Unexpected reactions of cationic carbyne complexes of manganese and rhenium with mixed-dimetal carbonyl anions. A new route to dimetal bridging carbyne complexes

Article abstract of DOI:10.1021/om9800400

The reaction of a cationic carbyne complex of manganese, [η-C₅H₅(CO)₂Mn≡CC₆H ₅]BBr₄ (1), with (Ph₃P)₂NFeCo(CO)₈ (3) in THF at low temperature gave a heteronuclear dimetal bridging carbyne complex [MnCo(μ-CC₆H₅)(CO)₅(η-C ₅H₅)] (5) and a bridging carbene complex [MnCo{μ-C(CO)C₆H₅}(CO)₅(η-C ₅H₅)] (6). Ph₃P)₂NWCo(CO)₉ (4) also reacted with 1 to give the same products 5 and 6. The analogous reaction of the cationic carbyne complex of rhenium, [η-C₅H₅(CO)₂Re≡CC₆H ₅]BBr₄ (2), with 3 or 4 afforded the corresponding bridging carbyne complex [ReCo(μ-CC₆H₅)(CO)₅(η-C ₅H₅)] (7) and bridging carbene complex [ReCo{μ-C(CO)C₆H₅}(CO)₅(η-C ₅H₅)] (8). 5 can convert to 6 by reaction with carbon monoxide gas. 5 or 6 reacted with Fe₂(CO)₉ to afford a trimetal bridging carbyne complex [MnFeCo(μ₃-CC₆H₅)-(μ-CO)(CO) ₇(η-C₅H₅)] (9). Analogous reaction of 7 or 8 with Fe₂(CO)₉ yielded the trimetal bridging carbyne complex [ReFeCo(μ₃-CC₆H₅)(CO) ₈(η-C₅H₅)] (10). The structures of 5, 7, 8, 9 and 10 have been established by X-ray diffraction studies.

Full text of DOI:10.1021/om9800400

Organometallics 1998, 17, 2945-2952
2945
Articles
Un exp ected 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 Mixed -Dim eta l Ca r bon yl
An ion s. A New 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, China
Received J anuary 22, 1998
The reaction of a cationic carbyne complex of manganese, [η-C5H5(CO)2MntCC6H5]BBr4
(1), with (Ph3P)2NFeCo(CO)8 (3) in THF at low temperature gave a heteronuclear dimetal
bridging carbyne complex [MnCo(µ-CC6H5)(CO)5(η-C5H5)] (5) and a bridging carbene complex
[MnCo{µ-C(CO)C6H5}(CO)5(η-C5H5)] (6). Ph3P)2NWCo(CO)9 (4) also reacted with 1 to give
the same products 5 and 6. The analogous reaction of the cationic carbyne complex of
rhenium, [η-C5H5(CO)2RetCC6H5]BBr4 (2), with 3 or 4 afforded the corresponding bridging
carbyne complex [ReCo(µ-CC6H5)(CO)5(η-C5H5)] (7) and bridging carbene complex [ReCo{µ-
C(CO)C6H5}(CO)5(η-C5H5)] (8). 5 can convert to 6 by reaction with carbon monoxide gas. 5
or 6 reacted with Fe2(CO)9 to afford a trimetal bridging carbyne complex [MnFeCo(µ3-CC6H5)-
(µ-CO)(CO)7(η-C5H5)] (9). Analogous reaction of 7 or 8 with Fe2(CO)9 yielded the trimetal
bridging carbyne complex [ReFeCo(µ3-CC6H5)(CO)8(η-C5H5)] (10). The structures of 5, 7, 8,
9 and 10 have been established by X-ray diffraction studies.
In tr od u ction
nuclear dimetal bridging carbyne and bridging carbene
complexes. These products reacted further with Fe2-
(CO)9 to give the trimetal bridging carbyne complexes.
Herein, we describe these unusual reactions and the
structures of the resulting products.
The current interest in the synthesis, structure, and
chemistry of dimetal bridging carbene and bridging
carbyne complexes stems from the possible involvement
of these species in some reactions catalyzed by organo-
metallic compounds.1,2 We have recently shown the
reactions of a cationic carbyne complexes of rhenium
and manganese, [η-C5H5(CO)2MtCC6H5]BBr4 (M ) Re,
Mn), with the carbonyliron dianion such as (NEt4)2-
Fe2(CO)8 and Na2Fe3(CO)11, where the two metals are
homonuclear, to yield dimetal bridging carbene com-
plexes.3,4 This represents a new route to dimetal
bridging carbene complexes. We are now interested in
examining the effect of different nucleophiles containing
heteronuclear dimetal anions on the reactivities of the
cationic carbyne complexes and the reaction products.
Thus, we chose the mixed-dimetal carbonyl anions
Ph3P)2NFeCo(CO)8 (3) and Ph3P)2NW-Co(CO)9 (4) as
nucleophiles for the reactions with the cationic carbyne
complexes of manganese and rhenium, [η-C5H5(CO)2-
MntCC6H5]BBr4 (1) and [η-C5H5(CO)2RetCC6H5]BBr4
(2). These reactions afforded the unexpected hetero-
Exp er im en ta l Section
All reactions were performed under a dry, oxygen-free N2
atmosphere by using standard Schlenk techniques. All sol-
vents employed were reagent grade and dried by refluxing over
the appropriate drying agents and storing over 4 Å molecular
sieves under a N2 atmosphere. The tetrahydrofuran (THF)
and diethyl ether (Et2O) were distilled from sodium benzophe-
none ketyl, while petroleum ether (30-60 °C) was distilled
from CaH2 and CH2Cl2 from P2O5. The neutral SiO2 (Scientific
Adsorbents Inc., 40 µm Flash) used for chromatography was
deoxygenated at room temperature under high vacuum for 12
h and stored under N2. [η-C5H5(CO)2MntCC6H5]BBr4 (1)5 and
[η-C5H5(CO)2RetCC6H5]BBr4 (2)6 were prepared as previously
described. Ph3P)2NFeCo(CO)8 (3) and Ph3P)2NWCo(CO)9 (4)
were prepared by literature methods.7
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-
(1) Rofer Depooeter, C. K. Chem. Rev. 1981, 81, 447.
(2) Wilkinson, S. G.; Stone, F. G. A.; Abel, E. W. Comprehensive
Organometallic Chemistry; Pergamon Press: Oxford, U.K., 1982; Vol.
8, p 40.
(3) Chen, J .-B.; Yu, Y.; Liu, K.; Wu, G.; Zheng, P.-J . Organometallics
1993, 12, 1213.
(5) Fischer, E. O.; Meineke, E. W.; Kreissl, F. R. Chem. Ber. 1977,
110, 1140.
(6) Fischer, E. O.; Chen, J .-B.; Scherzer, K. J . Organomet. Chem.
1983, 253, 231.
(4) Yu, Y.; Chen, J .-B.; Chen, J .; Zheng, P.-J . J . Chem. Soc., Dalton
Trans. 1996, 1443.
(7) Ruff, J . K. Inorg. Chem. 1968, 7, 1818.
S0276-7333(98)00040-5 CCC: $15.00 © 1998 American Chemical Society
Publication on Web 06/10/1998

2946 Organometallics, Vol. 17, No. 14, 1998
Ta ble 1. Cr ysta l Da ta a n d Exp er im en ta l Deta ils for Com p lexes 5, 7, 8, 9, a n d 10
Tang et al.
5
7
8
9
10
formula
fw
C
17H10O5MnCo
C17H10O5ReCo
539.40
C18H10O6ReCo
567.42
C40H20O16Mn2Co2Fe2 C40H20O16Re2Co2Fe2
408.13
1096.02
1358.56
space group
a (Å)
b (Å)
P21/c (No. 14)
7.717(3)
14.822(5)
14.366(8)
98.96(4)
1623(1)
4
P21/a (No. 14)
14.421(3)
14.966(2)
7.723(2)
98.78(2)
1647.3(5)
4
P21/n (No. 14)
8.514(1)
14.860(3)
14.093(2)
98.38(1)
1763.9(5)
4
Pnna (No. 52)
14.640(7)
26.229(6)
21.572(5)
P21/n (No. 14)
13.540(2)
14.016(2)
22.211(4)
93.03(1)
4209(1)
4
2.144
c (Å)
â (deg)
V (Å3)
8283(7)
8
1.758
Z
dcalcd (g/cm3)
cryst size (mm)
µ(Mo KR) (cm-1
1.670
2.175
2.076
0.20 × 0.20 × 0.30 0.20 × 0.20 × 0.30 0.20 × 0.30 × 0.30 0.20 × 0.20 × 0.30
0.20 × 0.30 × 0.30
)
18.22
83.75
78.35
21.27
72.43
radiation (monochromated Mo KR (λ )
in incident beam)
diffractometer
temperature (°C)
orientation reflections:
no.; range (2θ) (deg)
scan method
data collection range,
2θ (deg)
Mo KR (λ )
0.710 69 Å)
Rigaku AFC7R
20
Mo KR (λ )
0.710 69 Å)
Rigaku AFC7R
20
Mo KR (λ )
0.716 09 Å)
Rigaku AFC7R
20
Mo KR (λ )
0.710 69 Å)
Rigaku AFC7R
20
0.710 69 Å)
Rigaku AFC7R
20
24; 13.5-21.3
21; 14.4-21.2
24; 18.4-21.4
25; 14.1-21.0
24; 18.5-21.7
ω-2θ
5-50
ω-2θ
5-50
ω-2θ
5-50
ω-2θ
5-50
ω-2θ
5-50
no. of unique data,
total with I > 3.00σ(I)
2630
2759
2976
8003
7755
1038
1708
1976
3014
4978
no. of params refined
correction factors,
max-min
217
217
235
559
560
0.8524-1.0000
0.7377-1.0000
0.8967-1.0828
0.6718-1.0000
0.8021-1.1125
Ra
0.056
0.057
1.63
0.039
0.045
1.47
0.029
0.030
1.20
0.058
0.051
1.34
0.031
0.033
1.22
b
Rw
quality-of-fit indicatorc
largest shift/esd. final cycle 0.00
0.00
0.84
-0.95
0.00
0.46
-0.61
0.00
0.54
-0.48
0.11
0.55
-0.69
largest peak, e-/Å3
0.59
minimum peak, e-/Å3
-0.46
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
.
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
P h 3P )2NF eCo(CO)8 (3) to give [Mn Co{µ-CC6H5}(CO)5(η-
C5H5)] (5) a n d [Mn Co{µ-C(CO)C6H5}(CO)5(η-C5H5)] (6). To
0.52 g (0.87 mmol) of 1 dissolved in 50 mL of THF at -90 °C
was added 0.76 g (0.87 mmol) of Ph3P)2NFeCo(CO)8 with
vigorous stirring. Immediately, the brick-red solution turned
dark red. The reaction mixture was stirred at -90 to -45 °C
for 3-4 h, during which time the dark red solution gradually
turned blackish-green. After the resulting solution was evapo-
rated in high vacuum at -45 to -40 °C to dryness, the dark
green residue was chromatographed on a silica gel column (1.6
× 15 cm) at -25 °C with petroleum ether as the eluant. After
the light yellow band containing Fe(CO)5 (caution) was eluted
from the column, the blackish-green band was eluted with
petroleum ether/CH2Cl2 (10:1) and was collected, and then the
brown-red band was eluted with petroleum ether/CH2Cl2 (5:
1). The solvents were removed from the above two eluates
under vacuum, and the residues were recrystallized from
petroleum ether or petroleum ether/CH2Cl2 solution at -80
°C. From the first fraction, 0.291 g (81%, based on 1) of
blackish-green crystals of 5 were obtained: mp 80-82 °C (dec);
IR (νCO) (CH2Cl2) 2054 (s), 2022 (w), 1990 (vs), 1970 (s), 1889
Rea ction of [η-C5H5(CO)2RetCC6H5]BBr 4 (2) w ith 3 To
Give [ReCo{µ-CC6H5}(CO)5(η-C5H5)] (7) a n d [ReCo{µ-
C(CO)C6H5}(CO)5(η-C5H5)] (8). Compound 2 (0.31 g, 0.43
mmol) was treated, in a manner similar to that described above
for the reaction of 1 with 3, with Ph3P)2NFeCo(CO)8 (0.38 g,
0.43 mmol). Immediately, the orange solution turned red. The
reaction mixture was stirred at -90 to -45 °C for 4-5 h,
during which time the solution gradually turned purple-red
until blackish-green. Further treatment of the resulting
solution similar to that in the reaction of 1 with 3 afforded
0.183 g (80%, based on 2) of blackish-green crystals of 7 and
0.032 g (13%, based on 2) of 8 as brown-red crystals. 7: mp
68-70 °C (dec); IR (νCO) (CH2Cl2) 2050 (s), 2020 (vs), 1998
1
(s), 1978 (w), 1931 (s, br) cm-1; H NMR (CD3COCD3) δ 7.87
(m, 2H, C6H5), 7.60 (m, 1H, C6H5), 7.50 (m, 2H, C6H5), 5.70 (s,
5H, C5H5); MS m/e 512 (M+ - CO), 484 (M+ - 2CO), 456 (M+
- 3CO), 400 (M+ - 5CO). Anal. Calcd for C17H10O5ReCo: C,
37.85; H, 1.77. Found: C, 37.86; H, 1.96. 8: mp 76-78 °C
(dec); IR (νCO) (CH2Cl2) 2006(vs), 2000 (vs), 1998 (w), 1983
1
(m), 1923 (s), 1850 (s) cm-1; H NMR (CD3COCD3) δ 7.35 (m,
5H, C6H5), 5.70 (s, 5H, C5H5); MS m/e 568 (M+), 540 (M+
-
CO), 484 (M+ - 3CO), 456 (M+ - 4CO), 428 (M+ - 5CO), 400
(M+ - 6CO). Anal. Calcd for C18H10O6ReCo: C, 38.10; H, 1.78.
Found: C, 38.15; H, 1.84.
(s) cm-1
.
1H NMR (CD3COCD3) δ 7.82 (m, 2H, C6H5), 7.55 (m,
Rea ction of 1 w ith (P h 3P )2NWCo(CO)9 (4) To Give 5
a n d 6. Similar to the procedure for the reaction of 1 with 3,
compound 1 (0.52 g, 0.87 mmol) was treated with 0.90 g (0.87
mmol) of (Ph3P)2NWCo(CO)9 at -90 to -45 °C for 4 h, during
which time the orange-yellow solution gradually turned black-
ish-green. The solvent was removed at -45 to -40 °C in
vacuo. The dark red residue was chromatographed on SiO2
at -25 °C with petroleum ether/CH2Cl2 (10:1) as the eluant.
After the light yellow band containing W(CO)6 was eluted from
the column, the blackish-green band was eluted with petro-
leum ether/CH2Cl2/Et2O (10:1:1), and then the brown-red band
was eluted with petroleum ether/CH2Cl2/Et2O (5:1:1). The
solvents were removed from the above two eluates under
3H, C6H5), 5.07 (s, 5H, C5H5); MS m/e 408 (M+), 380 (M+
-
CO), 352 (M+ - 2CO), 324 (M+ - 3CO), 296 (M+ - 4CO), 268
(M+ - 5CO). Anal. Calcd for C17H10O5MnCo: C, 50.03; H,
2.47. Found: C, 49.91; H, 2.40. From the second fraction,
0.040 g (11%, based on 1) of brown-red crystals of 6 were
obtained: mp 109-110 °C (dec); IR (νCO) (CH2Cl2) 2054 (vs),
2022 (w), 1991 (vs), 1969 (s), 1891 (w), 1845 (m) cm-1; 1H NMR
(CD3COCD3) δ 7.81 (m, 2H, C6H5), 7.55 (m, 3H, C6H5), 5.06 (s,
5H, C5H5); MS m/e 436 (M+), 408 (M+ - CO), 380 (M+ - 2CO),
352 (M+ - 3CO), 324 (M+ - 4CO), 268 (M+ - 6CO). Anal.
Calcd for C18H10O6MnCo: C, 50.55; H, 2.65. Found: C, 50.10;
H, 2.30.

Reactions of Cationic Carbynes of Mn and Re
Ta ble 2. Selected Bon d Len gth s (Å)a a n d An gles (d eg)a for Com p lexes 5, 7, a n d 8
Compound 5
Organometallics, Vol. 17, No. 14, 1998 2947
Mn-Co
2.608(3)
1.85(1)
1.77(1)
1.77(2)
1.78(2)
Co-C(3)
Co-C(4)
Co-C(5)
C(8)-C(14)
1.80(1)
1.76(2)
1.76(2)
1.50(2)
Mn-C(8)
Co-C(8)
Mn-C(1)
Mn-C(2)
Co-Mn-C(8)
Mn-Co-C(8)
Mn-C(8)-Co
Co-Mn-C(1)
Co-Mn-C(2)
Mn-Co-C(3)
42.9(4)
45.2(4)
91.9(6)
68.8(5)
111.8(5)
100.1(5)
Mn-Co-C(4)
118.4(5)
123.8(6)
135.3(10)
132.8(10)
121(1)
Mn-Co-C(5)
Mn-C(8)-C(14)
Co-C(8)-C(14)
C(8)-C(14)-C(15)
C(8)-C(14)-C(19)
121(1)
7
8
7
8
Re-Co
2.710(2)
2.01(1)
1.82(1)
1.91(2)
1.92(2)
1.79(2)
2.720(1)
2.121(8)
2.021(8)
1.95(1)
1.89(1)
1.838(10)
Co-C(4)
1.83(2)
1.78(2)
1.800(1)
1.77(1)
1.987(8)
1.46(1)
1.40(1)
1.194(9)
Re-C(8)
Co-C(8)
Re-C(1)
Re-C(2)
Co-C(3)
Co-C(5)
Co-C(7)
C(8)-C(14)
C(7)-C(8)
C(7)-O(7)
1.45(2)
Re-Co-C(8)
Co-Re-C(8)
Re-C(8)-Co
Co-Re-C(1)
Co-Re-C(2)
Re-Co-C(3)
Re-Co-C(4)
Re-Co-C(5)
Re-Co-C(7)
48.0(4)
42.2(4)
89.9(5)
110.4(5)
70.3(4)
97.0(5)
118.8(5)
124.3(5)
50.5(2)
47.4(2)
82.1(3)
78.6(3)
111.9(3)
94.2(3)
93.5(3)
160.1(3)
71.4(3)
C(7)-Co-C(8)
40.9(3)
70.8(5)
Co-C(7)-C(8)
Re-C(8)-C(7)
Re-C(8)-C(14)
Co-C(8)-C(7)
Co-C(8)-C(14)
C(8)-C(14)-C(15)
C(8)-C(14)-C(19)
104.0(5)
133.2(6)
68.2(5)
125.2(6)
123.0(7)
119.8(7)
136(1)
133(1)
118(1)
122(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 lexes 9 a n d 10
9, M ) Mn
10, M ) Re
9, M ) Mn
10, M ) Re
M(1)-Co(1)
M(1)-Fe(1)
Co(1)-Fe(1)
M(1)-C(8)
Fe(1)-C(8)
Co(1)-C(8)
C(8)-C(9)
2.575(3)
2.570(2)
2.549(3)
1.94(1)
1.91(1)
1.94(1)
1.51(1)
1.82(1)
2.32(1)
2.707(1)
2.707(2)
2.542(2)
2.052(8)
1.936(8)
1.922(7)
1.48(1)
M(1)-C(2)
Fe(1)-C(2)
Co(1)-C(3)
Co(1)-C(4)
Co(1)-C(5)
Fe(1)-C(20)
Fe(1)-C(21)
Fe(1)-C(22)
1.83(1)
2.26(1)
1.80(1)
1.79(1)
1.83(2)
1.75(2)
1.80(2)
1.81(1)
1.922(10)
2.504(9)
1.834(10)
1.79(1)
1.791(10)
1.81(1)
1.78(1)
1.77(1)
M(1)-C(1)
Co(1)-C(1)
1.941(10)
2.539(10)
Fe(1)-Co(1)-M(1)
Co(1)-Fe(1)-M(1)
Co(1)-M(1)-Fe(1)
Co(1)-C(8)-M(1)
Fe(1)-C(8)-M(1)
Co(1)-C(8)-Fe(1)
Co(1)-M(1)-C(8)
M(1)-Co(1)-C(8)
Fe(1)-Co(1)-C(8)
60.21(7)
60.41(7)
59.38(7)
83.2(4)
83.9(4)
83.0(4)
48.4(3)
48.4(3)
48.0(3)
62.00(4)
61.99(4)
56.01(4)
85.8(3)
85.4(3)
82.4(3)
45.1(2)
49.1(2)
49.0(2)
Co(1)-Fe(1)-C(8)
M(1)-Fe(1)-C(8)
Fe(1)-M(1)-C(8)
Fe(1)-C(2)-M(1)
Co(1)-C(1)-M(1)
M(1)-C(8)-C(9)
Fe(1)-C(8)-C(9)
Co(1)-C(8)-C(9)
49.1(3)
48.6(3)
47.6(3)
77.2(5)
76.0(5)
132.8(8)
130.7(8)
125.7(8)
48.5(2)
49.1(2)
45.5(2)
74.1(3)
73.0(3)
129.4(6)
130.0(6)
127.5(5)
a
Estimated standard deviations in the least significant figure are given in parentheses.
vacuum, and the residues were recrystallized from petroleum
ether/CH2Cl2 solution at -80 °C. From the first fraction, 0.275
g (76%, based on 1) of blackish-green crystals of 5 were
obtained, which was identified by its mp and IR, 1H NMR,
and mass spectra. From the second fraction, 0.055 g (14%,
based on 1) of brown-red crystals of 6 were obtained, which
30 mL of THF at -50 to -40 °C for 6 h, during which time
the blackish-green solution gradually turned brown green.
After removal of the solvent in vacuo, the residue was
chromatographed on SiO2 with petroleum ether/CH2Cl2 (10:
1) as the eluant. The brown band was eluted and collected.
The solvent was removed, and the residue was recrystallized
from petroleum ether/CH2Cl2 solution at -80 °C to give 0.019
g (70%, based on 5) of brown-red crystals of 6, which was
1
was identified by its mp and IR, H NMR, and mass spectra.
Rea ction of 2 w ith 4 To Give 7 a n d 8. As described above
for the reaction of 1 with 3, compound 2 (0.23 g, 0.32 mmol)
was treated with 0.33 g (0.32 mmol) of 4 at -90 to -70 °C for
5 h, during which time the orange-red solution gradually
turned dark purple. Further treatment of the resulting
solution in a manner similar to that described in the reaction
of 1 with 4 afforded 0.064 g (37%, based on 2) of blackish-
green crystalline 7 and 0.103 g (57%, based on 2) of brown-
red crystals of 8, which were identified by their mp and IR,
1H NMR, and mass spectra.
1
identified by its mp and IR, H NMR, and mass spectra.
Rea ction of 5 w ith F e2(CO)9 To Give [Mn F eCo(µ3-
CC6H5)(µ-CO)2(CO)6(η-C5H5)] (9). To 27 mg (0.066 mmol)
of 5 dissolved in 50 mL of THF at -40 °C was added 90 mg
(0.247 mmol) of Fe2(CO)9. The mixture was stirred at -40 to
0 °C for 10 h, during which time the dark green solution
gradually turned brown-red. After the solution was evapo-
rated at 0 °C under vacuum to dryness, the residue was
chromatographed on SiO2 at -15 to -20 °C with petroleum
ether/CH2Cl2 (10:1) as the eluant. The purple-red band was
Rea ction of 5 w ith CO To Give 6. Carbon monoxide gas
was bubbled though a solution of 0.025 g (0.06 mmol) of 5 in

2948 Organometallics, Vol. 17, No. 14, 1998
Tang et al.
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 26 mg (72%, based
on 5) of purple-red crystals of 9: mp 91-92 °C (dec); IR (νCO)
(CH2Cl2) 2078 (vs), 2054 (w), 2031 (vs), 1984 (w), 1964 (m),
1889 (s), 1831 (m) cm-1; 1H NMR (CD3COCD3) δ 7.72 (m, 2H,
C6H5), 7.51 (m, 2H, C6H5), 7.33 (m, 1H, C6H5), 4.90 (s, 5H,
C5H5); MS m/e 548 (M+), 464 (M+ - 3CO), 408 (M+ - 5CO),
380 (M+ - 6CO), 324 (M+ - 8CO). Anal. Calcd for C20H10O8-
MnFeCo: C, 43.83; H, 1.84. Found: C, 43.78; H, 1.83.
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 5, 7, 8,
9, and 10 are given in Table 1. Selected bond lengths and
angles are listed in Tables 2 and 3. Atomic coordinates and
Biso/Beq, anisotropic displacement parameters, complete bond
lengths and angles, and least-squares planes for 5, 7, 8, 9, and
10 are given in the Supporting Information. The molecular
structures of 5, 7, 8, 9, and 10 are given in Figures 1, 2, 3, 4,
and 5, respectively.
Rea ction of 6 w ith F e2(CO)9 To Give 9. To 25 mg (0.057
mmol) of 6 dissolved in 40 mL of THF at -40 °C was added
93 mg (0.256 mmol) of Fe2(CO)9. The mixture was stirred at
-20 to 5 °C for 8 h, during which time the brown-green
solution gradually turned brown-red. Further treatment of
the resulting solution in a manner similar to that described
in the reaction of 5 with Fe2(CO)9 afforded 22 mg (71%, based
on 6) of purple-red crystalline 9, which was identified by its
Resu lts a n d Discu ssion
[η-C5H5(CO)2MntCC6H5]BBr4 (1) was treated with an
equimolecular amount of Ph3P)2NFeCo(CO)8 (3) in THF
at low temperature (-90 to -45 °C) for 3-4 h. After
removal of the solvent under high vacuum, the residue
was chromatographed on a SiO2 column at low temper-
ature and the crude products were recrystallized from
petroleun ether/CH2Cl2 at -80 °C to give blackish-green
complex 5, [MnCo{µ-CC6H5}(CO)5(η-C5H5)], and brown-
red complex 6, [MnCo{µ-C(CO)C6H5}(CO)5(η-C5H5)] (eq
1), in 81% and 11% isolated yields, respectively.
1
mp and IR, H NMR, and mass spectra.
Rea ction of 7 w ith F e2(CO)9 To Give [ReF eCo(µ3-
CC6H5)(µ-CO)2(CO)6-(η-C5H5)] (10). To 28 mg (0.052 mmol)
of 7 dissolved in 50 mL of THF at -40 °C was added 75 mg
(0.206 mmol) of Fe2(CO)9. The mixture was stirred at -20 to
0 °C for 10 h, during which time the dark green solution
gradually turned brown-red. Further treatment of the result-
ing solution as described above in the reaction of 5 with Fe2-
(CO)9 yielded 26 mg (74%, based on 7) of black-red crystalline
10: mp 86-88 °C dec; IR (νCO) (CH2Cl2) 2074 (vs), 2054 (w),
1
2025 (vs), 1970 (w), 1954 (w), 1909 (s), 1854 (m, br) cm-1; H
NMR (CD3COCD3) δ 7.53 (m, 2H, C6H5), 7.45 (m, 2H, C6H5),
7.22 (m, 1H, C6H5), 5.62 (s, 5H, C5H5). Anal. Calcd for
C20H10O8ReFeCo: C, 35.36; H, 1.48. Found: C, 35.60; H, 1.59.
Rea ction of 8 w ith F e2(CO)9 To Give 10. To 23 mg (0.041
mmol) of 8 dissolved in 40 mL of THF at -40 °C was added
65 mg (0.179 mmol) of Fe2(CO)9. The mixture was stirred at
-20 to 5 °C for 8 h, during which time the orange-red solution
gradually turned dark red. Further treatment as described
above in the reaction of 5 with Fe2(CO)9 gave 21 mg (75%,
based on 8) of black-red crystalline 10, which was identified
by its mp and IR and 1H NMR spectra.
X-r a y Cr ysta l Str u ctu r e Deter m in a tion s of Com p lexes
5, 7, 8, 9, a n d 10. Single crystals of 5, 7, 8, 9, and 10 suitable
for X-ray diffraction study were obtained by recrystallization
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 2630, 2759, 2976,
8003, and 7755 independent reflections, of which 1038, 1708,
1976, 3014, and 4978 with I > 3.00 σ (I) were observable, were
collected with a Rigaku AFC7R diffractometer at 20 °C using
Mo KR radiation with a ω-2θ scan mode within the ranges
5° e 2θ e 50° for 5, 7, 8, 9, and 10, respectively.
Analogous reaction of [η-C5H5(CO)2RetCC6H5]BBr4
(2) with 3 under the same conditions afforded blackish-
green crystalline 7, [ReCo{µ-CC6H5}(CO)5(η-C5H5)], and
brown-red crystalline 8, [ReCo{µ-C(CO)C6H5}(CO)5(η-
C5H5)] (eq 2), in 80% and 13% yields, respectively.
The structures of 5, 7, 8, and 9 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 based
on 1038, 1708, 1976, and 3014 observed reflections (I > 3.00σ-
(I)) and 217, 217, 235, and 559 variable parameters and
converged with unweighted and weighted agreement factors
of R ) 0.056 and Rw ) 0.057 for 5, R ) 0.039 and Rw ) 0.045
for 7, R ) 0.029 and Rw ) 0.030 for 8, and R ) 0.058 and Rw
) 0.051 for 9. For 10, the structure was solved by 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 4978
observed reflections (I > 3.00σ(I)) and 560 variable parameters
and converged with unweighted and weighted agreement
factors of R ) 0.031 and Rw ) 0.033. All of the calculations

Reactions of Cationic Carbynes of Mn and Re
Organometallics, Vol. 17, No. 14, 1998 2949
F igu r e 2. Molecular structure of 7, showing the atom-
numbering scheme.
F igu r e 1. Molecular structure of 5, showing the atom-
numbering scheme.
in 5 with the shorter Mn-Fe separation (2.572(1) Å)
found in analogous bridging carbyne complex [(CO)(η-
C5H5)Fe(µ-COEt)(µ-CO)Mn(η-C5H4Me)(CO)].8 But the
Mn-Co bond in 5 is slightly shorter than the similar
bond in the bridging carbene complex [MnFe(µ-C(CO-
Et)Ph}(η-C5H5)(CO)5] (2.6929(8) Å).4 The C(8)-Mn
linkage in 5 is slightly longer than the corresponding
distance (1.839(4) Å) in [(CO)(η-C5H5)Fe(µ-COEt)(µ-
CO)Mn(η-C5H4Me)(CO)]8 but is significantly shorter
than that in [MnFe(µ-C(COEt)Ph}(η-C5H5)(CO)5] (2.021-
(4) Å).4 The C(8)-Co distance in 5 (1.77(1) Å) is as
expected for a CdCo bond, which is obviously shorter
than corresponding distance in [(CO)(η-C5H5)Fe(µ-
COEt)(µ-CO)Mn(η-C5H4Me)(CO)] (1.843(4) Å)8 and [Mn-
Fe(µ-C(COEt)Ph}(η-C5H5)(CO)5] (2.020(4) Å).4
The molecular structure of complex 7 shown in Figure
2 resembles that of complex 5, as can be visualized in
the ORTEP diagrams of 5 and 7 represented in Figures
1 and 2. This investigation was carried out in order to
extend the scope of the structural data available for
heteronuclear dimetal bridging carbyne complexes. In
7 the dimensions of the dimetallacyclopropene ring are
Re-Co 2.710(2), C(8)-Re 2.01(1), and C(8)-Co 1.82(1)
Å. Since the radii of Re and W are approximately the
same, we can compare the metal-metal bond distance
in 7 with the slightly longer Co-W separation (2.758-
(1) Å) found in analogous carbyne complex [CoW(µ-
CC6H4Me4)(CO)3(η-C5H5)(η-C5Me5)].9 The Re-Co bond
length in 7 is somewhat longer than the similar bonds
found in [ReFe(µ-CC6H5)(µ-CO)(CO)3-(η-C5H5)(COC2-
B10H10)] (Re-Fe ) 2.682(2) Å).10 The C(8)-Re bond
distance in 7 is significantly longer than the corre-
sponding distance (1.86(4) Å) in [ReFe(µ-CC6H5)(µ-CO)-
Compound 1 also reacted with Ph3P)2NWCo(CO)9 (4)
under the same conditions to produce products 5 and 6
(eq 3) in similar yield. Complex 2 reacted similarly with
4 under the same conditions (eq 4), however, the main
product was complex 8 (57%) instead of complex 7 (37%).
THF
(Ph P) NWCo(CO)
1 +
2 +
-90 to -45 °C8 5 + 6 (3)
3
2
9
4
THF
(Ph P) NWCo(CO)
-90 to -45 °C8 7 + 8 (4)
3
2
9
4
On the basis of elemental analyses, spectroscopic evi-
dence, and X-ray crystallography, complexes 5 and 7 are
formulated as heteronuclear dimetal bridging carbyne
complexes, and complexes 6 and 8 are formulated as
heteronuclear dimetal bridging carbene complexes with
a CO group bonded to the bridging carbene carbon and
a Co atom through the carbon atom.
Complexes 5-8 are readily soluble in polar organic
solvents but sparingly soluble in nonpolar solvents.
They are sensitive to air and temperature in solution
but relatively stable as the solid. The compositions of
complexes 5-8 were established by elemental analysis
1
and IR, H NMR, and mass spectroscopy (see Experi-
mental Section), all of which are consistent with the
structures shown. The X-ray diffraction studies for
complexes 5, 7, and 8 were carried out in order to firmly
establish their structures.
The results of the X-ray diffraction work of complex
5 are summarized in Table 1, and the structure is shown
in Figure 1. In 5 the Mn-Co bond is bridged by CC6H5,
giving a dimetallacyclopropene ring. The dimensions
of the dimetallacyclopropene ring are: Mn-Co 2.608-
(3), C(8)-Mn 1.85(1), and C(8)-Co 1.77(1) Å. Since the
radii of coblt and iron are nearly the same, it is
interesting to compare the metal-metal bond distance
(8) Fong, R. H.; Lin, C.-H.; Idmoumaz, H.; Hersh, W. H. Organo-
metallics 1993, 12, 503.
(9) Abad, J . A.; Bateman, L. W.; J effery, J . C.; Mead, K. A.; Razay,
H.; Stone, F. G. A.; Woodward, P. J . Chem. Soc., Dalton Trans. 1983,
2075.

2950 Organometallics, Vol. 17, No. 14, 1998
Tang et al.
The possible reaction pathway to complexes 5 and 7
-
(eqs 1-4) could proceed via a synthon for Co(CO)3
,
which attacked on the carbyne carbon of cationic car-
byne complex 1 or 2 with bonding of the Co atom to the
Mn or Re atom to construct a dimetallacyclopropene
ring, since the analogous reaction13 of the Co(CO)4
-
anion with complex 1 or 2 under the same conditions
gave no bridging carbyne complex 5 or 7 but bridging
-
carbene complex 6 or 8. The clever synthon of Co(CO)3
could come from either expulsion of Fe(CO)5 or W(CO)6
-
-
directly from the FeCo(CO)8 or WCo(CO)9 anion in
the presence of complex 1 or 2 or a carbene intermediate
[η-C5H5(CO)2MdC(C6H5)M′Co(CO)n] (M ) Mn or Re, M′
) Fe or W, n ) 8 or 9) formed by attack of the
[M′Co(CO)n]- anion on the carbyne carbon of 1 or 2. The
carbene intermediate then underwent expulsion of Fe-
(CO)5 or W(CO)6 to generate the Co(CO)3- moiety. We
have indeed isolated Fe(CO)5 and W(CO)6 in the course
of the column chromatography (Experimental Section).
The formation of 6 or 8 could proceed via intermediate
complex 5 or 7. To explore this possibility, we investi-
gated the reaction of CO gas with complex 5. This
reaction gave complex 6 in 70% yield (eq 5). This result
THF
5 + CO -50 to -40 °C8 6
(5)
F igu r e 3. Molecular structure of 8, showing the atom-
numbering scheme.
shows that complex 5 can indeed convert to complex 6
and suggests that 6 was derived from 5 by addition of
one CO molecule generated by cleavage of the dimetal
carbonyl anions or other species.
(CO)3(η-C5H5)(COC2B10H10)]10 but somewhat shorter
than the corresponding distance in [ReFe(µ-CHC6H5)-
(CO)6(η-C5H5)] (2.120(5) Å).3 The C(8)-Co distance
(1.82(1) Å) in 7 is also as expected for a CdCo bond
based on the comparable µ-CdCo separation (1.77(1) Å)
found in 5.
A number of dimetal bridging carbyne complexes have
prepared by Stone et al. by reactions14 of alkylidyne
complexes with low-valent metal species or by reac-
tions15 of anionic carbyne complexes with cationic metal
compounds. Complexes 5 and 7, as heteronuclear
dimetal bridging carbyne complexes, were synthesized
first by reactions of the cationic carbyne complexes with
the mixed-dimetal carbonyl anions. Undoubtedly, this
is a new, direct, and convenient method for the synthesis
of dimetal bridging carbyne complexes.
The structure of complex 8 (Figure 3) resembles that
of [ReFe{µ-C(n-C4H9S)C6H5}(CO)5(η-C5H5)],11 except that
the substituent on the bridging carbene carbon is a
bridged CO group in 8 but a bridged n-C4H9S group in
the latter. The Re-Co bond is bridged by C(CO)C6H5,
giving a dimetallacyclopropane ring, and the CO group
is bridged to a µ-C-Co bond through the C(7) atom, thus
giving the Co an 18-electron configuration. The C(8)-
C(7) bond distance is only 1.40(1) Å. The Co-C(7)
distance of 1.987(8) Å is close in value to the similar
bond in [Fe(COC6H4CF3-p)(η-C5H5)(CO)2] (1.972(4) Å).12
The bond length of C(7)-O(7) (1.194(9) Å) is slightly
shorter than that in [Fe(COC6H4CF3-p)(η-C5H5)(CO)2]
(1.217(6) Å).12 In 8 the dimensions of the dimetallacy-
clopropane ring are Re-Co 2.720(1), C(8)-Re 2.121(8),
and C(8)-Co 2.021(8) Å. The Re-Co bond length in 8
is slightly shorter than the similar bonds found in
[ReFe(µ-CHC6H5)(CO)6(η-C5H5)] (2.7581(8) Å)3 and [ReFe-
(µ-C(n-C4H9S)C6H5}(CO)5(η-C5H5)] (2.784(2) Å)11 but is
nearly the same as that of 7. The C(8)-Re bond
distance in 8 is the same within experimental error as
the corresponding distance in [ReFe(µ-C(n-C4H9S)C6H5}-
(CO)5(η-C5H5)] (2.128(10) Å)11 but is somewhat longer
than that in 7 (2.01(1) Å). The C(8)-Co distance (2.021-
(8) Å) is markedly longer than that (1.82(1) Å) in 7.
Interestingly, complex 5 reacted with an excess of Fe2-
(CO)9 in THF at -40 to 0 °C for 10 h. After workup as
described in the Experimental Section, the purple-red
compound 9, [MnFeCo(µ3-CC6H5)(µ-CO)(CO)7(η-C5H5)],
was isolated in 72% yield (eq 6). Surprisingly, complex
6 can also react with Fe2(CO)9 under similar conditions
to give the same product 9 (eq 7) in nearly the same
yield.
Complex 7 or 8 reacted similarly with Fe2(CO)9 under
similar conditions to give blackish-red crystalline com-
pound 10, [ReFeCo(µ3-CC6H5)(CO)8(η-C5H5)], in 74-75%
yields (eqs 8 and 9).
Complexes 9 and 10 are formulated as the hetero-
(13) Tang, Y.-J .; Sun, J .; Chen, J .-B. Inorg. Chem. submitted for
publication.
(14) (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.
(15) (a) Ashworth, T. V.; Howard, J . A. K.; Laguna, M.; Stone, F. G.
A. J . Chem. Soc., Dalton Trans. 1980, 1593. (b) 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) Zhu, B.; Yu, Y.; Chen, J .-B.; Wu, Q.-J .; Liu, Q.-T. Organome-
tallics 1995, 14, 3963.
(11) Qiu, Z.-L.; Sun, J .; Chen, J .-B. Organometallics 1998, 17, 600.
(12) Chen, J .-B.; Yin, J .-G.; Lei, G.-X.; Wang, Y.-Y.; Lin, G.-D. J .
Chem. Soc., Dalton Trans. 1989, 635.

Reactions of Cationic Carbynes of Mn and Re
Organometallics, Vol. 17, No. 14, 1998 2951
nuclear trimetal bridging carbyne complexes whose
structures have been established by X-ray diffraction
studies.
The molecular structure of 9 is shown in Figure 4. It
is very interesting that complex 9 crystallizes with two
independent molecules in the asymmetric unit. How-
ever, its 1H NMR spectrum showed that the two
molecules are separated in solution, giving a single
normal molecule. Although two independent molecules
in an asymmetric unit is not unusual in crystallography,
this structure was observed in the trimetal bridging
carbyne complexes for first time.
F igu r e 4. Molecular structure of 9, showing the atom-
numbering scheme.
In 9 the triangular MnFeCo arrangement with a
capping µ3-CC6H5 ligand is confirmed. The three metal
atoms construct an approximate isosceles triangle (Mn-
(1)-Fe(1) ) 2.570(2) Å, Mn(1)-Co(1) ) 2.575(3) Å, and
Fe(1)-Co(1) ) 2.549(3) Å). The µ-C(8)-Mn(1), µ-C(8)-
Fe(1), and µ-C(8)-Co(1) distances are 1.94(1), 1.91(1),
and 1.94(1) Å, respectively. Compound 9 appears to be
the first example of a species with Mn-Co, Mn-Fe, and
Fe-Co bonds studies by X-ray crystallography, and
hence, comparison of these metal-metal bond distances
with others involving these elements is not possible.
In 9, the Fe and Co atoms each carry three terminal
carbonyl groups and the Mn atom carries one bridged
carbonyl group to Fe, with a second CO on Mn being
semi-bridging to Co (Mn(1)-C(2)-O(2) ) 155(1)°, Fe-
(1)-C(2) ) 2.26(1) Å; Mn(1)-C(1)-O(1) ) 160(1)°, Co-
(1)-C(1) ) 2.32(1) Å), thus giving each metal atom an
18-electron configuration.
The molecular structure of complex 10 shown in
Figure 5 has many common features with that of
complex 9. Similar to that found in 9, there are two
independent molecules in the asymmetric unit of 10.
The two molecules in the cell are the same. The
molecule of 10 possesses a trimetalatetrahedrane CRe-
FeCo core. The three metal atoms construct an ap-
proximate isosceles triangle (Re(1)-Fe(1) ) 2.707(2) Å,
Re(1)-Co(1) ) 2.707(1) Å, and Fe(1)-Co(1) ) 2.542(2)
Å). The Re-Co bond length is closely related to that of
known complexes [Co2Re(µ3-CC6H4Me-4)(CO)10] (aver-
F igu r e 5. Molecular structure of 10, showing the atom-
numbering scheme.
age Re-Co ) 2.70 Å)16 and [ReCo2(µ3-CC6H5)(µ-CO)2-
(CO)5(η-C5H5)(COC2B10H10)] (2.669(3) Å).10 The µ-C-
Re, µ-C-Fe, and µ-C-Co distances are 2.052(8), 1.936(8),
and 1.922(7) Å, respectively, of which the µ-C-Co bond
length is comparable to that found in [Co2Re(µ3-CC6H4-
Me-4)(CO)10] (average 1.89 Å)16 and [ReCo2(µ3-CC6H5)-
(µ-CO)2(CO)5(η-C5H5)(COC2B10H10)] (average 1.93 Å),10
while the µ-C-Re bond length is nearly the same as that
in [ReCo2(µ3-CC6H5)(µ-CO)2(CO)5(η-C5H5)(COC2B10H10)]
(2.01(1) Å)10 but somewhat shorter than that in [Co2-
Re(µ3-CC6H4Me-4)(CO)10] (average 2.189(6) Å).16
In 10 the Co and Fe atoms each carry three terminal
carbonyl groups and the Re atom carries two carbonyl
groups being semibridging to the Co and Fe atoms,
(16) J effery, J . C.; Lewis, D. B.; Lewis, G. E.; Stone, F. G. A. J . Chem.
Soc., Dalton Trans. 1985, 2001.

2952 Organometallics, Vol. 17, No. 14, 1998
Tang et al.
respectively (Re(1)-C(1)-O(1) ) 166.8(9)°, Co(1)-C(1)
) 2.539(10) Å; Re(1)-C(2)-O(2) ) 165.2(9)°, Fe(1)-C(2)
) 2.504(9) Å). Complex 10 is a 48 CVE (cluster valence
electron) complex, where the Re and Fe atoms formally
have 19 and 17 electrons, respectively, which probably
accounts for the presence of the semibridging carbonyl.
In 10 the semibridging CO ligand reveals itself in the
IR spectrum with a band at 1854 cm-1. The analogous
48-valence-electron structure was found in the complex
[MW2{µ3-C2R2)(CO)7(η-C5H5)2] (M ) Ru or Os).17
A series of trimetal bridging carbyne complexes have
been synthesized by Stone et al. by reactions14a,c,18 of
alkylidyne complexes, such as [W(tCC6H4Me-4)(CO)2-
(η-C5H5)], with low-valent metal species. Complexes 9
and 10, as heteronuclear trimetal bridging carbyne
complexes, were obtained by the reaction of dimetal
bridging carbyne or bridging carbene complexes with
Fe2(CO)9. Only one analogous reaction is known.14c
Stone et al. reported that the carbyne complex
[M(tCC6H4Me-4)(CO)2(η-C5H5)] (M ) Mo or W) reacted
with an excess of Fe2(CO)9 to afford a trimetal bridging
carbyne complex, [MFe2{µ3-C(C6H4Me-4)}(CO)9(η-C5H5)]
(M ) Mo, W).14c In this reaction, the initially formed
dimetal bridging carbyne intermediate [MFe(µ-CC6H4-
Me-4)(η-C5H5)(CO)6] reacted further with Fe2(CO)9 to
give the trimetal species. The reaction of a dimetal
bridging carbene complex with low-valent metal species
giving a trimetal bridging carbyne complex is unusual.
To our knowledge, no such reaction has been reported.
The reaction of the dimetal bridging carbene complexes
with Fe2(CO)9 afforded the heteronuclear trimetal bridg-
ing carbyne complexes, which may represent a new
route to 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 atomic
coordinates and Biso/Beq, anisotropic displacement parameters,
complete bond lengths and angles, and least-squares planes
for 5, 7, 8, 9, and 10 (58 pages). Ordering information is given
on any current masthead page.
(17) 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.
(18) Chetcuti, M. J .; Chetcuti, P. A. M.; J effery, J . C.; Mills, R. M.;
Mitrprachachon, P.; Pickering, S. J .; Stone, F. G. A.; Woodward, P. J .
Chem. Soc., Dalton Trans. 1982, 699.
OM9800400