Unusual reactions of cationic carbyne complexes of manganese and rhenium with reactive salts [Et3NH][(μ-CO)(μ-RS)Fe2(CO)6]. A route to bimetal bridging carbene complexes

Article abstract of DOI:10.1021/om9706267

The reaction of a cationic carbyne complex of manganese, [η-C₅H₅(CO)₂Mn-CC₆H ₅]BBr₄ (1) with the reactive salt [Et₃NH][μ-CO)(μ-n-C₄H₉S)Fe ₂(CO)₆] (3) in THF at low temperature gave the dimetal bridging carbene complex [MnFe{μ-C(n-C₄H₉S)C₆H₅}(CO) ₅(η-C₅H₅)] (8) and [Fe(CO)₃(n-C₄H₉S)]2 (7). 1 reacted with [Et₃NH][μ-CO)(μ-C₆H₅S)Fe ₂(CO)₆] (4) to give the bridging carbene complex [MnFe{μC(C₆H₅S)C₆H₅}(CO) ₅(η-C₅H₅)] (11) and the manganese phenylthiocarbene complex [η-C₅H₅(CO)₂MnC(C₆H ₅S)C₆H₅] (12), besides [Fe(CO)₃C₆H₅S]₂ (10). 1 also reacted with [Et₃NH][(μ-CO)(μ-p-CH₃C₆H ₄S)Fe₂(CO)₆] (5) to yield [Fe(CO)₃(p-CH₃C₆H₄S)]₂ (13) and the bridging carbene complex [MnFe{μ-C(p-CH₃C₆H₄S)C₆H ₅}(CO)₅-(η-C₅H₅)] (14). Analogous reactions of the cationic rhenium carbyne complex [η-C₅H₅(CO)₂-Re≡CC₆H ₅]BBr₄ (2) with 3 and 4 gave the corresponding bridging carbene complexes [ReFe{μ-C(n-C₄H₉S)C₆H₅}(CO) ₅(η-C₅H₅)] (16) and [ReFe{μ-C(C₆H₅S)C₆H₅}(CO) ₅(η-C₅H₅)] (17) and the phenylthiocarbene complex [η-C₅H₅(CO)₂ReC(C₆H ₅S)C₆H₅] (18), respectively. The structures of 8, 11, 12, 16, and 18 have been established by X-ray diffraction studies.

Full text of DOI:10.1021/om9706267

600
Organometallics 1998, 17, 600-606
Un u su a l 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 Rea ctive Sa lts
[Et3NH][(µ-CO)(µ-RS)F e2(CO)6]. A Rou te to Dim eta l
Br id gin g Ca r ben e Com p lexes
Zhilei Qiu, 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, China
Received J uly 22, 1997
The reaction of a cationic carbyne complex of manganese, [η-C5H5(CO)2MntCC6H5]BBr4
(1), with the reactive salt [Et3NH][(µ-CO)(µ-n-C4H9S)Fe2(CO)6] (3) in THF at low temperature
gave the dimetal bridging carbene complex [MnFe{µ-C(n-C4H9S)C6H5}(CO)5(η-C5H5)] (8) and
[Fe(CO)3(n-C4H9S)]2 (7). 1 reacted with [Et3NH][(µ-CO)(µ-C6H5S)Fe2(CO)6] (4) to give the
bridging carbene complex [MnFe{µ-C(C6H5S)C6H5}(CO)5(η-C5H5)] (11) and the manganese
phenylthiocarbene complex [η-C5H5(CO)2MnC(C6H5S)C6H5] (12), besides [Fe(CO)3C6H5S]2
(10). 1 also reacted with [Et3NH][(µ-CO)(µ-p-CH3C6H4S)Fe2(CO)6] (5) to yield [Fe(CO)3(p-
CH3C6H4S)]2 (13) and the bridging carbene complex [MnFe{µ-C(p-CH3C6H4S)C6H5}(CO)5-
(η-C5H5)] (14). Analogous reactions of the cationic rhenium carbyne complex [η-C5H5(CO)2-
RetCC6H5]BBr4 (2) with 3 and 4 gave the corresponding bridging carbene complexes
[ReFe{µ-C(n-C4H9S)C6H5}(CO)5(η-C5H5)] (16) and [ReFe{µ-C(C6H5S)C6H5}(CO)5(η-C5H5)] (17)
and the phenylthiocarbene complex [η-C5H5(CO)2ReC(C6H5S)C6H5] (18), respectively. The
structures of 8, 11, 12, 16, and 18 have been established by X-ray diffraction studies.
In tr od u ction
have been extensively investigated, their reactions with
cationic transition metal carbyne complexes have not
been reported. We have studied the reactions of cationic
carbyne complexes of manganese and rhenium,
[η-C5H5(CO)2MntCC6H5]BBr4 (1) and [η-C5H5(CO)2-
RetCC6H5]BBr4 (2), with the reactive [Et3NH][(µ-CO)-
(µ-RS)Fe2(CO)6] salts, which afforded the novel heter-
onuclear dimetal bridging carbene complexes. In this
paper, we describe these reactions and the structures
of the resulting products.
Transition metal cluster complexes are important
intermediates in some catalytic reactions. Since many
transition metal bridging carbene and carbyne com-
plexes are transition metal clusters or the precursors
of transition metal cluster complexes, the chemistry of
transition metal bridging carbene and carbyne com-
plexes are one area of current interest. Recently, we
have shown that the reactions of the cationic carbyne
complex of rhenium or manganese, [η-C5H5-(CO)2Mt
CC6H5]BBr4 (M ) Re, Mn), with the carbonyliron
dianions gave unexpected dimetal bridging carbene
complexes.1,2 This represents a new route to dimetal
bridging carbene complexes.
In the meantime, we have noted the chemistry of the
reactive salts [Et3NH][(µ-CO)(µ-RS)Fe2(CO)6], developed
by Seyferth and co-workers in the late 1980s.3,4 In their
reactions, the Fe-Fe bond and RS-Fe bond are re-
tained and the bridging CO is usually replaced by
another bridging ligand. Although these reactive salts
Exp er im en ta l Section
All procedures 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
the appropriate drying agents and stored over 4 Å molecular
sieves under a N2 atmosphere. Tetrahydrofuran (THF) and
diethyl ether (Et2O) were distilled from sodium benzophenone
ketyl, while petroleum ether (30-60 °C) was distilled from
CaH2 and CH2Cl2 from P2O5. The neutral alumina (Al2O3)
used for chromatography was deoxygenated at room temper-
ature under high vacuum for 16 h, deactivated with 5% w/w
N2-saturated water, and stored under N2. [η-C5H5(CO)2-
MntCC6H5]BBr4 (1)5 and [η-C5H5(CO)2RetCC6H5]BBr4 (2)6
were prepared as previously described. [Et3NH][(µ-CO)(µ-RS)-
Fe2(CO)6] (3, R ) n-C4H9; 4, R ) C6H5; 5, R ) p-CH3C6H4)
were prepared by a literature method.3a
(1) Chen, J .-B.; Yu, Y.; Liu, K.; Wu, G.; Zheng, P.-J . Organometallics
1993, 12, 1213.
(2) Yu, Y.; Chen, J .-B.; Chen, J .; Zheng, P.-J . J . Chem. Soc., Dalton
Trans. 1996, 1443.
(3) (a) Seyferth, D.; Womack, G. B.; Dewan, J . C. Organometallics
1985, 4, 398. (b) Seyferth, D.; Archer, C. M. Organometallics 1986, 5,
2572. (c) Seyferth, D.; Hoke, J . B.; Wheeler, D. R. J . Organomet. Chem.
1988, 341, 421. (d) Seyferth, D.; Womack, G. B.; Archer, C. M.; Dewan,
J . C. Organometallics 1989, 8, 430. (e) Seyferth, D.; Hoke, J . B.;
Womack, G. B. Organometallics 1990, 9, 2662. (f) Seyferth, D.;
Anderson, L. L.; Villafane, F.; Cowie, M.; Hilts, R. W. Organometallics
1992, 11, 3262.
IR spectra were measured on a Shimadzu IR-440 spectro-
photometer. All 1H NMR spectra were recorded at ambient
temperature in acetone-d6 solution with TMS as the internal
(5) Fischer, E. O.; Meineke, E. W.; Kreissl, F. R. Chem. Ber. 1977,
(4) Abel, E. W.; Stone, F. G. A.; Wilkinson, G. Comprehensive
Organometallic Chemistry II; Pergamon: New York, 1995; Vol. 7, p
62.
110, 1140.
(6) Fischer, E. O.; Chen, J .-B.; Scherzer, K. J . Organomet. Chem.
1983, 253, 231.
S0276-7333(97)00626-2 CCC: $15.00 © 1998 American Chemical Society
Publication on Web 01/28/1998

Reactions of Cationic Carbyne Complexes
Organometallics, Vol. 17, No. 4, 1998 601
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.
R ea ct ion of [η-C5H 5(CO)2Mn tCC6H 5]BBr 4 (1) w it h
in 50 mL of THF was added 0.32 mL (3.20 mmol) of C6H5SH
and 0.44 mL (3.20 mmol) of Et3N with stirring. The mixture
was stirred at room temperature for 40 min. The resulting
brown-red solution of 4 was cooled to -90 °C and then treated,
in a manner similar to that described above, with 1.90 g (3.20
mmol) of 1 at -90 to -70 °C for 3.5 h, during which time the
brown-red solution gradually turned deep red to dark red. The
solvent was removed from -45 to -40 °Cin vacuo. The dark
red residue was chromatographed on alumina at -25 °C with
petroleum ether followed by petroleum ether/CH2Cl2 (20:1) as
the eluant. The brown-red band which eluted first was
collected, and then the green band was eluted with petroleum
ether/CH2Cl2 (5:1). A third brown-yellow band was eluted with
petroleum ether/CH2Cl2/Et2O (10:1:1). The solvents were
removed from the above three eluates under vacuum, and the
residues were recrystallized from petroleum ether/CH2Cl2
solution at -80 °C. From the first fraction, 0.080 g (5%, based
on 1) of orange-red crystals of 109 were obtained: mp 150 °C
(dec) (lit.9 153 °C); IR (νCO) (hexane) 2080 (m), 2050 (s), 2005
(vs), 1998 (m), 1965 (w), 1950 (s) cm-1 (lit.9 (CCl4) 2073 (s),
2038 (vs), 2003 (vs), 1957 (w) cm-1); MS m/e 498 (M+), 470
[E t 3NH ][(µ-CO)(µ-n -C4H 9S)F e2(CO)6] (3) To
Give
[η-C5H5Mn (CO)3] (6), [F e(CO)3(n -C4H9S)]2 (7), [Mn F e{µ-
C(n -C4H 9S)C6H 5}(CO)5(η-C5H 5)] (8), a n d [(η-C5H 5)-
(CO)2Mn C(C6H5)F e(CO)3(n -C4H9S)] (9). To a solution of
1.60 g (3.20 mmol) of Fe3(CO)12 in 50 mL of THF was added
0.35 mL (3.20 mmol) of n-C4H9SH and 0.44 mL (3.20 mmol)
of Et3N with stirring. The mixture was stirred at room
temperature for 40 min. The resulting brown-red solution of
3 was cooled to -90 °C, and then 1.90 g (3.20 mmol) of 1 was
added portionwise with vigorous stirring. The mixture was
stirred at -90 to -70 °C for 3 h, during which time the brown-
red solution gradually turned deep red and finally dark red.
The resulting mixture was evaporated to dryness under high
vacuum from -50 to -40 °C. The dark red residue was
chromatographed on an alumina (neutral, 200-300 mesh)
column (1.6 × 15 cm) at -25 °C with petroleum ether as the
eluant. The orange band which eluted first was collected, then
a green band was eluted with petroleum ether/CH2Cl2 (20:1).
A third brown band was eluted with petroleum ether/CH2Cl2/
Et2O (10:1:1). The solvents were removed from the above three
eluates under vacuum, and the residues were recrystallized
from petroleum ether/CH2Cl2 at -80 °C. From the first
fraction, yellow crystals of 6 and red crystals of 7 were
obtained. The first fraction, a mixture of 6 and 7, was again
chromatographed in the same manner as described above to
give yellow and orange fractions. The solvent was removed
from each fraction in vacuo, and the residues were recrystal-
lized from petroleum ether or petroleum ether/CH2Cl2 at -80
°C. This gave yellow crystals of 67 (0.020 g, 3% based on 1)
and red crystals of 78 (0.053 g, 4% based on 1). 6 is a known
compound and was identified by comparison of its melting
(M+ - 2CO), 442 (M+ - 3CO), 414 (M+ - 4CO), 386 (M+
-
5CO), 358 (M+ - 6CO). From the second fraction, 1.40 g (84%,
based on 1) of dark green crystals of 11 were obtained: mp
85-86 °C (dec); IR (νCO) (hexane) 2050 (m), 1992 (s), 1962
(s), 1958 (s), 1902 (m) cm-1 1H NMR (CD3COCD3) δ 7.75-
;
7.05 (m, 10H, C6H5), 4.65 (s, 5H, C5H5); MS m/e 486 (M+- CO),
402 (M+ - 4CO), 374 (M+ - 5CO), 318 (M+ -5CO - Fe). Anal.
Calcd for C23H15O5SMnFe: C, 53.72; H, 2.94. Found: C, 53.44;
H, 2.86. From the third fraction, 0.110 g (9%, based on 1) of
12 as orange-red crystals were obtained: mp 69-70 °C (dec);
IR (νCO) (hexane) 1982 (s), 1928 (s) cm-1 1H NMR (CD3-
;
COCD3) δ 7.10-6.60 (m, 10H, C6H5), 4.89 (s, 5H, C5H5); MS
m/e 744 (M+), 346 (M+ - CO), 318 (M+ - 2CO). Anal. Calcd
for C20H15O2SMn: C, 64.17; H, 4.04. Found: C, 64.30; H, 3.95.
Rea ction of 1 w ith [Et 3NH][(µ-CO){µ-p-CH3C6H4S}F e2-
(CO)6] (5) To Give [F e(CO)3(p-CH3C6H4S)]2 (13) a n d
[Mn F e{µ-C(p-CH3C6H4S)C6H5}(CO)5(η-C5H5)] (14). Com-
pound 1 (1.90 g, 3.20 mmol) was treated, in a manner similar
to that described in the reaction of 1 with 4, with 5, prepared
(in situ) by the reaction of 1.60 g (3.20 mmol) of Fe3(CO)12 in
50 mL of THF with 0.34 mL (3.20 mmol) of p-CH3C6H4SH and
0.44 mL (3.20 mmol) of Et3N at -90 to -70 °C for 3.5 h, during
which time the brown-red solution gradually turned dark red.
Further treatment as described above in the reaction of 1 with
4 gave 0.050 g (3%, based on 1) of orange-red crystals of 1310
and 1.48 g (88%, based on 1) of dark green crystalline 14. 13:
mp 102-104 °C (dec) (lit.10 105 °C); IR (νCO) (hexane) 2050
(w), 2000 (m), 1998 (s), 1980 (w) cm-1 (lit.10 (CH2Cl2) 2065 (s),
2030 (s), 1995 (s) cm-1); 1H NMR (CD3COCD3) δ 7.30 (m, 4H,
C6H4CH3), 7.13 (m, 4H, C6H4CH3), 2.27 (s, 3H, C6H4CH3), 2.23
(s, 3H, C6H4CH3) (lit.10 (CDCl3) δ 7.16 (d, 2H), 7.14 (d, 2H),
6.96 (d, 4H), 2.21 (s, 6H)); MS m/e 526 (M+), 470 (M+ - 2CO),
442 (M+ - 3CO), 414 (M+ - 4CO), 386 (M+ - 5CO), 358 (M+
- 6CO). Anal. Calcd for C20H14O6S2Fe2: C, 45.66; H, 2.68.
Found: C, 45.31; H, 2.90. 14: mp 90 °C (dec); IR (νCO)
1
point and IR and H NMR spectra with those of an authentic
sample.7 7: mp 38-40 °C (dec); IR (νCO) (hexane) 2050 (s),
1959 (vs), 1920 (m) cm-1 (lit.8 (KBr) 2080, 2035, 1999, 1986
cm-1); 1H NMR (CD3COCD3) δ 2.52 (t, 2H), 1.62 (m, 2H), 1.44
(m, 2H), 0.90 (t, 3H); MS m/e 458 (M+), 430 (M+ - CO), 402
(M+ - 2CO), 374 (M+ - 3CO), 346 (M+ - 4CO), 318 (M+
-
5CO), 290 (M+ - 6CO), 234 (M+ - 6CO - Fe). Anal. Calcd
for C14H18O6S2Fe2: C, 31.46; H, 3.96. Found: C, 31.68; H, 3.94.
From the second fraction, 1.50 g (85%, based on 1) of dark
green crystals of 8 were obtained: mp 68-70 °C dec; IR (νCO)
(hexane) 2050 (m), 1986 (s), 1962 (s), 1956 (s), 1908 (m) cm-1
;
1H NMR (CD3COCD3) δ 7.65 (d, 2H, C6H5), 7.46 (t, 2H, C6H5),
7.29 (t, 1H, C6H5), 4.61 (s, 5H, C5H5), 2.19 (m, 1H, C4H9), 1.68
(m, 1H, C4H9), 1.48 (m, 2H, C4H9), 1.24 (m, 2H, C4H9), 0.77 (t,
3H, C4H9); MS m/e 494 (M+), 438 (M+ - 2CO), 410 (M+ - 3CO),
382 (M+ - 4CO), 354 (M+ - 5CO), 298 (M+ - 5CO - Fe). Anal.
Calcd for C21H19O5SMnFe: C, 51.04; H, 3.87. Found: C, 51.22;
H, 4.00. From the third fraction, 0.092 g (6%, based on 1) of
9 as reddish-brown crystals were obtained: mp 100-101 °C
(dec); IR (νCO) (hexane) 2040 (m), 1982 (s), 1960 (s), 1958 (s),
1902 (m) cm-1
;
1H NMR (CD3COCD3) δ 7.70-7.00 (m, 5H,
(hexane) 2040 (m), 1988 (s), 1960 (s), 1958 (s), 1902 (m) cm-1
;
C6H5), 4.58 (s, 5H, C5H5), 2.08 (m, 1H, C4H9), 1.64 (m, 1H,
C4H9), 1.45 (m, 2H, C4H9), 1.20 (m, 2H, C4H9), 0.79 (t, 3H,
C4H9); MS m/e 494 (M+), 438 (M+ - 2CO), 410 (M+ - 3CO),
382 (M+ - 4CO), 354 (M+ - 5CO), 298 (M+ - 5CO - Fe). Anal.
Calcd for C21H19O5SMnFe: C, 51.04; H, 3.87. Found: C, 50.72;
H, 3.97.
Rea ction of 1 w ith [Et3NH][(µ-CO)(µ-C6H5S)F e2(CO)6]
(4) To Give [F e(CO)3C6H5S]2 (10), [Mn F e{µ-C(C6H5S)-
C6H5}(CO)5(η-C5H5)] (11), a n d [η-C5H5(CO)2Mn C(C6H5S)-
C6H5] (12). To a solution of 1.60 g (3.20 mmol) of Fe3(CO)12
1H NMR (CD3COCD3) δ 7.70-6.90 (m, 9H, C6H5 and C6H4-
CH3), 4.61 (s, 5H, C5H5), 2.16 (s, 3H, C6H4CH3); MS m/e 472
(M+ - 2CO), 444 (M+ - 3CO), 416 (M+- 4CO), 388 (M+
-
5CO), 332 (M+ - 5CO - Fe). Anal. Calcd for C24H17O5-
SMnFe: C, 54.57; H, 3.24. Found: C, 54.55; H, 3.26.
Rea ction of [η-C5H5(CO)2RetCC6H5]BBr 4 (2) w ith 3 To
Give [η-C5H5Re(CO)3] (15) a n d [ReF e{µ-C(n -C4H9S)C6H5}-
(CO)5(η-C5H5)] (16). Similar to the procedures for the reac-
tion of 1 with 3, compound 2 (0.50 g, 0.68 mmol) was treated
with 3, prepared (in situ) by the reaction of Fe3(CO)12 (0.382
(7) Piper, T. S.; Cotton, F. A.; Wilkinson, G. J . Inorg. Nucl. Chem.
1955, 1, 165.
(8) Nametkin, N. S.; Tyurin, V. D.; Kukina, M. A. J . Organomet.
Chem. 1978, 149, 355.
(9) Hieber, W.; Beck, W. Z. Anorg. Allg. Chem. 1960, 305, 265.
(10) Treichel, P. M.; Crane, R. A.; Mathews, R.; Bonnin, K. R.;
Powell, D. J . Organomet. Chem. 1991, 402, 233.
(11) Abad, Izv. Nauk. SSSR Ser., Khim. 1974, 710.

602 Organometallics, Vol. 17, No. 4, 1998
Ta ble 1. Cr ysta l Da ta a n d Exp er im en ta l Deta ils for Com p lexes 8, 11, 12, 16, a n d 18
Qiu et al.
8
11
12
16
18
formula
fw
space group
a (Å)
b (Å)
c (Å)
C
21H19O5SFeMn
C23H15O5SFeMn
514.21
P21/c (No. 14)
7.156(3)
17.637(5)
17.169(4)
C20H15O2SMn
748.67
C21H19O5SReFe
625.49
C20H15O2SRe
494.22
P21/c (No. 14)
8.739(4)
23.057(9)
10.589(6)
505.60
Pbca (No. 61)
23.291(6)
12.555(2)
12.2817(8)
90
90
90
3591(2)
8
1.870
P1h (No.1)
10.459(5)
10.687(6)
8.417(4)
92.59(5)
106.92(4)
77.30(4)
877.8(8)
1
P1h (No. 2)
10.426(2)
24.127(6)
8.852(2)
94.90(2)
90.50(2)
94.79(2)
2210.5(8)
4
R (deg)
â (deg)
91.67(5)
96.86(3)
γ (deg)
V (Å3)
2132(1)
4
1.539
2151(1)
4
1.587
Z
dcalcd (g/cm3)
cryst size (mm)
µ(Mo KR) (cm-1
1.416
1.879
0.20 × 0.20 × 0.30 0.20 × 0.20 × 0.30 0.20 × 0.20 × 0.30 0.20 × 0.30 × 0.30 0.20 × 0.20 × 0.40
)
13.98
13.89
8.78
62.52
68.94
radiation (monochromated
in incident beam)
diffractometer
temperature (°C)
orientation of reflns [no.;
range (2θ) (deg)
scan method
data collection range, 2θ (deg) 5-45.1
no. of unique data
total no. of data with
I > 3.00σ(I)
Mo KR (λ )
0.710 69)
Rigaku AFC7R
20.0
Mo KR (λ )
0.710 69)
Rigaku AFC7R
20.0
Mo KR (λ )
0.710 69)
Rigaku AFC7R
20.0
Mo KR (λ )
0.710 69)
Rigaku AFC7R
20.0
Mo KR (λ )
0.710 69)
Rigaku AFC7R
20.0
18; 18.7-22.6
14; 18.5-26.5
19; 14.5-19
15; 18.6-21.8
17; 24.0-26.4
ω-2θ
ω-2θ
5-45
2931
1293
ω-2θ
5-45
2290
1867
ω-2θ
5-45
4964
3727
ω-2θ
5-45
2680
1622
2430
1100
no. of params refined
correction factors, max, min
Ra
263
280
430
523
217
1.1228, 0.8064
0.056
0.059
1.74
0.09
0.36
1.000, 0.8954
0.042
0.035
1.25
0.00
0.38
0.9988, 0.7685
0.051
0.063
1.93
0.07
0.69
1.0000, 0.7869
0.029
0.033
1.40
0.01
0.52
1.0937, 0.9482
0.028
0.034
1.34
0.04
0.63
b
Rw
quality-of-fit indicatorc
largest shift/esd. final cycle
largest peak, e-/Å3
minimum peak, e-/Å3
-0.37
-0.30
-0.40
-0.46
-0.59
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-Nparams)]1/2
.
g, 0.76 mmol) with 0.08 mL (0.76 mmol) of n-C4H9SH and 0.10
mL (0.76 mmol) of Et3N at -90 to -70 °C for 3.5 h, during
which time the orange-red solution gradually turned deep red
until it finally turned dark red. Further treatment of the
resulting mixture as described in the reaction of 1 with 3
afforded 0.015 g (6%, based on 2) of yellow crystals of 1511 and
0.170 g (40%, based on 2) of orange-red crystals of 16. 15 is a
known compound and was identified by comparison of its
melting point and IR and 1H NMR spectra with those of an
authentic sample. 16: mp 70 °C (dec); IR (νCO) (hexane) 2020
(m), 1990 (w), 1980 (vs), 1966 (m), 1960 (s), 1950 (s), 1904 (s),
(hexane) 1980 (s), 1908 (s) cm-1; 1H NMR (CD3COCD3) δ 7.20-
6.72 (m, 10H, C6H5), 5.49 (s, 5H, C5H5); MS m/e 506 (M+), 478
(M+ - CO), 450 (M+ - 2CO). Anal. Calcd for C20H15O2SRe:
C, 47.51; H, 2.99. Found: C, 47.65; H, 2.94.
Rea ction of 11 w ith P P h 3 To Give 12. A solution of PPh3
(0.031 g, 0.12 mmol) in 10 mL of petroleum ether was added
dropwise to a solution of 11 (0.050 g, 0.097 mmol) in 40 mL of
petroleum ether at -55 °C. The reaction mixture was stirred
at -55 to -10 °C for 6 h. The solvent was removed under
vacuum, and the residue was chromatographed on alumina
at -25 °C with petroleum ether followed by petroleum ether/
CH2Cl2 (20:1) as the eluant. After elution of the green band
which contains unreacted 11, the brown-yellow band was
eluted with petroleum ether/CH2Cl2/Et2O (10:1:1). The solvent
was removed in vacuo, and the residue was recrystallized from
petroleum ether/CH2Cl2 solution at -80 °C to give 0.014 g
(39%, based on 11) of orange crystals of 12, which was
identified by its melting point and IR, 1H NMR, and mass
spectra.
X-r a y Cr ysta l Str u ctu r e Deter m in a tion s of Com p lexes
8, 11, 12, 16, a n d 18. The single crystals of 8, 11, 12, 16, and
18 suitable for X-ray diffraction study were obtained by
recrystallization from petroleum ether/CH2Cl2 solution at -80
°C. Single crystals of 8, 11, 12, 16, and 18 were sealed in
capillaries under an N2 atmosphere. The X-ray diffraction
intensity data for 8, 11, 12, 16, and 18 were collected with a
Rigaku AFC7R diffractometer at 20 °C using Mo KR radiation
with an ω-2θ scan mode within the ranges 5° E 2θ E 45°.
The structures of 8, 11, 16, and 18 were solved by direct
methods and expanded using Fourier techniques. For the four
complexes, the non-hydrogen atoms were refined anisotropi-
cally. The hydrogen atoms were included but not refined. The
final cycle of full-matrix least-squares refinement was, respec-
tively, based on 1100, 1293, 3727, and 1622 observed reflec-
tions (I > 3.00σ(I)) and 263, 280, 523, and 217 variable
parameters and converged with unweighted and weighted
agreement factors of R ) 0.056 and Rw ) 0.059 for 8, R ) 0.042
1898 (m) cm-1 1H NMR (CD3COCD3) δ 7.60-6.80 (m, 10H,
;
C6H5), 5.40 (s, 5H, C5H5), 5.26 (s, 5H, C5H5), 2.49 (m, 2H, C4H9),
1.62 (m, 2H, C4H9), 1.47 (m, 4H, C4H9), 1.22 (m, 4H, C4H9),
0.76 (m, 6H, C4H9); MS m/e 625 (M+), 597 (M+ - CO), 569
(M+ - 2CO), 542 (M+ - 3CO), 514 (M+ - 4CO), 486 (M+
-
5CO), 430 (M+ - 5CO - Fe). Anal. Calcd for C21H19O5-
SReFe: C, 40.32; H, 3.06. Found: C, 40.51; H, 3.02.
Rea ction of 2 w ith 4 To Give 10, [ReF e{µ-C(C6H5S)-
C6H5}(CO)5(η-C5H5)] (17), a n d [η-C5H5(CO)2ReC(C6H5S)-
C6H5] (18). As described above for the reaction of 1 with 4,
compound 2 (0.47 g, 0.66 mmol) was treated with 4, prepared
(in situ) by the reaction of 0.37 g (0.73 mmol) of Fe3(CO)12 with
0.075 mL (0.73 mmol) of C6H5SH and 0.10 mL (0.73 mmol) of
Et3N at -90 to -70 °C for 3.5 h, during which time the orange-
red solution gradually turned dark red. Further treatment
in a manner similar to that described in the reaction of 1 with
4 yielded 0.020 g (6%, based on 2) of orange-red crystals of
10, 0.142 g (32%, based on 2) of red crystals of 17, and 0.053
g (16%, based on 2) of 18 as gold-yellow crystals. 10 was
identified by its melting point and IR and 1H NMR spectra.
17: mp 86-88 °C (dec); IR (νCO) (hexane) 2000 (m), 1988 (s),
1979 (s), 1962 (m), 1958 (s), 1912 (m), 1900 (s), 1892 (m) cm-1
1H NMR (CD3COCD3) δ 7.61-6.70 (m, 10H, C6H5), 5.30 (s, 5H,
C5H5); MS m/e 589 (M+ - 2CO), 505 (M+ - 5CO), 449 (M+
;
-
5CO - Fe). Anal. Calcd for C23H15O5SReFe: C, 42.80; H, 2.34.
Found: C, 43.11; H, 2.55. 18: mp 156 °C (dec); IR (νCO)

Reactions of Cationic Carbyne Complexes
Organometallics, Vol. 17, No. 4, 1998 603
F igu r e 1. Molecular structure of 8 and the atom-number-
ing scheme.
F igu r e 3. Molecular structure of 12 and the atom-
numbering scheme, showing only one of the two indepen-
dent molecules for clarity.
(in situ) [(µ-CO)(µ-n-C4H9S)Fe2(CO)6][Et3NH] (3) in THF
at -90 to -70 °C for 3 h. Yellow crystals of 6, red crys-
tals of 7, dark green crystals of 8, and reddish-brown
crystalline 9 (eq 1) were isolated in 3, 4, 85, and 6%
yields, respectively, on workup, among which 67 and 78
are known compounds.
F igu r e 2. Molecular structure of 11 and the atom-
numbering scheme.
and Rw ) 0.035 for 11, R ) 0.029 and Rw ) 0.033 for 16, and
R ) 0.028 and Rw ) 0.034 for 18, respectively. While the
structure of 12 was solved by the heavy-atom Patterson
methods and expanded using Fourier techniques. The non-
hydrogen atoms were refined anisotropically. The hydrogen
atoms were included but not refined. The final cycle of full-
matrix least-squares refinement was based on 1867 observed
reflections (I > 3.00σ(I)) and 430 variable parameters and
converged with unweighted and weighted agreement factors
of R ) 0.051 and Rw ) 0.063. All the calculations were
performed using the teXsan crystallographic software package
of Molecular Structure Corp.
The details of the crystallographic data and the procedures
used for data collection and reduction information for 8, 11,
12, 16, and 18 are given in Table 1. The positional parameters
and temperature factors of the non-hydrogen atoms, H atomic
coordinates and Biso/Beq, anisotropic displacement parameters,
the bond lengths and angles, and least-squares planes for 8,
11, 12, 16, and 18 are given in the Supporting Information.
The molecular structures of 8, 11, 12, 16, and 18 are given in
Figures 1-5, respectively.
Resu lts a n d Discu ssion
Compound [η-C5H5(CO)2MntCC6H5]BBr4 (1) was
treated with equimolecular amounts of freshly prepared

604 Organometallics, Vol. 17, No. 4, 1998
Qiu et al.
96 h. However, only dark green crystals of 8 were
obtained in 95% yield. The parent ion (M+) and the
principal fragment ions in the mass spectrum and C,H
elemental analyses of 9 indicate the same composition,
(η-C5H5)(CO)2MnC(C6H5)Fe(CO)3(n-C4H9S), as that of 8.
The phenyl signals (δ 7.70-7.00) and the Cp signal (δ
1
4.58) in its H NMR spectrum are different from those
of 8 (δ 7.65-7.29 for phenyl and δ 4.61 for Cp). The
ν(CO) absorptions of 9 are similar to those of 8. At
present, there is not sufficient evidence to assign a
structure to 9.
In order to examine the effect of different substituents
on the RS group on the reactivity of the reactive salts
and on the reaction products, [Et3NH][(µ-CO)(µ- C6H5S)-
Fe2(CO)6] (4), where the substituent on RS is a phenyl
group, and the p-tolyl analog were used in the reaction
with 1 under the same conditions. The known thiolato-
bridged iron carbonyl compound 10,9 bridging carbene
complex 11, and phenylthiocarbene complex 12 (eq 2)
were formed in 5, 84, and 9% yields, respectively, in the
case of [Et3NH][(µ-CO)(µ-C6H5S)Fe2(CO)6]. The struc-
F igu r e 4. Molecular structure of 16 and the atom-
numbering scheme, showing only one of the two indepen-
dent molecules for clarity.
F igu r e 5. Molecular structure of 18 and the atom-
numbering scheme.
tures of complexes 11 and 12 have been established by
X-ray diffraction analyses.
Analogous products ([Fe(CO)3(p-CH3C6H4S)]2 (13)
and [MnFe{µ-C(p-CH3C6H4S)C6H5}(CO)5(η-C5H5)] (14))
were obtained in the reaction of [Et3NH][(µ-CO)(µ-p-
CH3C6H4S)Fe2(CO)6] (5) with 1.
Complex 8 is formulated as a dimetal bridging car-
bene complex, which has been confirmed by its single-
crystal X-ray diffraction study. The structure of com-
plex 9 is not known since we were unable to obtain
crystals suitable for an X-ray study and spectroscopic
studies did not result in an unambiguous proof of
structure. In solution, complex 9 was transformed into
The molecular structure of complex 8 (Figure 1)
confirmed that it is a novel Mn-Fe dimetal bridging
carbene complex. The S atom bridges the carbene
carbon (C(3)) atom and the Fe atom and provides two
electrons for Fe to satisfy the 18-electron configuration.
The Mn-Fe distance of 2.705(4) Å is somewhat longer
than that found in the analogous bridging carbene
complex [MnFe{µ-C(COEt)Ph}(η-C5H5)(CO)5] (2.6929-
(8)Å)2 but is obviously longer than that in the analogous
carbyne complex [(η-C5H5)(CO)Fe(µ-CO)(µ-COEt)Mn-
(CO)(η-MeC5H4)] (2.572(1) Å).12 The µ-C-Fe distance-
(1.94(1) Å) in 8 is not only shorter than that in the
bridging carbene complexes [MnFe{µ-C(COEt)Ph}(η-
1
complex 8, as observed by H NMR spectroscopy. The
acetone-d6 solution of 9 whose NMR spectrum had been
measured was kept at room temperature for about 0.5
h, during which time the solution changed from red-
brown to dark green. Its 1H NMR spectrum now
showed only the proton signals attributable to the
phenyl, cyclopentadienyl, and butyl protons of 8 but
none of the original proton signals assigned to 9,
confirming the transformation of 9 into 8. Further
evidence for this transformation came from the recrys-
tallization of complex 9. In order to obtain X-ray quality
crystals, recrystallization of complex 9 was attempted
from petroleum ether/CH2Cl2 solution at -80 °C for 72-
(12) Fong, R. H.; Lin, C.-H.; Idmouaz, H.; Hersh, W. H. Organome-
tallics 1993, 12, 503.
(13) Garcia, M. E.; J effery, J . C.; Sherwood, P.; Stone, F. G. A. J .
Chem. Soc., Dalton Trans. 1987, 1209.

Reactions of Cationic Carbyne Complexes
Organometallics, Vol. 17, No. 4, 1998 605
C5H5)(CO)5] (2.020(4) Å)2 and [C8H8(CO)2Fe{µ-
C(OC2H5)C6H4CF3-p}Fe(CO)2] (average 2.037 Å),14 but
is also shorter than that in the carbyne-bridged complex
[(CO)2(η-C5H5)Mo(µ-C(C6H4CH3-4)Fe(CO)4] (2.008(5) Å)13
and is comparable to that in the iron carbene complex
[C10H16(CO)2FeC(OC2H5)C6H4CH3-o] (1.915(15) Å).15 The
S-Fe distance of 2.265(5) Å in 8 is the same as the
normal distance of the S-Fe bond (2.270 Å) found in
[NEt3H][(µ-SO2)(µ-(CH3)3CS)Fe2(CO)6].16 The C(6)-S
distance of 1.76(1) Å is nearly the same as the C(3)-
S(1) distance (1.74(1) Å) in carbene complex 12.
indeed be broken, since 11 was converted to complex
12 by loss of the Fe(CO)3 moiety. However, complex 8
did not react with PPh3 under the same conditions.
It is found that the central metal exerts a great affect
on the reactivities of cationic transition metal carbyne
complexes.1,2,18,19 To further examine this effect, the
cationic rhenium carbyne complex 2 was used in reac-
tions with the reactive salts under the same conditions.
Similar to the reaction of 1 with 3, 2 was treated with
3 to afford yellow crystals of 15 and orange-yellow
crystals of 16 (eq 4) in 6 and 40% yields, respectively,
of which 15 is known11 and 16 is a Re-Fe bridging
carbene complex. Complex 2 reacted similarly with
The structure of complex 11 (Figure 2) resembles that
of 8, except that the substituent on the S atom is a
phenyl group instead of a butyl group. The Mn-Fe
bond length (2.704(2) Å) is the same within experimen-
tal error as that in 8. The C(6)-Mn distance of 2.057-
(9) Å is slightly longer than that in 8, but the C(6)-Fe
distance of 1.897(9) Å is somewhat shorter. The S-C(6)
distance of 1.799(9) Å and S-Fe distance of 2.279(3) Å
are both slightly longer than those found in 8.
The molecular structure of complex 12 shown in
Figure 3 has many common features of previously
determined analogous alkoxycarbene complexes.1,17 In-
terestingly, there are two independent molecules in the
asymmetric unit of the complex 12, which is similar to
1
that found in complex 16 (below). However, its H NMR
spectrum showed that the two molecules are separated
in solution, giving a single normal molecule. The two
molecules in the unit cell are the same. The sum of the
three angles around the C(3) atom is exactly 360°, which
means that the Mn(1), C(3), C(4), and S atoms are in
one plane. The Mn-Ccarbene distance of 1.84(1) Å in 12
is close to that in the analogous carbene complex
[CpMn(CO)2C(OEt)Ph] (1.865(14) Å).17
reactive salt 4 under the same conditions to give 10,
the rhenium-iron bridging carbene complex 17, and the
rhenium phenyl-thiocarbene complex 18 (eq 5) in 6, 32,
and 16% yields, respectively. The structures of products
Complex 12 might be produced by loss of an Fe(CO)3
moiety from the Fe(CO)3(SPh)- anion involving the
breaking of Fe-S bond of 4 or by cleavage of the carbene
intermediate [(η-C5H5)MndC(C6H5)Fe(CO)3(C6H5S)] to
generate a PhS- species, which then becomes bonded
to the carbene carbon to afford complex 12. Both
possibilities result from the stabilization of the negative
charge on the S atom by the phenyl group. To our
knowledge, no such Fe-S bond cleavage in reactions of
the [Et3NH][(µ-CO)(µ-RS)Fe2(CO)6] salts has been re-
ported. In order to explore this possibility, we investi-
gated the reaction of PPh3 with complex 11. This
reaction gave orange-red crystals of 12 in 39% yield (eq
3). This result shows that the S-Fe bond of 11 can
16, 17, and 18 were supported by their elemental
1
analyses and IR, H NMR, MS, and X-ray diffraction
studies.
(15) Chen, J .-B.; Lei, G.-X.; J in, Z.-S.; Hu, L.-H.; Wei, G.-C. Orga-
nometallics 1988, 7, 1652.
(16) Seyferth, D.; Womack, G. B.; Archer, C. M.; Fackler, J . P., J r.;
Marler, D. O. Organometallics 1989, 8, 433.
(17) Schubert, U. Organometallics 1982, 1, 1085.
(18) Chen, J .-B.; Lei, G.-X.; Zhang, Z.-Y.; Tang, Y.-Q. Acta Chim.
Sinica 1986, 4, 311.
(19) Chen, J .-B.; Lei, G.-X.; Zhang, Z.-Y.; Tang, Y.-Q. Acta Chim.
Sinica (Chinese Edition) 1989, 47, 31.
(14) Chen, J .-B.; Li, D.-S.; Yu, Y.; J in, Z.-S.; Zhou, Q.-L.; Wei, G.-C.
Organometallics 1993, 12, 3885.

606 Organometallics, Vol. 17, No. 4, 1998
Qiu et al.
It is very interesting that the bridging carbene
complex 16 crystallizes with two independent molecules
in the asymmetric unit. Although the two independent
molecules in an asymmetric unit is not unusual in
crystallograpy, this structure was observed in the bridg-
ing carbene complexes for the first time. The two
molecules in the unit cell are nearly the same. The Re-
Fe distance of 2.784(2) Å in 16 is very close to that in
the analogous complex [ReFe{µ-C(H)C6H5}(CO)6(η-
C5H5)] (2.7581(8) Å)1 but is slightly longer than that
found in [ReFe(µ-CC6H5)(µ-CO)(CO)3(η-C5H5)(COC2-
HB10H10)] (2.682(6) Å).20 The µ-C-Re(1) distance (2.128-
(10) Å) is nearly the same as that in [ReFe{µ-C(H)-
C6H5}(CO)6(η-C5H5)] (2.120(5) Å).1 But the µ-C-Fe(1)
distance of 1.951(1) Å is shorter than that found in
[ReFe{µ-C(H)C6H5}(CO)6(η-C5H5)] (2.097(5) Å).1
tetrahedron is the Cp ring. The sum of the three angles
around C(3) is 359.9°, the same as that in complex 12.
The Re-C(3)carbene distance of 1.966(9) Å is slightly
shorter than that found in the analogous carbene
complex [η-C5H5(CO)2RedC(OC2H5)C6H5] (1.990(5) Å).1
The bond length of S-C(3) (1.749(9) Å) in 18 is close to
that of S(1)-C(6) (1.785(9) Å) in complex 16.
The title reaction demonstrates a novel and conve-
nient route for the preparation of heteronuclear dimetal
bridging carbene 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, bond lengths and
angles, and least-squares planes for 8, 11, 12, 16, and 18 (53
pages). Ordering information is given on any current mast-
head page.
The molecular structure of complex 18, shown in
Figure 5, demonstrates that the coordination of the Re
atom is that of a distorted tetrahedron. The apex of this
(20) Zhu, B.; Yu, Y.; Chen, J .-B.; Wu, Q.-J .; Liu, Q.-T. Organome-
tallics 1995, 14, 3963.
OM9706267