-C5H5)] (18). To 0.025 g (0.037 mmol) of 12
dissolved in 50 mL of THF at -20 °C was added 0.042 g (0.115
mmol) of Fe2(CO)9. The mixture was stirred at -20 to 5 °C for
6-7 h, during which time the orange-red solution gradually
turned brown-red. After removal of the solvent at 0 °C, the
dark red residue was chromatographed on SiO2 at -15 to -20
°C with petroleum ether/CH2Cl2 (10:1) as the eluant. The
purple-red band was eluted. The solvent was removed from
the red eluate in vacuo, and the crude product was recrystal-
lized from petroleum ether/CH2Cl2 at -80 °C to yield 0.020 g
(70%, based on 12) of purple-red crystals of 18:14 mp 91-92
°C dec; IR (CH2Cl2) ν CO 2078 (vs), 2054 (w), 2031 (vs), 1984
Rea ction of 2 w ith Na [η-C5H5F e(CO)2] (6) To Give
[ReF e{C(CO)C6H5}-(CO)3(η-C5H5)2] (14). To 0.50 mL of 0.8%
Na/Hg in 50 mL of THF was added 0.074 g (0.21 mmol) of
[η-C5H5Fe(CO)2]2. The mixture was stirred at room tempera-
ture for 2 h. The resulting light yellow solution of Na[η-C5H5-
Fe(CO)2]20,21 was cooled to -90 °C, then poured rapidly onto
0.306 g (0.42 mmol) of 2 previously cooled to -90 °C. The
orange-red solution turned rapidly dark red. After stirring at
-90 to -40 °C for 5-6 h, further treatment of the resulting
mixture as described in the reaction of 1 with 3 gave 0.18 g
(75%, based on 2) of brown-red crystals of 14: mp 92-95 °C
dec; IR (CH2Cl2) ν CO 2053 (s), 2008 (sh), 1968 (vs, br), 1925
(m), 1896 (m), 1884 (s) cm-1; 1H NMR (CD3COCD3) δ 7.46 (m,
2H, C6H5), 7.34 (m, 2H, C6H5), 7.13 (m, 1H, C6H5), 5.62 (s, 5H,
C5H5), 4.71 (s, 5H, C5H5); MS m/e 572 (M+), 544 (M+ - CO),
516 (M+ - 2CO), 488 (M+ - 3CO), 460 (M+ - 4CO), 336 [C5H5-
Re(CO)3+], 308 [C5H5Mn(CO)2+]. Anal. Calcd for C21H15O4-
ReFe: C, 43.99; H, 2.64. Found: C, 44.25; H, 2.91.
1
(w), 1963 (m), 1890 (s), 1831 (m) cm-1; H NMR (CD3COCD3)
δ 7.72 (m, 2H, C6H5), 7.51 (m, 2H, C6H5), 7.32 (m, 1H, C6H5),
4.89 (s, 5H, C5H5); MS m/e 548 (M+), 492 (M+ - 2CO), 464
(M+ - 3CO), 408 (M+ - 5CO), 380 (M+ - 6CO). Anal. Calcd
for C20H10O8MnFeCo: C, 43.83; H, 1.84. Found: C, 43.59; H,
2.04.
Rea ction of 1 w ith (P h 3P )2N[F e(CO)3NO] (7) To Give
[Mn F e(µ-CC6H5)-(CO)4(NO)(η-C5H5)] (15). To 0.605 g (1.02
mmol) of 1 dissolved in 50 mL of THF at -90 °C was added
0.719 g (1.02 mmol) of (Ph3P)2N[Fe(CO)3NO] with stirring. The
brick-red solution turned rapidly green. The mixture was
stirred at -90 to -45 °C for 6 h, during which time the green
solution turned blackish-green. After vacuum removal of the
solvent at -45 to -40 °C, the residue was chromatographed
on Al2O3 at -25 °C with petroleum ether/CH2Cl2 (5:1) as the
eluant, the blackish-green band was eluted. The solvent was
removed in vacuo, and the residue was recrystallized from
petroleum ether/CH2Cl2 solution at -80 °C to give 0.384 g
(93%, based on 1) of blackish-green crystals of 15: mp 86-87
°C dec; IR (CH2Cl2) ν CO 2054 (s), 1994 (m), 1970 (s), 1885
(w) cm-1; 1H NMR (CD3COCD3) δ 7.80 (m, 2H, C6H5), 7.61 (m,
2H, C6H5), 7.19 (m, 1H, C6H5), 5.07 (s, 5H, C5H5); MS m/e 379
(M+ - CO), 323 (M+ - 3CO), 204 [C5H5Mn(CO)3+], 176 [C5H5-
Mn(CO)2+]. Anal. Calcd for C16H10O5NMnFe: C, 47.21; H, 2.48;
N, 3.44. Found: C, 46.97; H, 2.36; N, 3.23.
Rea ction of 13 w ith F e2(CO)9 To Give [ReF eCo(µ3-
CC6H5)(CO)8(η-C5H5)] (19). Compound 13 (0.040 g, 0.050
mmol) was treated as described in the reaction of 12 with
Fe2(CO)9 with 0.073 g (0.201 mmol) of Fe2(CO)9 at -20 to 5 °C
for 7-8 h, during which time the orange-red solution gradually
turned dark red. Further treatment of the resulting solution
similar to that in the reaction of 12 with Fe2(CO)9 yielded 0.025
g (74%, based on 13) of blackish-red crystalline 19:14 mp 85-
87 °C dec; IR (CH2Cl2) ν CO 2073 (s), 2052 (w), 2025 (vs), 1970
(w), 1954 (w), 1908 (m), 1854 (m, br) cm-1; 1HNMR (CD3COCD3)
δ 7.53 (m, 2H, C6H5), 7.45 (m, 2H, C6H5), 7.22 (m, 1H, C6H5),
5.62 (s, 5H, C5H5); MS m/e 650 (M+ - CO). Anal. Calcd for
C
20H10O8ReFeCo: C, 35.36; H, 1.48. Found: C, 35.36; H, 1.41.
X-r a y Cr ysta l Str u ctu r e Deter m in a tion s of Com p lexes
10, 13, a n d 15. Single crystals of complexes 10, 13, and 15
suitable for X-ray diffraction study were obtained by recrys-
tallization from petroleum ether/CH2Cl2 solution at -80 °C.
Single crystals were mounted on a glass fiber and sealed with
epoxy glue. The X-ray diffraction intensity data for 3485, 6273,
and 3271 independent reflections, of which 1852 and 3871 with
I > 2.50σ(I) for 10 and 13 and 2532 with I > 3.00σ(I) for 15
were observable, were collected with a Rigaku AFC7R diffrac-
tometer at 20 °C using Mo KR radiation with an ω -2θ scan
mode within the ranges 5° e 2θ e 50° for 10 and 13, 5° e 2θ
e 52° for 15, respectively.
The structures of 10, 13, and 15 were solved by direct
methods and expanded using Fourier techniques. For 10 and
15, the non-hydrogen atoms were refined anisotropically. The
hydrogen atoms of 10 were included but not refined, while the
hydrogen atoms of 15 were refined isotropically. For 13, the
some non-hydrogen atoms were refined anisotropically, while
the rest were refined isotropically. The hydrogen atoms were
included but not refined. The final cycle of full-matrix least-
squares refinement was respectively based on 1852, 3871, and
2532 observed reflections and 263, 410, and 258 variable
parameters and converged with unweighted and weighted
agreement factors of R ) 0.046 and Rw ) 0.046 for 10, R )
0.046 and Rw ) 0.052 for 13, and R ) 0.032 and Rw ) 0.039
Rea ction of 2 w ith 7 To Give [ReF e(µ-CC6H5)(CO)4-
(NO)(η-C5H5)] (16). Compound 2 (0.205 g, 0.28 mmol) was
treated, in a manner similar to that in the reaction of 1 with
7, with (Ph3P)2N[Fe(CO)3NO] (0.20 g, 0.28 mmol) at -90 to
-45 °C for 6 h. Further treatment of the resulting solution as
described in the reaction of 1 with 7 gave 0.130 g (86%, based
on 2) of blackish-green crystals of 16: mp 96-97 °C dec; IR
(CH2Cl2) ν CO 2053 (s), 2024 (m), 1963 (vs, br), 1900 (w), cm-1
;
1H NMR (CD3COCD3) δ 7.90 (m, 1H, C6H5), 7.62 (m, 3H, C6H5),
7.57 (m, 1H, C6H5), 5.26 (s, 5H, C5H5); MS m/e 539 (M+), 511
(M+ - CO), 483 (M+ - 2CO), 455 (M+ - 3CO), 427 (M+ - 4CO),
397 (M+ - 4CO - NO), 336 [C5H5Re(CO)3+]. Anal. Calcd for
C
16H10O5NMnFe: C, 47.21; H, 2.48; N, 3.44. Found: C, 46.97;
H, 2.36; N, 3.23.
Rea ction of 15 w ith F e2(CO)9 To Give [Mn F e2(µ3-
CC6H5)(CO)7(NO)(η-C5H5)] (17). To 0.025 g (0.061 mmol) of
15 dissolved in 50 mL of THF at -20 °C was added 0.085 g
(0.234 mmol) of Fe2(CO)9. The mixture was stirred at -5 to 0
°C for 6 h, during which time the blackish-green solution

76 Organometallics, Vol. 19, No. 1, 2000
Ta ble 1. Cr ysta l Da ta a n d Exp er im en ta l Deta ils for Com p lexes 10, 13, a n d 15
Tang et al.
10
13‚CH2Cl2
15
formula
fw
C
22H15O5MnW
C36H27O5Cl2PReCo
886.63
C16H10O5NFeMn
407.04
598.15
space group
a (Å)
b ( Å)
P21/c (No. 14)
9.582(2)
12.966(3)
15.807(2)
99.09(1)
1939.2(6)
4
2.049
1144.00
66.17
P21/a (No. 14)
15.835(3)
12.552(3)
17.131(2)
95.11(1)
3391(1)
4
1.736
1736.00
P21/c (No. 14)
7.684(2)
14.802(3)
14.202(3)
99.65(3)
1592.5(7)
4
1.689
c (Å)
â (deg)
V ( Å3)
Z
Dcalcd (g /cm3)
F(000)
816.00
17.27
Mo KR (λ ) 0.71069 Å)
µ(Mo KR) (cm-1
)
43.03
radiation (monochromated
in incident beam)
diffractometer
Mo KR (λ ) 0.71069 Å)
Mo KR (λ ) 0.71069 Å)
Rigaku AFC7R
20
Rigaku AFC7R
20
Rigaku AFC7R
20
temperature (°C)
orientation reflections: no.;
range (2θ) (deg)
18; 14.0-16.2
17; 13.5-21.3
25; 18.3-21.6
scan method
ω-2θ
5-50
3485
1852
263
0.7016-1.0000
0.046
0.046
1.25
0.00
0.86
ω-2θ
5-50
6273
3871
410
0.9283-1.0000
0.046
0.052
1.43
0.02
1.50
ω-2θ
data coll. range, 2θ (deg)
no. of unique data, total
with I > 2.50σ(I)
5-52
3271
2532 (I >3.00σ(I))
258
0.8145-1.0000
0.032
0.039
1.53
0.00
0.47
no. of params refined
correction factors, max. min.
Ra
b
Rw
quality-of-fit indicatorc
largest shift/esd final cycle
largest peak, e-/Å3
min. peak, e-/Å3
-1.36
-1.72
-0.56
a
b
2
R ) ∑||Fo| - |Fc||/∑|Fo|. Rw ) [∑w(|Fo| - |Fc|)2/∑w|Fo| ]1/2; w ) 1/σ2(|Fo|). c Quality-of-fit ) [∑w(|Fo| - |Fc|)2/(Nobs - Nparameters)]1/2
.
Ta ble 2. Selected Bon d Len gth s (Å)a a n d An gles (d eg)a for Com p lexes 10 a n d 13
10 (M ) Mn,
M′ ) W)
13 (M ) Re,
M′ ) Co)
10 (M ) Mn,
M′ ) W)
13 (M ) Re,
M′ ) Co)
M-M′
2.905(2)
2.05(1)
2.15(1)
2.25(2)
1.38(2)
1.21(2)
1.48(2)
44.9(3)
47.5(4)
87.5(5)
63.8(4)
75.6(9)
36.7(5)
67.7(8)
147(1)
144(1)
2.717(2)
2.136(10)
2.00(1)
1.94(1)
1.40(1)
1.20(1)
1.48(1)
51.2(3)
46.8(3)
82.0(3)
71.6(3)
66.8(6)
41.7(4)
71.4(6)
147(1)
M-C(1)
1.78(2)
1.81(2)
1.94(2)
1.92(2)
1.89(1)
1.88(1)
1.80(1)
1.79(1)
2.196(3)
2.30
M-C(8)
M-C(2)
M′ -C(8)
M′ -C(3)
M′ -C(7)
M′ -C(4)
C(7)-C(8)
M′ -P
C(7)-O(7)
M-C(Cp) (av)
M′-C(Cp) (av)
M-C(8)-C(14)
M′-C(8)-C(14)
M-M′-P
2.14
2.34
129.8(9)
130.7(9)
C(8)-C(14)
M-M′-C(8)
M′-M-C(8)
M-C(8)-M′
M-M′-C(7)
M′-C(8)-C(7)
C(8)-M′-C(7)
M′-C(7)-C(8)
C(8)-C(7)-O(7)
M′-C(7)-O(7)
132.6(7)
131.3(7)
160.51(9)
110.4(3)
90.2(3)
176.4(10)
175(1)
178(1)
P-M′-C(8)
P-M′-C(7)
M-C(1)-O(1)
M-C(2)-O(2)
M′-C(3)-O(3)
M′-C(4)-O(4)
174(1)
170(1)
178(1)
178(1)
140.7(9)
174(1)
a
Estimated standard deviations in the least significant figure are given in parentheses.
Ta ble 3. Selected Bon d Len gth s (Å)a a n d An gles
(d eg)a for Com p lex 15
for 15, respectively. All the calculations were performed using
the teXsan crystallographic software package of Molecular
Structure Corporation.
Mn-Fe
2.6494(3)
1.865(3)
1.853(3)
1.658(3)
1.177(3)
1.455(3)
44.72(8)
44.37(2)
90.9(1)
Mn-C(1)
1.796(3)
1.816(3)
1.787(3)
1.852(3)
2.15
123.09(9)
179.2(3)
168.6(3)
176.0(3)
179.5(3)
108.3(1)
Mn-C(8)
Mn-C(2)
The details of the crystallographic data and the procedures
used for data collection and reduction information for 10, 13,
and 15 are given in Table 1. The selected bond lengths and
angles are listed in Tables 2 and 3, respectively. The atomic
coordinates and Biso/Beq, anisotropic displacement parameters,
complete bond lengths and angles, and least-squares planes
for 10, 13, and 15 are given in the Supporting Information.
The molecular structures of 10, 13, and 15 are given in Figures
1, 2, and 3, respectively.
Fe-C(8)
Fe-C(3)
Fe-C(4)
Mn-C(Cp) (av)
Mn-Fe-N
Mn-C(1)-O(1)
Mn-C(2)-O(2)
Fe-C(3)-O(3)
Fe-C(4)-O(4)
C(8)-Fe-N
Fe-N
N-O(5)
C(8)-C(14)
Mn-Fe-C(8)
Fe-Mn-C(8)
Mn-C(8)-Fe
Mn-C(8)-C(14)
Fe-C(8)-C(14)
137.0(2)
132.1(2)
a
Estimated standard deviations in the least significant figure
are given in parentheses.
Resu lts a n d Discu ssion
After vacuum removal of the solvent, the residue was
chromatographed on an alumina column at low tem-
perature, and the crude products were recrystallized
from petroleum ether/CH2Cl2 solution at -80 °C to give
The complex [η-C5H5(CO)2MntCC6H5]BBr4 (1) was
treated with equimolar quantity of Na[η-C5H5Mo(CO)3]
(3) in THF at low temperature (-90 to -45 °C) for 7 h.

Reactions of Cationic Carbyne Complexes
Organometallics, Vol. 19, No. 1, 2000 77
a ketenyl-bridged Mn-Mo complex [MnMo{C(CO)C6H5}-
(CO)4(η-C5H5)2] (8) (eq 7) in 93% yield. The analogous
reaction of [η-C5H5(CO)2RetCC6H5]BBr4 (2) with 3
under the same conditions afforded a ketenyl-bridged
Re-Mo complex [ReMo{C(CO)C6H5}(CO)4-(η-C5H5)2] (9)
(eq 8) in 90% yield.
F igu r e 1. Molecular structure of 10, showing the atom-
numbering scheme.
Fischer et al.23 by the reaction of [η-C5H5(CO)2Mnt
CC6H5]BCl4 with Na[Re(CO)5] and [MMn{{µ-C(CO)-
C6H4Me-p}(CO)6(η-C5H5)] (M ) Mn or Re) reported by
Stone and co-workers24 by the reactions of [η-C5H5-
(CO)2MtCC6H4Me-p]BF4 (M ) Mn or Re) with (Ph3P)2N-
[Mn(CO)5]. The X-ray diffraction study for complex 10
was carried out in order to firmly establish its structure.
The results of the X-ray diffraction work are sum-
marized in Table 1, and the structure is shown in Figure
1.
Like 3, compound Na[η-C5H5W(CO)3] (4) also reacted
with complexes 1 and 2 under the same conditions to
produce ketenyl-bridged Mn-W and Re-W complexes
[MnW{C(CO)C6H5}(CO)4(η-C5H5)2] (10) (eq 9) and [ReW-
{C(CO)C6H5}(CO)4(η-C5H5)2] (11) (eq 10) in 92% and
90% yields, respectively.
The structure of complex 10 resembled that of analo-
gous complexes [ReMn{µ-C(CO)C6H5}(CO)6(η-C5H5)]23
and [Mn2{{µ-C(CO)C6H4Me-p}(CO)6(η-C5H5)].24 In 10
the Mn-W bond (2.905(2) Å) is asymmetrically bridged
by the R-carbon atom of a phenyl ketenyl group [Mn-
C(8) 2.05(1), W-C(8) 2.15(1) Å]. A unique feature of the
structure is the presence of the C(7)O(7) group bonded
to C(8) with a C(7)-O(7) distance of 1.21(2) Å and a
C(8)-C(7) distance of 1.38(2) Å. The former distance
might correspond either to a CdO or to a CtO bond.
The latter distance, however, suggests CdC character
so that the C(CO)C6H5 group might be regarded as a
one-electron ketene bridge C6H5CdCdO rather than a
three-electron ylide bridge C-(C6H5)dC+dO across the
metal-metal bond.24 Thus, complexes 8-11 might be
better described as η1,η2-ketene complexes (A or A′)
(Scheme 1, see below).
The W-C(7) distance [2.25(2) Å] is much longer than
the corresponding Co-C(7) distance in [ReCo{µ-C(CO)-
C6H5}(CO)5(η-C5H5)] (1.987(8) Å)14 since the radius of
tungsten is larger than that of cobalt. Since the radii of
Mn and Re atoms are nearly the same, the metal-metal
bond distance in 10 is comparable with the longer Re-W
separation in analogous bridging carbene complexes
Compounds 8-11 are readily soluble in polar organic
solvents but sparingly soluble in nonpolar solvents.
They are air-sensitive in solution but relatively stable
as the solid. On the basis of elemental analyses, spec-
troscopic evidence, and X-ray crystallography, products
8-11 are formulated as possessing a ketenyl ligand
bonded to a carbene carbon atom, similar to the com-
plex [ReMn{µ-C(CO)C6H5}(CO)6(η-C5H5)] reported by
(23) Orama, O.; Schubert, U.; Kreissl, F. R.; Fischer, E. O. Z.
Naturforsch. B 1980, 35, 82.
(24) Martin-Gil, J .; Howard, J . A. K.; Navarro, R.; Stone, F. G. A.
J . Chem. Soc., Chem. Commun. 1979, 1168.

78 Organometallics, Vol. 19, No. 1, 2000
Tang et al.
Sch em e 1
[ReW{µ-C(H)C6H5}(CO)7(η-C5H5)] (3.0233(5) Å)13 and
(PPh3)2N[ReW{µ-C((H)C6H4Me-4}(CO)9] (3.033(1) Å).25
The C(8)-Mn linkage (2.05(1) Å) in 10 is close in value
to the similar bond in the bridging carbene complex
[MnFe{µ-C(COEt)C6H5}(CO)5(η-C5H5)] (2.021(4) Å)26
but is obviously longer than the similar bond in bridging
carbyne complexes [(CO)(η-C5H5)Fe(µ-COEt)(µ-CO)Mn-
(η-C5H4Me)(CO)] (1.839(4) Å)27 and [MnCo(µ-CC6H5)-
(CO)5(η-C5H5)] (1.85(1) Å).14
F igu r e 2. Molecular structure of 13, showing the atom-
numbering scheme. CH2Cl2 has been omitted for clarity.
The possible reaction pathway to complexes 8-11 (eqs
7-10) could involve initial formation of a carbene
intermediate [η-C5H5(CO)2MdC(C6H5)M′(CO)3(η-C5H5)]
(M ) Mn or Re, M′ ) Mo or W), where the M′(CO)3(η-
C5H5) moiety is directly bonded to the carbene carbon
through the M′ atom, by attack of the [M′(CO)3(η-
C5H5)]- anion on the cationic carbyne carbon of 1 or 2.
After initial metal-carbon bond formation, the migra-
tion of the M′dC bond of the carbene to a coordinated
CO gives a coordinatively unsaturated ketene complex
(B). Then addition of the MdCcarbene bond to the vacant
site at M′ completes the reaction to produce the η1,η2-
ketene complex (A or A′) (Scheme 1).
Interestingly, the PPh3-sustituted carbonylcobalt an-
ion compound Na[Co(CO)3PPh3] (5) can also react with
cationic carbyne complexes 1 and 2 to give PPh3-
coordinated ketenyl bridged complexes [MnCo{C(CO)-
C6H5}(CO)4(PPh3)(η-C5H5)] (12) (eq 11) and [ReCo-
{C(CO)C6H5}(CO)4(PPh3)(η-C5H5)] (13) (eq 12) in 89%
and 81% yields, respectively.
The formulas of complexes 12 and 13 are supported
by microanalytical and spectroscopic data as well as
X-ray crystallography. The formation pathway of com-
plexes 12 and 13 could be analogous to that of cyclo-
pentadienyl-substituted complexes 8-11.
The crystal structure of complex 13 shown in Figure
2 resembled that of [MCo{µ-C(CO)C6H5}(CO)5(η-C5H5)]
(M ) Mn, Re) synthesized14 by the reactions of (Ph3P)2-
NFeCo(CO)8 or (Ph3P)2NWCo(CO)9 with complexes 1
and 2, except that the substituents on the Co atom are
two CO and one PPh3 group in 13 but three CO ligands
in the latter. As expected, two terminal carbonyl groups
and one PPh3 ligand are attached to the Co and two
terminal CO to the Re atom. The Re-Co bond asym-
metrically bridged by the R-carbon atom of the ketenyl
group of C(CO)C6H5 [Re-C(8) 2.136(10), Co-C(8) 2.00(1)
Å] has a length of 2.717(2) Å, which is nearly the same
as that in [ReCo{µ-C(CO)C6H5}(CO)5(η-C5H5)] (2.720(1)
Å).14 The C(7)-O(7) and C(8)-C(7) bond lengths are
1.20(1) and 1.40(1) Å, respectively, which are the same
within experimental error as those in 10. Thus, the
C(CO)C6H5 group in 13 is also regarded as a ketenyl
ligand. The C(8)-Re distance is close to those in
bridging carbene complexes (PPh3)2N[ReW{µ-C(H)C6H4-
Me-4}(CO)9] (2.155(8) Å),25 [Re2(µ-H)2(µ-CHBut)(η-C6H6)]
(2.13(3) Å),28 and [ReFe{µ-C(H)C6H5}(CO)6(η-C5H5)]
(2.120(5) Å).10a
Unlike Mo, W, and Co anionic compounds 3, 4, and
5, the iron anion compound Na[η-C5H5Fe(CO)2] (6)
reacted only with 2 to form a ketenyl-bridged Re-Fe
complex [ReFe{C(CO)C6H5}(CO)3(η-C5H5)2] (14) (eq 13)
in a somewhat lower yield (75%), whose structure is
(25) J effery, J . C.; Orpen, A. G.; Stone, F. G. A.; Went, M. J . J . Chem.
Soc., Dalton Trans. 1986, 173.
(26) Yu, Y.; Chen, J .-B.; Chen, J .; Zheng, P.-J .J . Chem. Soc., Dalton
Trans. 1996, 1443.
1
supported by its elemental analysis and IR, H NMR,
(27) Fong, R. H.; Lin, C.-H.; Idmoumaz, H.; Hersh, W. H. Organo-
metallics 1993, 12, 503.
(28) Bandy, A.; Cloke, F. G. N.; Green, M. L. H.; O’Hare, D.; Prout,
K. J . Chem. Soc., Chem. Commun. 1984, 240.

Reactions of Cationic Carbyne Complexes
Organometallics, Vol. 19, No. 1, 2000 79
and mass spectra and by comparison of the 1H NMR
spectrum of 14 with those of complexes 8-11.
Fe distance (1.853(3) Å) in 15 is as expected for a CdFe
bond, which is obviously shorter than the correspond-
ing distance in [MnFe{µ-C(COEt)C6H5}(CO)5(η-C5H5)]
(2.020(4) Å).26
The possible reaction pathway to complexes 15 and
16 (eqs 14 and 15) could proceed via a synthon for
[Fe(CO)2NO]-, analogous to the reactions14 of (PPh3)2N-
[FeCo(CO)8] with complexes 1 and 2 (eq 3). The latter
was assumed via a synthon for Co(CO)3-, which at-
tacked on the carbyne carbon of cationic 1 or 2 with
bonding of the Co atom to the Mn or Re atom to
construct a dimetallacyclopropene ring. The synthon of
[Fe(CO)2NO]- could come from either an [Fe(CO)3NO]-
anion that lost a CO ligand in the presence of 1 or 2 or
a carbene intermediate [η-C5H5MdC(C6H5)Fe(CO)3NO]
(M ) Mn or Re) formed by attack of the [Fe(CO)3NO]-
anion on the carbyne carbon of 1 or 2. The carbene
intermediate then underwent cleavage of a CO group
to generate the [Fe(CO)2NO]- species. We have indeed
determined CO gas in the course of the reaction by gas
chromatography.
Although a number of dimetal bridging carbyne
complexes have been prepared by Stone et al. and us
as mentioned in the Introduction, complexes 15 and 16,
as heteronuclear dimetal bridging carbyne complexes,
were synthesized first by the reaction of the cationic
carbyne complex with the monometal carbonyl anion.
Undoubtedly, this is an another new and convenient
method for preparation of such bridging carbyne com-
plexes.
Of special interest are the reactions of compound
(Ph3P)2N[Fe(CO)3NO] (7). The reactions of 7 with
complexes 1 and 2 under similar conditions gave no
expected bridging carbene or ketene complexes but
heteronuclear dimetal bridging carbyne complexes [Mn-
Fe(µ-CC6H5)(CO)4(NO)(η-C5H5)] (15) (eq 14) and [ReFe-
(µ-CC6H5)CO)4(NO)(η-C5H5)] (16) (eq 15) in 93% and
86% yields, respectively.
Complex 15 reacted with an excess of Fe2(CO)9 in
THF at -5 to 0 °C for 6 h. After workup as described in
the Experimental Section, the purple-red heteronuclear
trimetal bridging carbyne complex 17, [MnFe2(µ3-CC6H5)-
(CO)7(NO)(η-C5H5)], was isolated in 76% yield (eq 16).
The formulas for complexes 15 and 16 shown in eqs
14 and 15 are based on elemental analysis and spec-
troscopic evidence. An X-ray study of 15 establishes its
structure (Figure 3). The structural features of the
dimetallacyclopropene part of 15 are very similar to that
in analogous bridging carbyne complex [MnCo(µ-CC6H5)-
(CO)5(η-C5H5)],14 except the µ-C-Fe bond distance
(1.853(3) Å) is slightly longer than the corresponding
bond in [MnCo(µ-CC6H5)(CO)5(η-C5H5)] (µ-C-Co 1.77(1)
Å).14 The Mn-Fe bond (2.6494(3) Å) in 15 is somewhat
longer than that in the analogous bridging carbyne
complex [(CO)(η-C5H5)Fe(µ-COEt)(µ-CO)Mn(η-C5H4Me)-
(CO)] (2.572(1) Å)27 but is slightly shorter than the
similar bond in the bridging carbene complex [MnFe-
{µ-C(COEt)C6H5}(CO)5(η-C5H5)] (2.6929(8) Å).26 The
C(8)-Mn linkage (1.865(3) Å) is slightly longer than
that found in [MnCo(µ-CC6H5)(CO)5(η-C5H5)] (1.85(1)
Å)14 but is obviously shorter than that in [MnFe{µ-
C(COEt)C6H5}(CO)5(η-C5H5)] (2.021(4) Å).26 The C(8)-
The structure of complex 17 shown in eq 16 is
established by an X-ray diffraction study,29 which gave
an R value of 0.15 due to serious decay. However, the
1
elemental analysis and IR, H NMR, and mass spectra
are consistent with this geometry. The IR spectrum in
the ν(CO) region of 17 showed an absorption band at
1840 cm-1 attributed to a bridging or semibridging
carbonyl ligand, in addition to six terminal CO absorp-
tion bands at 2065, 2023, 2012, 1985, 1963, and 1925
1
cm-1, indicative of a (CO)6Fe2Mn(µ-CO) moiety. The H
NMR spectrum showed the expected proton signals due
to the phenyl and cyclopentadienyl groups. The mass
spectrum provided further structural information (Ex-
perimental Section) showing the molecular ion peak and
(29) Sun, J .; Chen, J .-B. Unpublished work.

80 Organometallics, Vol. 19, No. 1, 2000
Tang et al.
Complexes 18 and 19 are known compounds14 syn-
thesized by the reactions of bridging carbyne complexes
[MCo(µ-CC6H5)(CO)5(η-C5H5)] (M ) Mn, Re) or bridging
carbene complexes [MCo{µ-C(CO)C6H5}(CO)5(η-C5H5)]
(M ) Mn, Re) with Fe2(CO)9. The possible formation
pathway of 18 and 19 shown in eqs 17 and 18 could
proceed either via a dimetal bridging carbene interme-
diate [MCo{µ-C(CO)C6H5}(CO)5(η-C5H5)] (M ) Mn or
Re) or via an unstable trimetal bridging carbyne inter-
mediate [MnFeCo(µ3-CC6H5)(CO)7(PPh3)(η-C5H5)] (M )
Mn or Re). The former, which is formed by displacement
of a PPh3 ligand of complex 12 or 13 by a CO ligand
derived from Fe2(CO)9, reacted14 with Fe2(CO)9 to give
compound 18 or 19. The latter, which is formed directly
by the reaction of 12 or 13 with Fe2(CO)9 as in the
reaction14 of [MCo{µ-C(CO)C6H5}(CO)5(η-C5H5)] (M )
Mn or Re) with Fe2(CO)9, occurred from PPh3 ligand
displacement by a CO ligand arising from the great
steric hindrance of the PPh3 ligand to afford stable
product 18 or 19. A series of trimetal bridging carbyne
complexes have been synthesized by Stone et al. by
reactions6a,c,30 of alkylidyne complexes with low-valent
metal species as mentioned in the Introduction. How-
ever, the reaction of η1,η2-ketene complex with low-
valent metal species giving a trimetal bridging carbyne
complex is unusual. This reaction was only found in the
reaction14 of [MCo{µ-C(CO)C6H5}(CO)5(η-C5H5)] (M )
Mn, Re) with Fe2(CO)9. Not all such η1,η2-ketene com-
plexes can react with Fe2(CO)9 to produce trimetal
bridging carbyne complexes since analogous ketene
complexes 8-11 and 14 do not react similarly under the
same conditions. This suggests that the Co moiety is
important; it probably promotes this reaction by forming
a stable trimetal µ3-CMFeCo core.
F igu r e 3. Molecular structure of 15, showing the atom-
numbering scheme.
the feature fragments generated by loss of CO ligands.
The formation of 17 is not surprising since the analo-
gous products 18 and 19 (see below) have been obtained
in the reactions14 of the bridging carbyne complexes
[MCo(µ-CC6H5)(CO)5(η-C5H5)] (M ) Mn, Re) with
Fe2(CO)9.
Surprisingly, complexes 12 and 13 can also react with
Fe2(CO)9 under similar conditions, leading to loss of the
PPh3 ligand to produce trimetal bridging carbyne com-
plexes [MnFeCo(µ3-CC6H5)(CO)8(η-C5H5)] (18) (eq 17)
and [ReFeCo(µ3-CC6H5)(CO)8(η-C5H5)] (19) (eq 18) in
>70% yields, respectively.
The title reaction shows that the reactions of the
carbonylmetal anions containing cyclopentadienyl, PPh3,
and NO ligands with the cationic carbyne complexes of
manganese and rhenium, 1 and 2, give the η1,η2-ketene
complexes or bridging carbyne complexes. Thus, the
cationic carbyne complexes of manganese and rhenium
reacted not only with the mixed-dimetal carbonyl an-
ions14 but also with the substituted monometal carbonyl
anions to yield the dimetal bridging carbyne complexes.
This offers a convenient and useful method for the
preparation of such dimetal 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 temperature factors, H atom coordi-
nates, anisotropic displacement parameters, complete bond
lengths and angles, and least-squares planes for 10, 13, and
15. This material is available free of charge via the Internet
at http://pubs.acs.org.
OM9906262
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M.; Mitrprachachon, P.; Pickering, S. J .; Stone, F. G. A.; Woodward,
P. J . Chem. Soc., Dalton Trans. 1982, 699. (b) Chetcuti, M. J .; Howard,
J . A. K.; Mills, R. M.; Stone, F. G. A.; Woodward, P. J . Chem. Soc.,
Dalton Trans. 1982, 1757. (c) Green, M.; Porter, S. J .; Stone, F. G. A.
J . Chem. Soc., Dalton Trans. 1983, 513. (d) Carriedo, G. A.; J effery, J .
C.; Stone, F. G. A. J . Chem. Soc., Dalton Trans. 1984, 1597. (e) J effery,
J . C.; Lewis, D. B.; Lewis, G. E.; Stone, F. G. J . Chem. Soc., Dalton
Trans. 1985, 2001. (f) Etches, S. J .; Hart, I. J .; Stone, F. G. A. J . Chem.
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