Unusual reactions of cationic carbyne complexes of manganese and rhenium with [NMe4][HFe(CO)4] to form heteronuclear dimetal carbene-bridged complexes

Article abstract of DOI:10.1039/a708910d

The reaction of a cationic carbyne complex of manganese [Mn(≡CPh)(η-C₅H₅)(CO)₂]BBr ₄ 1 with the salt [NMe₄][HFe(CO)₄] 3 in thf at low temperature gave [Mn(η-C₅H₅)(CO)₃] 4 and a novel dimetal carbene-bridged complex [MnFe{μ-C(H)Ph}(η-C₅H₅)(CO)₅] 5. The cationic rhenium carbyne complex [Re(≡CPh)(η-C₅H₅)-(CO)₂]BBr ₄ 2 similarly reacted with 3 to give [Re(η-C₅H₅)(CO)₃] 6 and [ReFe{μ-C(H)Ph}(η-C₅H₅)(CO)₆] 7. Complex 5 reacted with carbon monoxide gas leading to cleavage of the μ-C-Mn and Mn-Fe bonds to afford 4 and a novel benzene-co-ordinated acyltricarbonyliron complex [Fe(PhCHCO)(CO)₃] 8. The reaction of 7 with PPh₃ yielded [ReFe{μ-C(H)Ph}(η-C₅H₅)(CO)₅(PPh ₃)] 9. The structures of complexes 5, 8 and 9 have been established by X-ray diffraction studies.

Full text of DOI:10.1039/a708910d

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Unusual reactions of cationic carbyne complexes of manganese and
rhenium with [NMe4][HFe(CO)4] to form heteronuclear dimetal
carbene-bridged complexes
Yongjun Tang, Jie Sun and Jiabi Chen*
Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, China
᎐
The reaction of a cationic carbyne complex of manganese [Mn(᎐CPh)(η-C H )(CO) ]BBr 1 with the salt
᎐
5
5
2
4
[NMe4][HFe(CO)4] 3 in thf at low temperature gave [Mn(η-C5H5)(CO)3] 4 and a novel dimetal carbene-bridged
᎐
complex [MnFe{µ-C(H)Ph}(η-C H )(CO) ] 5. The cationic rhenium carbyne complex [Re(᎐CPh)(η-C H )-
᎐
5
5
5
5
5
(CO)2]BBr4 2 similarly reacted with 3 to give [Re(η-C5H5)(CO)3] 6 and [ReFe{µ-C(H)Ph}(η-C5H5)(CO)6] 7.
Complex 5 reacted with carbon monoxide gas leading to cleavage of the µ-C᎐Mn and Mn᎐Fe bonds to afford
4 and a novel benzene-co-ordinated acyltricarbonyliron complex [Fe(PhCHCO)(CO)3] 8. The reaction of 7
with PPh3 yielded [ReFe{µ-C(H)Ph}(η-C5H5)(CO)5(PPh3)] 9. The structures of complexes 5, 8 and 9 have
been established by X-ray diffraction studies.
Our interest in the synthesis, structure, and chemistry of di- and
tri-metal carbene- and carbyne-bridged complexes stems from
the possible involvement of these species in some reactions
catalysed by organometallic compounds.1,2 The chemistry of
the carbene- and carbyne-bridged complexes has been exten-
sively studied by Stone and co-workers and a number of
dimetal carbene-bridged complexes has been synthesized
by the reactions of carbene complexes with low-valent metal
species3,4 or of neutral carbyne complexes with metal hydrides.5,6
(EI) mass spectra on a Hewlett-Packard 5989A spectrometer.
Melting points obtained on samples in sealed nitrogen-filled
capillaries are uncorrected.
᎐
Reaction of [Mn(᎐CPh)(ç-C H )(CO) ]BBr 1 with [NMe ]-
᎐
5
5
2
4
4
[HFe(CO)4] 3 to give [Mn(ç-C5H5)(CO)3] 4 and [MnFe{ì-C(H)-
Ph}(ç-C5H5)(CO)5] 5
The compound [NMe4][HFe(CO)4] 3 (0.64 g, 2.63 mmol) was
dissolved in thf (80 cm3) and cooled to Ϫ90 ЊC. To this solution
was added portionwise 1 (1.57 g, 2.63 mmol) with vigorous
stirring. The reaction mixture was stirred at Ϫ90 to Ϫ45 ЊC for
4 h, during which time the orange solution gradually turned
dark purple-red. The resulting solution was evaporated to dry-
ness under high vacuum at Ϫ45 to Ϫ40 ЊC. The dark purple-red
residue was chromatographed on an alumina column (neutral,
200–300 mesh; 1.6 × 15 cm) at Ϫ25 ЊC with light petroleum as
the eluent. The orange band which eluted first was collected,
and then the purple-red band was eluted with light petroleum–
CH2Cl2 (20:1). The solvents were removed from the above two
eluates under vacuum, and the residues recrystallized from light
petroleum or light petroleum–CH2Cl2 solution at Ϫ80 ЊC. From
the first fraction, 0.15 g (25%, based on 1) of yellow crystals of
Recently, we reported the reaction of a cationic carbyne
᎐
complex [M(᎐CPh)(η-C H )(CO) ]BBr (M = Re or Mn) with
᎐
5
5
2
4
[Fe(CO)4]2Ϫ to yield unexpected dimetal carbene-bridged com-
plexes.7,8 This represents a new route to such complexes. We are
now interested in examining the application range of this new
synthetic method for dimetal carbene-bridged complexes and
the effect of different nucleophiles containing the carbonyliron
anion on the reactivities of cationic carbyne complexes and
on the reaction products. Thus, we chose the monoanion
[HFe(CO)4]Ϫ 3 as a nucleophile for the reaction with the
cationic carbyne complexes [M(᎐CPh)(η-C H )(CO) ]BBr
᎐
᎐
5
5
2
4
(M = Mn 1 or Re 2) which afforded new heteronuclear dimetal
carbene-bridged complexes. Herein we describe this unusual
reaction and the structures of the resulting products.
4
12 was obtained, a known compound identified by comparison
of its melting point, IR and 1H NMR spectra with those of the
actual sample. From the second fraction, 0.68 g (63%, based on
1) of 5 as purple-red crystals was obtained, m.p. 142–144 ЊC
(decomp.) IR (n-hexane): ν (CO) 2002s, 2000s, 1995s, 1952vs
Experimental
All reactions were performed under a dry, oxygen-free nitrogen
atmosphere 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 a nitrogen atmosphere. Tetrahydrofuran (thf) and diethyl
ether (Et2O) were distilled from sodium–benzophenone, while
light petroleum (b.p. 30–60 ЊC) was distilled from CaH2 and
CH2Cl2 from P2O5. The neutral alumina (Al2O3) used for
chromatography was deoxygenated at room temperature under
(br) and 1918s cmϪ1. H NMR (CD3COCD3): δ 10.26 (s, 1 H,
1
µ-CH), 7.34–7.13 (m, 5 H, C6H5) and 5.11 (s, 5 H, C5H5). Mass
spectrum m/z 406 (Mϩ) and 322 (Mϩ Ϫ 3CO) (Found: C, 49.60;
H, 2.55. Calc. for C17H11FeMnO5: C, 50.03; H, 2.73%).
᎐
Reaction of [Re(᎐CPh)(ç-C H )(CO) ]BBr 2 with [NMe ]-
᎐
5
5
2
4
4
[HFe(CO)4] 3 to give [Re(ç-C5H5)(CO)3] 6 and [ReFe-
{ì-C(H)Ph}(ç-C5H5)(CO)6] 7
high vacuum for 16 h, deactivated with 5% w/w N2-saturated
᎐
water, and stored under N . The compounds [Mn(᎐CPh)-
᎐
2
9
10
᎐
(η-C H )(CO) ]BBr 1 and [Re(᎐CPh)(η-C H )(CO) ]BBr 2
Compound 2 (0.47 g, 0.65 mmol) was treated, in a manner
similar to that described above, with [NMe4][HFe(CO)4] (0.16 g,
0.66 mmol). The reaction mixture was stirred at Ϫ90 to Ϫ50 ЊC
for 3.5 h, during which time the orange-yellow solution grad-
ually turned purple-red. Further treatment of the resulting
mixture as described above afforded 0.015 g (6%, based on 2) of
yellow crystals of 613 and 0.26 g (71%, based on 2) of brick-red
᎐
5
5
2
4
5
5
2
4
were prepared as previously described, as was [NMe4][HFe-
(CO)4] 3.11
The IR spectra were recorded on a Shimadzu-IR-440 spec-
trophotometer, 1H NMR spectra at ambient temperature
(20 ЊC) in (CD3)2CO solution with SiMe4 as internal reference
using a Bruker AM-300 spectrometer and electron ionization
J. Chem. Soc., Dalton Trans., 1998, Pages 931–936
931

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crystals of 7.7 Complex 6 was identified by comparison of its
melting point, IR and 1H NMR spectra with those of the actual
sample. Complex 7: m.p. 84–85 ЊC (decomp.) IR (CH2Cl2) ν
[Mn( CPh)(η-C5H5)(CO)2]BBr4 + [NMe4][HFe(CO)4]
1
3
2016s, 1996vs, 1950s (br) and 1891vs (br) cmϪ1 1H NMR
.
thf – 90 to – 45 °C
(CD3COCD3) δ 9.02 (s, 1 H, µ-CH), 7.42 (m, 2 H, C6H5), 7.21
(m, 2 H, C6H5), 7.00 (m, 1 H, C6H5) and 5.70 (s, 5 H, C5H5).
Mass spectrum m/z 566 (Mϩ, based on 187Re, 56Fe) (Found: C,
38.56; H, 2.15. Calc. for C18H11FeO6Re: C, 38.24; H, 1.96%).
H
C
CO
[Mn(η-C5H5)(CO)3] + (η-C5H5)Mn
Fe CO
Reaction of complex 5 with CO to give 4 and [Fe(PhCHCO)-
(CO)3] 8
CO
CO
CO
4
5
Carbon monoxide gas was bubbled through a solution of com-
plex 5 (0.037 g, 0.09 mmol) in thf (40 cm3) at Ϫ40 to Ϫ10 ЊC for
6 h, during which time the purple-red solution gradually turned
brown-red. After removal of the solvent in vacuo, the residue
was chromatographed on Al2O3 with light petroleum as the
eluent. The orange band which eluted first was collected, and
then the brown-red band was eluted with light petroleum–
CH2Cl2–Et2O (20:1:1). The solvents were removed from the
above two eluates under vacuum, and the residues recrystallized
from light petroleum or light petroleum–CH2Cl2 solution at
Ϫ80 ЊC. From the first fraction, 0.006 g (31%, based on 5) of
yellow crystals of 4 was obtained. From the second, 0.011 g
(46%, based on 5) of brown-red crystals of 8 was obtained: m.p.
66–68 ЊC (decomp.); IR (n-hexane) ν (CO) 2063s, 2004vs, 1994vs
[Re( CPh)(η-C5H5)(CO)2]BBr4 + [NMe4][HFe(CO)4]
2
3
thf – 90 to – 50 °C
H
C
CO
CO
[Re(η-C5H5)(CO)3] + (η-C5H5)Re
Fe CO
CO
6
CO
CO
7
Scheme 1
1
and 1788s cmϪ1; H NMR (CD3COCD3) δ 7.30–7.17 (m, 5 H,
C6H5) and 6.13 (s, 1 H, CH); mass spectrum m/z 258 (Mϩ)
and 202 (Mϩ Ϫ 2CO) (Found: C, 50.85; H, 2.50. Calc. for
C11H6FeO4: C, 51.21; H, 2.34%).
was applied which resulted in transmission factors ranging from
0.96 to 1.00.
The structures of complexes 5 and 9 were solved by direct
methods and expanded using Fourier techniques. The non-
hydrogen atoms were refined anisotropically for 9, but only the
Fe and Mn were anisotropic for 5. The hydrogen atoms were
included but not refined. The final cycle of full-matrix least-
squares refinement was based on 704 and 2860 observed reflec-
tions and 107 and 442 variable parameters and converged with
unweighted and weighted agreement factors of R = 0.090 and
RЈ = 0.092 for 5 and 0.049 and 0.057 for 9, respectively. For 8
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 864 observed reflections and 145
variables and converged with R = 0.031 and RЈ = 0.035. All the
calculations were performed using the TEXSAN software
package.15
Reaction of complex 7 with PPh3 to give [ReFe{ì-C(H)Ph}-
(ç-C5H5)(CO)5(PPh3)] 9
To complex 7 (0.050 g, 0.09 mmol) dissolved in thf (30 cm3) at
Ϫ55 ЊC was added PPh3 (0.026 g, 0.10 mmol). The mixture was
stirred at Ϫ55 to 0 ЊC for 7 h, during which time the brown-red
solution turned gradually orange-red. After evaporation of the
solvent in vacuo, the residue was chromatographed on alumina
with light petroleum followed by light petroleum–CH2Cl2
(10:1) as the eluent. After leaving the orange-red band which
contains unchanged 7, the orange band was eluted with light
petroleum–CH2Cl2–Et2O (5:1:1) and collected. The solvent
was removed under vacuum, and the residue recrystallized from
light petroleum–CH2Cl2 solution at Ϫ80 ЊC to give 0.045 g
(52%, based on 7) of orange-yellow crystals of 9: m.p. 85–86 ЊC
(decomp.); IR (CH2Cl2) ν (CO) 2040w, 2033s, 1959vs and
Details of the crystallographic data and the procedures used
for data collection and reduction are given in Table 1, selected
bond lengths and angles in Tables 2 and 3, respectively.
CCDC reference number 186/861.
1
1878vs cmϪ1; H NMR (CD3COCD3) δ 8.50 (s, 1 H, µ-CH),
7.47–7.34 (m, 15 H, C6H5), 6.98–6.84 (m, 5 H, C6H5) and 5.47
(s, 5 H, C5H5); mass spectrum m/z 543 (Mϩ Ϫ H Ϫ PPh3), 515
(Mϩ Ϫ H Ϫ PPh3 Ϫ CO), 431 (Mϩ Ϫ H Ϫ PPh3 Ϫ 4CO) and
403 (Mϩ Ϫ H Ϫ PPh3 Ϫ 5CO) (Found: C, 44.60; H, 2.90. Calc.
for C35H26FePReO5ؒ2CH2Cl2: C, 45.10; H, 3.15%).
Results and Discussion
᎐
The complex [Mn(᎐CPh)(η-C H )(CO) ]BBr 1 was treated
᎐
5
5
2
4
Crystallography
with an equimolecular amount of [NMe4][HFe(CO)4] 3 in thf at
Ϫ90 to Ϫ45 ЊC for 4 h. After removal of the solvent under high
vacuum, the residue was chromatographed on an alumina
column at low temperature and the crude products were
recrystallized from light petroleum–CH2Cl2 at Ϫ80 ЊC to give
yellow crystals of 4 and purple-red crystals of 5 (Scheme 1) in
25 and 63% isolated yields, respectively. Complex 4 is a known
compound [Mn(η-C5H5)(CO)3]12 and 5 is a novel heteronuclear
dimetal carbene-bridged complex with the composition
[MnFe{µ-C(H)Ph}(η-C5H5)] the structure of which has been
Single crystals of complexes 5, 8 and 9 suitable for X-ray dif-
fraction study were obtained by recrystallization from light
petroleum–CH2Cl2 solutions at Ϫ80 ЊC. They were sealed in
capillaries under a nitrogen atmosphere. X-Ray diffraction data
were collected with a Rigaku AFC7R diffractometer at 20 ЊC
using Mo-Kα radiation (λ 0.710 69 Å) and the ω–2θ scan mode
within the ranges 5 р 2θ р 40Њ for 5, 5 р 2θ р 50Њ for 8, and
5 р 2θ р 45Њ for 9, respectively. Intensity data for 1649, 1106
and 3788 independent reflections, of which 704, 864 and 2860
had I > 2.00σ(I) (for 5) and I > 3.00σ(I) (for 8 and 9), were
corrected for Lorentz-polarization effects. An empirical absorp-
tion correction using the program DIFABS14 was applied which
resulted in transmission factors ranging from 0.66 to 0.97 and
0.84 to 1.17 for 5 and 9, respectively. For 8, an empirical absorp-
tion correction based on azimuthal scans of several reflections
confirmed by X-ray crystallography.
᎐
The complex [Re(᎐CPh)(η-C H )(CO) ]BBr 2 reacted simi-
᎐
5
5
2
4
larly under the same conditions to afford yellow crystals of 6
and the brick-red crystals of 7 in 6 and 71% yields, respectively.
Complexes 6 and 7 are known compounds, the former is
[Re(η-C5H5)(CO)3]13 and the latter, a dimetal carbene-bridged
932
J. Chem. Soc., Dalton Trans., 1998, Pages 931–936

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H
C
thf
O
4 +
C
5 + CO
– 40 to 10 °C
Fe CO
CO
CO
8
H
C
CO
(η-C5H5)Re
CO
CO
Fe CO
thf
7 + PPh3
– 55 to 0 °C
Ph3P
CO
9
Scheme 2
Fig. 2 Molecular structure and atom labelling for [Fe(PhCHCO)-
(CO)3] 8
the result undoubtedly confirms the overall structure of 5. The
molecular structure 5 shows a bridge system in which two
carbon atoms[C(12) and C(13)] of the phenyl ring are bonded
to the Fe atom to construct a ferracyclopropane ring. However,
there is no 1H NMR evidence for this because no high-field shift
attributed to the proton attached to the ‘olefinic’ bond was
observed. We tentatively explain it by the C(12) and C(13)
atoms being involved in η2 instead of η1,η1 bonding to the Fe
atom; thus in solution the phenyl group rotates about the
C(11)᎐C(12) bond on the NMR timescale at room temperature
(20 ЊC) as that observed in the analogous complex [CoW{µ-
η1 :η3-CH(C6H4Me-4)}(η-C5H5)(η-C5Me5)(CO)3][BF4] which
showed dynamic behaviour for the tolyl group at 25 ЊC, ceasing
at Ϫ70 ЊC.16 The Mn–Fe distance of 2.770(7) Å in 5 is some-
what longer than that found in analogous carbene-bridged
complexes [MnFe{µ-C(COEt)Ph}(η-C5H5)(CO)5] [2.6929(8)
Å]8 and [ReFe{µ-C(H)Ph}(η-C5H5)(CO)6] [2.7581(8) Å].7
The molecular structure of complex 8 (Fig. 2) shows that the
Fig. 1 Molecular structure and atom labelling for [MnFe{µ-C(H)Ph}-
(η-C5H5)(CO)5] 5
complex, is identical with that produced by the reaction7 of 2
with [NEt4]2[Fe2(CO)8], Na2[Fe(CO)4] or Na2[Fe3(CO)11].
Interestingly, the reaction of complex 5 with carbon mon-
oxide gas in thf at Ϫ40 to Ϫ10 ЊC led to heterolytic cleavage of
the Mn–Fe bond and breaking of the µ᎐C᎐Mn bond of 5 to
afford 4 and brown-red crystals of 8 (Scheme 2) in 31 and 46%
yields, respectively. Compound 8 is formulated as a novel
benzene-co-ordinated acyltricarbonyliron complex with the
composition [Fe(Ph2CHCO)(CO)3] the structure of which has
been established by X-ray diffraction analysis. However, com-
plex 7 did not react with carbon monoxide gas under the same
conditions. When a stoichiometric amount of CO gas was used
for the reaction with 5 no product 8 was isolated, indicating that
an excess of CO is necessary. It is equally interesting that
complex 7 when treated with PPh3 in thf at Ϫ55 to 0 ЊC
gave [ReFe{µ-C(H)Ph}(η-C5H5)(CO)5(PPh3)] 9, in which a CO
ligand on iron has been displaced by PPh3, in 52% yield.
Unexpectedly, the reaction of 5 with PPh3 under the same
conditions gave no analogous PPh3-substituted complex, as in
the reaction of [PtW{µ-η1 :η3-CH(C6H4Me-4)}(η-C5H5)(CO)2-
(PEt3)2][BF4]16 or complex 7 with PPh3, but decomposition
products such as [Fe(CO)3(PPh3)2].17
Complexes 5, 8 and 9 are readily soluble in polar organic
solvents but slightly soluble in non-polar solvents, and sensitive
to air and temperature in solution but relatively stable as solids.
Their structures were confirmed by elemental analyses, spectro-
scopic data (Experimental section) and X-ray diffraction
analyses.
The molecular structure of complex 5 is shown in Fig. 1.
Owing to serious intensity decay of the crystal during the data
collection at room temperature (20 ЊC), only reflections within
the range 5 р 2θ р 40Њ were collected, so that only 668 reflec-
tions with I > 3.00σ(I) were observable, which led to a poor
refinement and larger errors for the bond parameters. However,
benzene ring is still bonded to the Fe atom, and a formyl (C᎐O)
᎐
group is bonded to the original alkylidene carbon [C(11)] and
the Fe atom through the C(18) atom and provides one electron
for the Fe atom to satisfy an 18-electron configuration. The
molecular structure reveals a bridge system in which two car-
bon atoms [C(12) and C(13)] of the aryl ring form an η2
attachment to the iron, so that the C(H)Ph group as a whole
adopts an η3-bonding mode to the metal as that of µ-C(H)-
C6H4Me in [PtW{µ-η1 :η3-CH(C6H4Me-4)}(η-C5H5)(CO)2-
(PMe3)2]BF4.16 However, the 1H NMR data for 8 at 20 ЊC show
dynamic behaviour for the phenyl group and reveal that in
solution it rotates about the C(11)᎐C(12) bond on the NMR
timescale as in 5.
The molecular structure of complex 9 (Fig. 3) resembles that
of 7, except that the substituents on the Fe atom are three CO
and one PPh3 groups in 9 but four CO groups in 7. The co-
ordination geometry around the Re atom is that of a pseudo-
trigonal bipyramid if the (η5)-bonded cyclopentadienyl is
regarded as occupying a single polyhedral vertex, and the Fe
atom is in an approximately octahedral environment. The
Re᎐Fe bond length of 2.777(2) Å in 9 is slightly longer than that
of 7 [2.7581(8) Å].7 The alkylidene carbon asymmetrically
bridges the Re᎐Fe bond [µ-C᎐Re 2.17(1), µ-C᎐Fe 2.03(1) Å]
with an angle Re᎐C(7)᎐Fe of 82.7(5)Њ similar to that in 7
[µ-C᎐Re 2.120(5), µ-C᎐Fe 2.097(5) Å; Re᎐C(7)᎐Fe 81.7(2)Њ].
The µ-C᎐Re distance in 9 is comparable with that of 7 and the
complex [Re2(µ-H)2(µ-CHBut)(η-C6H6)2] [2.13(3) Å],18 and the
µ-C᎐Fe distance is close to that found in 5. The P᎐Fe bond
length of 2.258(4) Å is nearly the same as the normal P᎐Fe
bond distance {2.260(3) Å in [PFe(NO)2(CO)(PPh3)],19 2.244(1)
Å in [Fe(CO)4(PPh3)]20}. The P᎐Fe᎐C(7) and P᎐Fe᎐Re bond
angles are 96.7(4) and 147.3(1)Њ, respectively.
J. Chem. Soc., Dalton Trans., 1998, Pages 931–936
933

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Table 1 Crystal data and experimental details for complexes 5, 8 and 9
5
8
9
Formula
M
C17H11FeMnO5
C11H6FeO4
258.01
C37H29Cl4FeO5PRe
969.48
406.06
Crystal system
Space group
a/Å
b/Å
c/Å
α/Њ
β/Њ
Triclinic
P1 (no. 2)
Orthorhombic
P212121 (no. 19)
10.977(5)
14.384(3)
6.646(4)
Triclinic
P1 (no. 2)
¯
¯
7.326(7)
17.650(8)
6.809(4)
94.73(7)
113.93(6)
87.35(7)
801(1)
11.744(3)
16.132(3)
10.803(3)
100.32(2)
110.50(2)
91.14(2)
1878.4(9)
2
1.712
39.74
23 (13.6–21.5)
3788
2860
442
0.049
0.057
1.81
0.19
1.28, Ϫ1.63
γ/Њ
U/Å3
1049.4(8)
4
1.633
14.28
16 (18.5–21.7)
1106
864
145
0.031
0.035
1.26
Z
2
Dc/g cmϪ3
1.681
17.13
12 (6.6–18.6)
1649
704 [I > 2.00σ(I)]
107
0.090
0.092
2.04
0.07
µ(Mo-Kα)/cmϪ1
Orientation reflections: 2θ range/Њ
No. unique data, total
with I > 3.00σ(I)
No. parameters refined
Ra
RЈb
Goodness of fitc
Largest shift/e.s.d. in final cycle
0.00
0.31, Ϫ0.23
Maximum, minimum electron density/e ÅϪ3 0.79, Ϫ0.62
¹
¹
a Σ Fo| Ϫ |Fc /Σ|Fo|. b [Σw(|Fo| Ϫ |Fc|)2/Σw|Fo|2]²; w = 1/σ2(|Fo|). c [Σw(|Fo| Ϫ Fc|)2/(No Ϫ Np)]², where No, Np = numbers of observations and parameters.
Fig. 3 Molecular structure and atom labelling for [ReFe{µ-C(H)Ph}(η-C5H5)(CO)5(PPh3)] 9
The possible reaction pathway to complex 5 (Scheme 1) could
involve initial formation of a carbene intermediate [(OC)2-
(CO)3], and [PtW(µ-CC6H4Me-4)(η-C5H5)(CO)2(PR3)2] (PR3 =
PMe3, PMe2Ph, or PMePh2) with HBF4ؒEt2O, or by the re-
action22 of the neutral carbyne complex [W(᎐CC H Me-4)-
᎐
(η-C H )Mn᎐C(Ph)FeH(CO) ], where the FeH(CO) moiety is
᎐
᎐
5
5
4
4
6
4
directly bonded to the carbene carbon through Fe, by attack of
the [HFe(CO)4]Ϫ anion on the cationic carbyne carbon of 1.
The carbene intermediate would then undergo a hydrogen
migration from Fe to the carbene carbon and bonding of the
Fe to Mn accompanied by loss of one CO ligand from the
Fe(CO)4 moiety and co-ordination of the benzene ring to the Fe
atom. Analogous heteronuclear dimetal carbene-bridged com-
plexes, [MW{µ-η1 :η3-CH(C6H4Me-4)}(η-C5H5)(CO)2(Ln)][BF4]
[MLn = Cr(η-C5H5)(CO)(NO), Co(CO)(η-C5Me5), or Pt(PR3)2]
(η-C5H5)(CO)2] with the cationic metal hydride trans-[Pt(H)-
(PEt3)2(Me2CO)][BF4].
The reaction pathway to complex 8 (Scheme 2) might
proceed by an initial attack of CO on the µ-C᎐Mn or/and
Mn᎐Fe bond of 5 which could then suffer heterolytic cleavage
of these bonds with addition of one CO molecule to the Mn
and the insertion of another CO molecule into the µ-C᎐Fe
bond to form complexes 4 and 8, respectively. The formation of
8 is not surprising since the analogous insertion of CO into the
Fe᎐C (carbene) bond of an η3-co-ordinated carbene ligand to
give an (vinylketene)iron complex with an η4-co-ordinated acyl
ligand has been observed in the reaction of tricarbonyl-
(η3-vinylcarbene)iron with carbon monoxide.23
and
[PtW{µ-η1 :η3-CH(C6H4Me-4)}(η-C5H5)(CO)2(PEt3)2]-
[BF4], with the co-ordination of the benzene ring to the metal,
have been reported by Stone and co-workers16,21 by protonation
of dimetal carbyne-bridged complexes [CrW(µ-CC6H4Me-4)(η-
C5H5)2(CO)3(NO)], [CoW(µ-CC6H4Me-4)(η-C5H5)(η-C5Me5)-
The heteronuclear dimetal carbene-bridged complexes 5 and
934
J. Chem. Soc., Dalton Trans., 1998, Pages 931–936

View Article Online
Table 2 Selected bond lengths (Å) for complexes 5, 8 and 9
5
8
5
8
Fe᎐Mn
Fe᎐C(4)
2.770(7)
1.75(4)
2.05(3)
2.24(3)
Fe᎐C(3)
Fe᎐C(5)
Fe᎐C(12)
Mn᎐C(1)
Mn᎐C(6)
Mn᎐C(8)
Mn᎐C(10)
O(1)᎐C(1)
O(3)᎐C(3)
O(5)᎐C(5)
O(6)᎐C(18)
C(11)᎐C(12)
C(12)᎐C(17)
C(14)᎐C(15)
C(11)᎐C(18)
1.73(4)
1.73(4)
2.09(3)
1.71(4)
2.15(4)
2.18(4)
2.05(3)
1.15(4)
1.14(4)
1.18(3)
1.869(6)
1.772(6)
2.177(5)
1.784(6)
2.088(5)
2.274(5)
1.914(6)
Fe᎐C(11)
Fe᎐C(13)
Fe᎐C(18)
Mn᎐C(2)
Mn᎐C(7)
Mn᎐C(9)
Mn᎐C(11)
O(2)᎐C(2)
O(4)᎐C(4)
C(12)᎐C(13)
C(13)᎐C(14)
C(15)᎐C(16)
C(16)᎐C(17)
1.66(4)
2.16(4)
2.19(3)
1.92(3)
1.26(4)
1.17(3)
1.44(4)
1.39(4)
1.36(4)
1.40(4)
1.127(6)
1.136(7)
1.196(6)
1.396(8)
1.445(7)
1.360(9)
1.441(8)
1.148(6)
1.428(7)
1.412(8)
1.425(10)
1.335(10)
1.47(4)
1.44(4)
1.31(4)
Complex 9
B
Re᎐Fe
2.777(2)
1.91(2)
2.30(2)
2.31(2)
2.33(2)
1.78(2)
Fe᎐C(5)
P᎐C(19)
P᎐C(31)
O(2)᎐C(2)
O(4)᎐C(4)
C(7)᎐C(13)
1.78(2)
1.85(1)
1.81(2)
1.15(2)
1.13(2)
1.54(2)
Re᎐C(1)
1.72(2)
2.17(1)
2.23(2)
2.32(2)
2.258(4)
1.81(2)
Fe᎐C(7)
P᎐C(25)
O(1)᎐C(1)
O(3)᎐C(3)
O(5)᎐C(5)
2.03(1)
Re᎐C(2)
Re᎐C(8)
Re᎐C(10)
Re᎐C(12)
Fe᎐C(3)
Re᎐C(7)
Re᎐C(9)
Re᎐C(11)
Fe᎐P
1.84(2)
1.25(2)
1.15(2)
1.13(2)
Fe᎐C(4)
Estimated standard deviations in the least significant figure are given in parentheses.
Table 3 Selected bond angles (Њ) for complexes 5, 8 and 9
5
8
5
8
Mn᎐Fe᎐C(3)
Mn᎐Fe᎐C(5)
Mn᎐Fe᎐C(12)
C(11)᎐Fe᎐C(12)
C(12)᎐Fe᎐C(13)
Fe᎐Mn᎐C(2)
Fe᎐Mn᎐C(11)
Mn᎐C(2)᎐O(2)
Fe᎐C(4)᎐O(4)
Fe᎐C(11)᎐C(12)
Fe᎐C(12)᎐C(11)
Fe᎐C(12)᎐C(17)
C(11)᎐C(12)᎐C(17)
Fe᎐C(13)᎐C(12)
Fe᎐C(11)᎐C(18)
Fe᎐C(18)᎐O(6)
O(6)᎐C(18)᎐C(11)
C(13)᎐Fe᎐C(18)
C(3)᎐Fe᎐C(18)
C(12)᎐C(11)᎐C(18)
160(1)
107(1)
76.7(9)
41(1)
38(1)
71(1)
47.7(9)
168(3)
174(3)
70(1)
Mn᎐Fe᎐C(4)
84(1)
Mn᎐Fe᎐C(11)
Mn᎐Fe᎐C(13)
C(11)᎐Fe᎐C(13)
Fe᎐Mn᎐C(1)
C(1)᎐Mn᎐C(11)
C(2)᎐Mn᎐C(11)
Mn᎐C(1)᎐O(1)
Fe᎐C(3)᎐O(3)
43.9(8)
88.4(8)
73(1)
105(1)
80(1)
110(1)
175(3)
170(3)
178(3)
88(1)
128(2)
76(1)
38.2(2)
37.4(2)
67.6(2)
175.0(5)
74.4(3)
67.5(3)
124.0(4)
122.6(5)
67.6(3)
62.6(3)
144.9(5)
138.3(5)
81.2(2)
157.4(3)
116.6(5)
178.9(5)
178.5(6)
Fe᎐C(5)᎐O(5)
67(1)
Fe᎐C(11)᎐Mn
Mn᎐C(11)᎐C(12)
Fe᎐C(12)᎐C(13)
C(11)᎐C(12)᎐C(13)
C(5)᎐Fe᎐C(18)
Fe᎐C(13)᎐C(14)
C(12)᎐Fe᎐C(18)
C(4)᎐Fe᎐C(18)
C(11)᎐Fe᎐C(18)
Fe᎐C(18)᎐C(11)
124(2)
125(2)
64(1)
75.0(3)
118.8(5)
87.5(3)
121.8(4)
72.0(2)
99.8(3)
41.9(2)
75.5(3)
124(2)
126(2)
Complex 9
Fe᎐Re᎐C(1)
Fe᎐Re᎐C(7)
C(1)᎐Re᎐C(2)
Re᎐Fe᎐P
Re᎐Fe᎐C(4)
Re᎐Fe᎐C(7)
P᎐Fe᎐C(7)
108.8(6)
46.6(4)
83.3(8)
147.3(1)
106.3(5)
50.7(3)
Fe᎐Re᎐C(2)
76.1(5)
91.7(6)
117.1(6)
86.9(7)
96.7(6)
88.1(8)
116.3(5)
104.0(6)
C(25)᎐P᎐C(31)
Re᎐C(2)᎐O(2)
Fe᎐C(4)᎐O(4)
Re᎐C(7)᎐C(13) 122.3(9)
C(4)᎐Fe᎐C(7)
Fe᎐P᎐C(19)
102.1(7)
175(4)
174(1)
Re᎐C(1)᎐O(1)
Fe᎐C(3)᎐O(3)
Fe᎐C(5)᎐O(5)
Re᎐C(7)᎐Fe
Fe᎐C(7)᎐C(13)
Re᎐Fe᎐C(3)
175(1)
174(1)
176(1)
82.7(5)
125.4(9)
90.6(5)
87.1(6)
C(1)᎐Re᎐C(7)
C(2)᎐Re᎐C(7)
C(3)᎐Fe᎐C(4)
C(3)᎐Fe᎐C(7)
C(4)᎐Fe᎐C(5)
Fe᎐P᎐C(25)
156.6(6)
115.5(5)
116.4(5)
100.3(7)
96.7(4)
173.7(7)
Fe᎐P᎐C(31)
C(19)᎐P᎐C(31)
Re᎐Fe᎐C(5)
C(3)᎐Fe᎐C(5)
C(19)᎐P᎐C(25)
7 were synthesized by a new route. Thus, the cationic carbyne
complexes of manganese and rhenium not only react with the
carbonyliron dianion but also with the carbonyliron mono-
anion to produce dimetal carbene-bridged complexes. More-
over, the present method is a more simple and convenient
route to the preparation of such complexes.
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Acknowledgements
We thank the National Natural Foundation of China and the
Science Foundation of the Chinese Academy of Sciences for
financial support.
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Received 11th December 1997; Paper 7/08910D
936
J. Chem. Soc., Dalton Trans., 1998, Pages 931–936