Chemistry of vinylidene complexes. XX. Intramolecular carbonylation of vinylidene on the MnFe center: Spectroscopic and structural study. X-ray structure of the new trimethylenemethane type MnFe complex

Article abstract of DOI:10.1016/j.jorganchem.2010.10.035

Reactions of Fe₂(CO)₉ with Cp(CO)₂MnCCHPh (1) and Cp(CO)(PPh₃)MnCCHPh (3) gave the heterometallic trimethylenemethane complexes η⁴-{C[Mn(CO)₂Cp](CO) CHPh}Fe(CO)₃ (2) and η⁴-{C[Mn(CO)(PPh ₃)Cp](CO)CHPh}Fe(CO)₃ (4), respectively. The formation of the benzylideneketene [PhHCCCO] fragment included in complexes 2 and 4 occurs via intramolecular coupling of the carbonyl and vinylidene ligands. The structures of 3 and 4 were determined by single crystal XRD methods. The influence of the nature of the L ligands at the Mn atom on the structural and spectroscopic characteristics of η⁴-{C[Mn(CO)(L)Cp](CO)CHPh} Fe(CO)₃ (L = CO (2), PPh₃ (4)) is considered. According to the VT ¹H and ¹³C NMR spectra, complex 2 reversibly transforms in solution into μ-η¹:η¹-vinylidene isomer Cp(CO)₂MnFe(μ-CCHPh)(CO)₄ (2a), whereas complex 4 containing the PPh₃ ligand is not able to a similar transformation.

Full text of DOI:10.1016/j.jorganchem.2010.10.035

Journal of Organometallic Chemistry 696 (2011) 963e970
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Chemistry of vinylidene complexes. XX. Intramolecular carbonylation of
vinylidene on the MnFe center: Spectroscopic and structural study. X-ray
structure of the new trimethylenemethane type MnFe complexq,qq
,
a
b
,
,
Alla B. Antonova a , Oleg S. Chudin , Alexander D. Vasiliev c, Anatoly I. Rubaylo a c, Victor V. Verpekin a,
*
William A. Sokolenko a, Nina I. Pavlenko a, Oleg V. Semeikin d
a Institute of Chemistry & Chemical Technology, Siberian Branch of the Russian Academy of Sciences, K. Marx Street 42, Krasnoyarsk 660049, Russia
b Institute of Physics, Siberian Branch of the Russian Academy of Sciences, Akademgorodok 50-38, Krasnoyarsk 660036, Russia
c Siberian Federal University, Svobodny Prospect 79, Krasnoyarsk 660041, Russia
d A.N. Nesmeyanov Institute of Organo-Element Compounds, Russian Academy of Sciences, Vavilov Street 28, Moscow 119991, Russia
a r t i c l e i n f o
a b s t r a c t
Article history:
Reactions of Fe2(CO)9 with Cp(CO)2Mn]C]CHPh (1) and Cp(CO)(PPh3)Mn]C]CHPh (3) gave the
heterometallic trimethylenemethane complexes
h
4-{C[Mn(CO)2Cp](CO)CHPh}Fe(CO)3 (2) and
Received 26 July 2010
Received in revised form
17 October 2010
Accepted 18 October 2010
Available online 26 October 2010
h
4-{C[Mn(CO)(PPh3)Cp](CO)CHPh}Fe(CO)3 (4), respectively. The formation of the benzylideneketene
[PhHC]C]C]O] fragment included in complexes 2 and 4 occurs via intramolecular coupling of the
carbonyl and vinylidene ligands. The structures of 3 and 4 were determined by single crystal XRD
methods. The influence of the nature of the L ligands at the Mn atom on the structural and spectroscopic
characteristics of
h
4-{C[Mn(CO)(L)Cp](CO)CHPh}Fe(CO)3 (L ¼ CO (2), PPh3 (4)) is considered. According to
Keywords:
Manganese
Iron
the VT 1H and 13C NMR spectra, complex 2 reversibly transforms in solution into h1 1-vinylidene
m- :h
isomer Cp(CO)2MnFe(
m-C]CHPh)(CO)4 (2a), whereas complex 4 containing the PPh3 ligand is not able to
a similar transformation.
Carbonyl complexes
Ó 2010 Elsevier B.V. All rights reserved.
Heteronuclear vinylidene complexes
Intramolecular vinylidene carbonylation
Trimethylenemethane complexes
1. Introduction
As a rule, the [Fe(CO)4] fragment adds to the M]C1 bond
(M ¼ Mn, Rh) of the mononuclear vinylidene LM]C1]C2HR or
allenylidene LM]C1]C2]C3R2 complex to form the triangular
Transition metal complexes containing vinylidene ligands C]
CRR’ (R and R0 ¼ H, alkyl, aryl, etc.) attract attention due to their use
in stoichiometric syntheses of organometallic compounds and
valuable organic substances, as well as due to their participation as
intermediates in many catalytic processes [1e12].
MFe(
with the organic part of the molecule. The syntheses of the
stable Cp(CO)2MnFe[ -C]C(H)COOMe](CO)4, Cp(CO)2MnFe[ -C]
C]CPh2](CO)4 [14], Cp(i-Pr3P)RhFe( -C]CHR)( -CO)(CO)3 and
(i-Pr3P)RhFe2(m3-C]CHR)(
m
-C1) system, but does not participate in any other interactions
m
m
m
m
The reactions of the second metal atom M0 addition to the
mononuclear LM]C]CHR complexes represent
method for dinuclear heterometallic -vinylidene complexes
synthesis [1e6]. A wide series of dinuclear -vinylidene complexes
m
-CO)2(CO)4Cp (R ¼ H, Me, Ph) [15]
a
common
complexes can be mentioned as examples.
m
m
In contrast, the addition of the [Fe(CO)4] fragment to
Cp(CO)2Mn]C]CHPh (1) resulted not in the expected
dene Cp(CO)2MnFe( -C]CHPh)(CO)4 (2a), but in its isomer
4-{C[Mn(CO)2Cp](CO)CHPh}Fe(CO)3 (2) including the benzylide-
m-vinyli-
with the MneM0 (M0 ¼ Mo, W, Mn, Fe, Rh, Pd, Pt, Cu) [2,3,13,14],
ReeM0 (M0 ¼ Pd, Pt) [1] and RheM0 bonds (M0 ¼ Cr, Mn, Fe) [6a,15]
have been obtained based on the corresponding complexes
Cp(CO)2Mn]C]CHR (R ¼ Ph (1), COOMe), Cp(CO)2Re]C]CHPh
and Cp(i-Pr3P)Rh]C]CHR (R ¼ H, Me, Ph).
m
h
neketene fragment [PhHC]C]C]O] [16]. This reaction was the
first example of the vinylidene carbonylation by intramolecular
vinylidene-carbonyl coupling on a metal center, and complex 2
appeared to be the first heterometallic congener of trimethylene-
methane (TMM) transition metal complexes.
q
For Part XIX, see Ref. [1].
Abbreviations: Cp ¼
qq
h
5-C5H5; TMM ¼ trimethylenemethane; VT ¼ variable
Complex
Cp(CO)2Mn(
2
was also obtained by the reaction between
temperature; XRD ¼ X-ray diffraction.
h
2-HC^CPh) and Fe2(CO)9 in low yield [17]. The
* Corresponding author. Tel.: þ7 391 227 3835; fax: þ7 391 212 4720.
E-mail address: ale@kraslan.ru (A.B. Antonova).
formation of 2 was observed during the action of Fe2(CO)9 on
0022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.10.035

964
A.B. Antonova et al. / Journal of Organometallic Chemistry 696 (2011) 963e970
Cp(CO)2MnRh(
m
-C]CHPh)(Acac)(CO) [18] or [Cp(CO)2MnCu(
m
-C]
That is the evidence of the reversibility of the intramolecular
carbonyl-vinylidene coupling for this system.
CHPh)(
fragments by [Fe(CO)4].
Complex
4-{C[Fe(CO)3(Et3P)](CO)CH2}Fe(CO)2(Et3P) incorpo-
m-Cl)2]2 [19] occurring with the substitution of the Rh or Cu
In this article we describe the synthesis of the new hetero-
h
nuclear TMM complex h
4-{C[Mn(CO)(PPh3)Cp](CO)CHPh}Fe(CO)3
rating the vinylideneketene fragment [H2C]C]C]O] has also been
reported [20]. Its crystal structure corresponds to the “TMM type”,
(4), formed from the irreversible intramolecular vinylidene
carbonylation by treatment of Cp(CO)(PPh3)Mn]C]CHPh (3) with
Fe2(CO)9, and its investigation by XRD and spectroscopic methods.
The structure of the initial compound 3 has also been solved by
X-ray single crystal analysis. The interconversion of the complexes
2 and 2a caused by the reversible carbonylation of the vinylidene
ligand and decarbonylation of the benzylideneketene in the
absence of the electron donor ligand PPh3 at the Mn atom has been
studied by VT NMR spectroscopy.
but in solution the complex is in equilibrium with the
isomer Fe2( -C]CH2)(CO)6(PEt3)2.
The -vinylidene complex Mn2(CO)8[
m
-vinylidene
m
m
m
-C1]C2(H)C(OEt)]O]
containing the EtOC]O substituent at the C2 atom has been formed
by UV-irradiation of Mn2(CO)10 and HC^COEt in hexane solution
saturated with carbon monoxide [21]. Various methods have been
investigated to obtain complexes containing the h
1-vinylidene C1]
C2(C]O)RR0 (R ¼ Me, Ph, CHPh2, OMe, etc.) ligands [22]. However,
these complexes can not be attributed to vinylidene carbonylation
products in the strict sense of the word.
2. Results and discussion
The intramolecular vinylidene carbonylation has been observed
The synthetic routes employed for preparation of complexes
2e4 are shown in Scheme 1. The complexes were characterized by
the IR and NMR spectroscopy. The structures of 3 and 4 were solved
via the single crystal X-ray technique.
on the diplatinum center [23]. The action of PPh3 on (C6F5)2ꢀ(C3O)-
Pt2(
(C6F5)2(PPh3)Pt[(
neketene [PhC2H]C1]C3]O] ligand serves as
one of the Pt atoms, and forms a C1-Pt
-bond with the second Pt. The
formationofbenzylideneketene[PhC2H]C1]C3]O]isaresultof the
C-C coupling of the C3O and -C1]C2HPh ligands.
m
-C1]C2HPh)(PPh3)2 resulted in the unusual complex
h
3-PhC2HC1C3O)Pt(PPh3)2], in which the benzylide-
3-allylic ligand on
h
2.1. Syntheses of
4-{C[Mn(CO)(PPh3)Cp](CO)CHPh}Fe(CO)3 (4)
h
4-{C[Mn(CO)2Cp](CO)CHPh}Fe(CO)3 (2) and
s
h
m
The vinylidene carbonylation reactions do not have common
features, as it follows from the above rare examples. At the same
time, the intra- and intermolecular carbonylation reactions of
carbenes and carbynes on mono-, di- and polymetal centers
The reaction of Cp(CO)(PPh3)Mn]C]CHPh (3) with Fe2(CO)9
in benzene at 20 ꢁC for 3 h resulted in the formation of
h
4-{C[Mn(CO)(PPh3)Cp](CO)CHPh}Fe(CO)3 (4) (Scheme 1).
The new compound 4 was isolated in 70% yield as the stable
black crystals easily soluble in polar and moderately soluble in
nonpolar organic solvents.
resulting in the formation of free ketenes, coordinated
h
2-ketene,
h
1- and 2-ketenyl groups, are quite common and have been
h
intensively investigated [24e31]. The formation of ketene ligands
by insertion of CO into the metal-carbene bond is considered to be
the key step in useful synthetic reactions such as Dötz’s benzan-
nulation reaction [24] and other carbon chain growth processes. In
addition, the interest in carbonylation reactions is caused by the
organometallic compounds participating in similar reactions
considered as models of probable intermediates in the Fischer-
Tropsch process [8,32,33].
Complex 2 was synthesized earlier from complex 1 and Fe2(CO)9
(Scheme 1) and characterized by the X-ray, IR and mass spec-
trometry data [16]. The ion peaks at m/z 130 belonging to the
benzylideneketene ion [PhCH]C]C]O]þ were found in the mass
spectra of complexes 2 and 4.
2.2. X-ray diffraction study of Cp(CO)(PPh3)Mn]C]CHPh (3)
Recently, we have briefly reported [3,34] that the hetero-tri-
methylenemethane form of complex 2,
CHPh}Fe(CO)3, exists in solutions in equilibrium with the
Complex 3 was synthesized earlier [13] by the photochemical
reaction of Cp(CO)2Mn]C]CHPh (1) with PPh3. The structure of 3
was proposed on the base of the IR, NMR and elemental analysis
data [13,35].
h
4-{C[Mn(CO)2Cp](CO)-
m
-vinylidene form Cp(CO)2MnFe(m-C]CHPh)(CO)4 (2a) (Scheme 1).
O
Ph
H
C
2
C
3
O
1
C
O
3
Mn
Ph
H
O
1
2
Ph
C
C
C
C
+
C
[Fe(CO)4]
2
C
1
3
Mn
C
C
3
Mn
Fe
CO
O
H
Fe
C
C
C
C
C
O
O
O
C
C
O
C
O
O
O
O
(1)
(2a)
(2)
- CO
+ PPh3
PPh3
C
O
1
Mn
Ph
2
Ph
C
C
+
3
Fe2(CO)9
1
2
C
H
C
3
Mn
C
O
Fe
H
C
O
C
PPh3
O
C
C
O
O
(3)
(4)
Scheme 1.

A.B. Antonova et al. / Journal of Organometallic Chemistry 696 (2011) 963e970
965
Table 1
Crystallographic data and refinement details for complexes 3 and 4.
Complex
3
4
Empirical formula
Colour
Formula weight
T (K)
C32H26MnOP
Dark red
512.44
C36H26FeMnO5P ꢂ 0.5(C6H14
Black
723.41
)
296
288
Crystal system
Space group
a (Å)
b (Å)
c (Å)
Triclinic
Pe1
Triclinic
Pe1
8.674 (1)
10.060 (1)
16.134 (2)
104.748 (2)
99.377 (2)
101.054 (1)
1302.5 (3)
1.307
11.132 (7)
11.439 (7)
15.281 (9)
105.767 (7)
97.754 (8)
102.599 (7)
1788 (2)
1.344
a
b
g
(ꢁ)
(ꢁ)
(ꢁ)
V (Å3)
rc (g/cmꢀ3
)
Z
m
2
2
(MoKa) (mmꢀ1
)
0.591
0.845
Ntot
10993
14173
Nuniq (Rint
2
)
5610 (0.0169)
54
6985 (0.0283)
52
qmax (ꢁ)
R1
0.0402
0.0502
wR2
GooF
Drmin
0.1204
1.015
ꢀ0.22/0.52
0.1575
1.015
ꢀ0.41/0.71
Fig. 1. Molecular structure of Cp(CO)(PPh3)Mn]C]CHPh (3). Hydrogen atoms of C5H5
and C6H5 groups are omitted for clarity. Selected interatomic distances (Å) and bond
angles (ꢁ): Mn]C(1) 1.752(2); C(1)]C(2) 1.328(3); C(2)eC(4) 1.486(3); MneC(3) 1.769
(3); MneP 2.2378(7); C(3)eO(3) 1.157(3); MneCp 2.150(2); MneC(1)eC(2) 178.6(2);
C(1)eC(2)eC(4) 125.7(2); MneC(3)eO(3) 177.9(3); C(1)eMneC(3) 91.4(1); C(1)e
MneP 91.34(7); C(3)eMneP 89.29(9).
/Drmax
2.3. X-ray diffraction study of h
4-{C[Mn(CO)(PPh3)Cp](CO)CHPh}Fe-
Whereas the [Fe(CO)4] unit adds to complex 3 to give 4, no
addition of [CuCl] and [Pt(PPh3)] fragments occurs, contrary to
complex 1. We have supposed that the bulky PPh3 ligand at the Mn
atom hinders this joining.
The X-ray diffraction study of a single crystal was performed to
determine the structure of 3 (Fig. 1). The selected crystallographic
data are given in Table 1.
The structures of the [Cp(CO)Mn]C]CHPh] fragments in
complexes 1 [36] and 3 are similar. The MneC(1)eC(2) angle in 3 is
more near to linear one than that in 1 (174(2)ꢁ). The Mn]C(1) bond
in 3 is substantially longer and the C(1)]C(2) bond in 3 is slightly
shorter than the similar bonds in 1 (1.68(2) and 1.34(3) Å,
respectively).
In contrast to 1, where the metallaallene Mn]C(1)]C(2)
system is weakly shielded by other ligands and can easily be
attacked even by bulky reagents [3], the Mn]C(1)]C(2) system of
complex 3 is strongly shielded by the PPh3 ligand on the one side,
and by phenyl group on the other side.
(CO)3 (4)
The structure of 4 is shown in Fig. 2. The main crystallographic
data are given in Table 1. The selected geometrical parameters of 2
and 4 are given in Table 2.
The benzylideneketene [PhC2H]C1]C3]O3] together with the
[Mn(CO)(PPh3)Cp] group form the unusual organometallic ligand
{C1[Mn(CO)(PPh3)Cp](C3O3)C2HPh} which is
Fe atom.
h
4-coordinated to the
The structure of 4 is similar to that of 2 [16] and classical TMM
complexes
4-[C(CH2)3]Fe(CO)3 [38] and 4-[C(CH2)2(CHPh)]Fe-
(CO)3 [39] (Scheme 3).
The {C(1)(Mn)[C(3)O]C(2)HPh} fragment in 2 is an almost planar
conjugated system, and the central C(1) atom is displaced from the
MnC(2)C(3) plane by 0.10 Å opposite to the Fe atom [16]. In the
h
h
molecules
h h
4-[C(CH2)3]Fe(CO)3 [38] and 4-[C(CH2)2(CHPh)]Fe-
(CO)3 [39] such displacement is 0.3 Å. The C(1) atom in complex 4 is
displaced from the MnC(2)C(3) plane by 0.302 Å.
The facile formation of 4 from 3 can be explained by assumption
The Fe atom attached to the
fragment of 4 has octahedral configuration which is typical for the
trimethylenemethane iron complexes. The methylene groups in h4
[C(CH2)3]Fe(CO)3 [38] and
4-[C(CH2)2(CHPh)]Fe(CO)3 [39] are in
a staggered conformation in relation to the CO groups. The Fe(CO)3
and C(1)MnC(2)C(3) fragments of 2 and 4 (see Fig. 2b) are also
mutually staggered. The axis of the Fe(CO)3 group, having the C3v
h
4-{C[Mn(CO)(PPh3)Cp](CO)CHPh}
that the first step of the reaction of 3 with Fe2(CO)9 is the h2
-
coordination of the [Fe(CO)4] fragment to the S(1)]S(2) bond. The
following intramolecular carbonylation within an intermediate 4a
results in the final product 4 (Scheme 2).
The possibility of the intermediate 4a formation in this reaction
was shown by the quantum chemical DFT-B3LYP calculations [37a].
-
h
O
C
PPh3
PPh3
C
.
,
3
O
1
O
Mn
Mn
Ph
H
Ph
2
3
1
2
C
+
[Fe(CO)4]
C
C
C
1
3
C
Mn
C
C
3
2
H
C
Fe
O
CO
C
Fe
Ph
PPh3
O
C
O
C
C
C
H
C
O
O
O
O
(4)
(3)
(4a)
Scheme 2.

966
A.B. Antonova et al. / Journal of Organometallic Chemistry 696 (2011) 963e970
Fig. 2. Molecular structure of
h
4-{C[Mn(CO)(PPh3)Cp](CO)CHPh}Fe(CO)3 (4). Two perspectives (a) and (b). Hydrogen atoms of C5H5 and C6H5 groups in both perspectives, and Ph
groups of the PPh3 ligand in (b) are omitted for clarity.
local symmetry, coincides with the FeeC(1) bond in all four
compounds.
presence of the PPh3 ligand which is very bulky and possesses the
stronger electron-donating ability, compared with the CO group at
the Mn atom in complex 2.
Therefore, the compound 4 belongs to the type of heterometallic
trimethylenemethane complexes where the “trimethylene-
methane” system is created by the isolobal replacement of one of
the [CH2] groups by [C(3)]O(3)], the second [CH2] e by the
[Mn(CO)(PPh3)Cp] group, and the phenylmethylene [CHPh] is the
third substituent at the central C(1) atom.
2.4. Spectroscopic study of
and
4-{C[Mn(CO)(PPh3)Cp](CO)CHPh}Fe(CO)3 (4)
h
4-{C[Mn(CO)2Cp](CO)CHPh}Fe(CO)3 (2)
h
The differences in behavior of complexes 2 and 4 in solutions
revealed by IR and NMR spectroscopy are considered in this section.
The IR spectrum of complex 4 in cyclohexane solution contains
The h
4-{C[Mn(CO)(PPh3)Cp](CO)CHPh} group in 4 contains the
somewhat shorter C(1)eC(2), C(1)eC(3) and MneC(1) bonds than
the corresponding bonds in the molecule 2 (Table 2). The bond
distance C(3)]O(3) of the benzylideneketene fragment PhC(2)H]
C(1)]C(3)]O(3) in complex 4 is somewhat longer than that in 2.
The MneFe distance 2.846(2) Å in complex 4 is longer than this
distance 2.760(4) Å in complex 2. The MneC1eC3 angle in complex
4 is 17ꢁ less than the similar angle in molecule 2. These features of
the complex 4 geometry can apparently be explained by the
five bands in the
n
(CO) region, one of which, at 1835 cmꢀ1, is
attributed to the C3]O3 group, that is consistent with the structure
found in the solid state (Fig. 2). A similar band of the S3]P3 group
at 1844 cmꢀ1 has been found in the IR spectrum of 2 [16]. Unlike
complex 4, the IR spectrum of 2 contains the increased number of
the
the
n
(CO) bands (8 bands instead of 6) (Table 3). The IR spectrum of
-vinylidene complex Cp(CO)2MnFe( -C]CHCOOMe)(CO)4
(CO) bands from 2090 to 1930 cmꢀ1 is
m
m
[14] which contains five
n
given in Table 3 for comparison.
The 1H NMR spectrum of complex 4 in d6-acetone solution
contains the doublet signal of the cyclopentadienyl ligand protons
Table 2
Selected bond lengths (Å) and angles (ꢁ) for complexes 2 and 4.
at
at
d
4.57 ppm (3JPH ¼ 2.05 Hz). A similar signal of the C5H5 protons
2 [16]
4
d
4.65 ppm (3JPH ¼ 1.15 Hz) is observed for the initial compound 3
Bond lengths (Å)
MneFe
MneC1
C1eC2
C1eC3
C3]O3
FeeC1
FeeC2
FeeC3
MneP
C4eO4
[35]. The singlet signal of the proton C2H of 4 is observed at
2.760 (4)
2.03 (2)
1.44 (2)
1.45 (2)
1.16 (2)
2.00 (1)
2.22 (1)
2.08 (2)
e
2.846 (2)
2.012 (4)
1.409 (5)
1.410 (5)
1.190 (5)
2.017 (4)
2.141 (4)
2.066 (4)
2.303 (2)
1.164 (4)
1.776 (4)
2.175 (2)
d
3.27 ppm. It should be noted that the 1H NMR spectrum of the
TMM complex
4-[C1(C3H2)2(C2HPh)]Fe(CO)3 contains the C2HPh
proton resonance at 4.28 ppm [39].
h
d
The signal of the central S1 atom of complex 4 is observed in the
13S NMR spectrum at
d
101.60 ppm with 2JPC ¼ 34.04 Hz. The signal
of the carbonyl group Mn-CO at d 241.51 ppm has the similar value
of the coupling constant JPC ¼ 39.59 Hz. The signal of C2 at
2
73.49 ppm has a considerably smaller constant 3JPC ¼ 2.77 Hz.
1.17 (2)
1.79 (2)
2.18 (2)
d
MneC4
MneCp (av.)
The chemical shifts of the proton S2H and carbon S1 signals of
complexes 2 and 4 (Table 3) are close to the corresponding signals
in the NMR spectra of the known complexes (TMM)Fe(CO)3
[40e42]. The signals of the C2HR proton of the TMM complexes
Bond angles (ꢁ)
MneC1eC2
MneC1eC3
C2eC1eC3
FeeC1eMn
FeeC1eC2
124.8 (1)
124.4 (1)
119.8 (1)
86.3 (6)
86.3 (6)
72.1 (1)
152.5 (2)
125.3 (3)
107.2 (3)
116.5 (3)
89.9 (2)
75.0 (2)
71.7 (2)
151.2 (4)
with various R substituents are in the range of
the signals of C1 in the 13S NMR spectra are near
The 31P NMR spectrum of complex 4 contains a signal at
87.57 ppm which is close to the value of 89.8 ppm for the initial
complex 3 [35].
d
2.8e4.8 ppm and
d
100 ppm.
FeeC1eC3
C1eC3eO3
d
d

A.B. Antonova et al. / Journal of Organometallic Chemistry 696 (2011) 963e970
967
H2C
H2C
H2C
Ph Cp(CO)(PPh3)Mn
Cp(CO)2Mn
Ph
H
Ph
H
2
2
1
1
1
2
1
C
C
C
C
C
C
C
CH2
3
3
3
H
3
C
H2C
C
3
O
O
Fe
Fe
Fe
Fe
C
O
O
C
O
C
O
C
O
C
C
C
C
C
C
O
O
C
C
O
O
O
O
O
[38]
[39]
(2) [16]
(4)
Scheme 3.
The behavior of 2 in CD2Cl2 solution was investigated by the
NMR spectroscopy in the temperature range from ꢀ60 to þ30 ꢁC.
The 1H NMR spectrum of 2 at ꢀ60 ꢁC containing one set of signals
at þ22 ꢁC have different widths (Fig. 3). The wide signals of the
TMM form 2 and one of isomers 2a indicate a rapid interconversion
between these forms. Narrower signals of another isomer 2a
demonstrate a slower interconversion with the TMM form of 2.
According to the quantum chemical DFT-B3LYP calculations, the
energy barriers of the conversions 2 / 2a-E and 2 / 2a-Z are 25
and 12 kcal/mol, respectively [37b]. On the base of these data and
at d
4.99 (C5H5), 4.25 (C2H) is consistent with the structure of 2 found
in the solid state [16]. Gradual warming of the solution up to þ10 ꢁC
leads to the appearance of the new additional signals at d 4.94 (C5H5)
and 8.22 ppm (]C2H) in a 5:1 ratio of their integral intensity (Fig. 3).
A significant broadening of the signals at
d
4.99 (C5H5), 4.27 (C2H) and
the VT NMR data, the set of broad signals at
(C2H) may be attributed to the 2a-Z isomer, and the set of narrow
signals at 4.79 and 8.29 to the 2a-E isomer.
d 4.94 (S5O5) and 8.23
4.94 (C5H5), 8.23 (]C2H) ppm is observed and the third set of narrow
signals at 4.79 and 8.29 ppm appears additionally at þ22 ꢁC.
d
The additional signals at
d
8.23 and 8.29 are in the region
The final equilibrium between complex 2 and isomers 2a-Z and
2a-E in the 3.7:1.3:1 ratio, respectively, was observed after warming
the solution up to þ22 ꢁS for 2 h.
typical for the signals of the vinylidene ligand
protons [3], indicating the formation of the -vinylidene complex
m
-C]C2HPh
m
Cp(CO)2MnFe(
m
-C]CHPh)(CO)4 (2a) in solution.
As follows from the above data, the interconversion of the E and
Z isomers of the 2a form occurs through the TMM form 2, as shown
in Scheme 6. It is additionally confirmed by quantum chemical
calculations [37b] which reveal that the energy barrier of the direct
interconversion between 2a-Z and 2a-E amounts to 27 kcal/mol.
Besides characteristic signals of the trimethylenemethane form
Cooling down to ꢀ60 ꢁC leads to the disappearance of the
additional signals of the m-vinylidene complex 2a.
The data obtained allow us to conclude that the cleavage of the
S1eS3 bond of the benzylideneketene [PhC2H]C1]C3]O3] frag-
ment and reversible formation of dinuclear m-vinylidene complex
2a occur when complex 2 is dissolved.
at
contains two additional signal sets. A broad singlet at
a narrow singlet at 253.91 correspond to the
-C1 atoms of the
d
95.84 (C1) and 76.30 (C2) ppm, the 13C NMR spectrum of 2 also
249.02 and
A similar dynamic process has been observed earlier [20] by 1H
d
NMR spectroscopy for the TMM complex
h
4-{C[Fe(CO)3(PEt3)](CO)-
m
CH2}Fe(CO)2(PEt3) which is in equilibrium with the
isomer in solution (Scheme 4).
m
-vinylidene
vinylidene isomers 2a-Z and 2a-E, respectively (Table 3).
On the contrary, no evidence of the formation of a compound
with the bridging coordination of the vinylidene ligand from
Some reversible cleavage reactions of the h
2-coordinated ketene
R2C]C]O into the carbene R2C and CO ligands on the metal
h
4-{C[Mn(CO)(PPh3)Cp](CO)CHPh}Fe(CO)3 (4) was found from the
centers Ir, Mn, MnCo2 have been reported [30,31a] (Scheme 5).
IR and NMR spectroscopic data.
The presence of two signals at
8.29 ppm (narrow singlet) (Fig. 3) in the 1H NMR spectrum of 2 in
solution indicates that two isomeric forms of -vinylidene complex
d 8.23 ppm (broad singlet) and
3. Conclusion
m
2a (E and Z) appear, which differ in the orientation of the Ph and H
The interaction of Fe2(CO)9 with Cp(CO)2Mn]C]CHPh (1) and
Cp(CO)(PPh3)Mn]C]CHPh (3) resulted in the formation of het-
substituents at the vinylidene C2 atom (Scheme 6).
erometallic trimethylenemethane complexes
h
4-{C[Mn(CO)2Cp]-
The rates of the interconversion between TMM complex 2 and
each of the 2a-E and 2a-Z forms are different. The signal set of one
of isomers 2a in the 1H NMR spectrum is not observed upon heating
of the solution up to þ10 ꢁC, but appears only at þ22 ꢁC. It is
noteworthy that the lines of the proton signals for each isomer of 2a
(CO)CHPh}Fe(CO)3 (2) and
h
4-{C[Mn(CO)(PPh3)Cp](CO)CHPh}Fe-
(CO)3 (4), respectively, due to the intramolecular carbonylation of
the bridging phenylvinylidene ligand on the dinuclear MnFe center.
The crystal and molecular structures of complexes 3 and 4 were
Table 3
The IR and NMR data for dinuclear complexes with the MneFe bonds.
Complex
NMR spectrum,
1H
d
, ppm, J, Hz
IR spectrum, (C6H12), cmꢀ1
13C
31P
a
h
4-{C1[Mn(CO)2Cp](C3O3)C2HPh}Fe(CO)3 (2)
4.25s (S2O),
4.99s (S5O5)
8.23s (S2O),
4.94s (S5O5)
8.29s (S2O),
4.79s (S5O5)
95.84s (S1)
e
2085, 2055, 2000, 1971, 1917, 1875,
1851 (C^O),
76.30s (S2)
b
Cp(CO)2MnFe(
Cp(CO)2MnFe(
m
m
-C1]C2HPh)(CO)4 (2a-Z)
-C1]C2HPh)(CO)4 (2a-E)
249.02s (
142.62s (S2)
253.91s (
-C1)
m
-C1)
e
1844 (C3]O3)
b
m
e
141.29s (S2)
c
2
h
4-{C1[Mn(CO)(PPh3)Cp](C3O3)C2HPh}Fe(CO)3 (4)
3.27s (S2O),
101.60d (C1, JPC ¼ 34.04 Hz),
87.57
2042, 1989, 1965,
1885 (C^O),
3
3
4.57d (S5O5, JPH ¼ 2.05 Hz)
73.49d (C2, JPC ¼ 2.77 Hz)
1835 (C3]O3)
CpMnFe(
m
-C]CHCOOMe)(CO)6 [14]
e
e
e
2090, 2040, 2015, 1975, 1930
a
The NMR spectrum of 2 in CD2Cl2 solution at ꢀ60 ꢁC.
b
c
The ratio of the 2a-Z and 2a-E isomers is 1.3:1 at þ22 ꢁC.
The NMR spectrum of 4 in d6-acetone solution.

968
A.B. Antonova et al. / Journal of Organometallic Chemistry 696 (2011) 963e970
Fig. 3. Variable temperature 1H NMR spectra of
The asterisk marks the signal of CH2Cl2.
h m-C]CHPh)(CO)4 (2a-Z and 2a-E) in CD2Cl2 solution.
4-{C1[Mn(CO)2Cp](C3O3)C2HPh}Fe(CO)3 (2) and isomers Cp(CO)2MnFe(
determined by X-ray single crystal analysis. The influence of the
nature of ligands L ¼ CO, PPh3 at the Mn atom on the structural and
4.1.1. Preparation of h
4-{C[Mn(CO)2Cp](CO)CHPh}Fe(CO)3 (2)
A mixture of Cp(CO)2Mn]C]CHPh (1) (0.550 g, 2 mmol) and
Fe2(CO)9 (0.690 g, 2 mmol) in hexane (20 ml) was stirred at 20 ꢁC
for 5 h. The reaction mixture was concentrated to a volume of
∼10 ml and filtered from the precipitated complex 2. The filtrate
was chromatographed on the silica column. The wide brown zone
was eluted with hexaneeether (25:1) mixture. The eluate was
evaporated in vacuum; the solid residue was combined with 2
precipitated from the reaction mixture and crystallized from
hexaneeether (1:1) mixture. The brown acicular crystals of
spectroscopic characteristic of complexes h
4-{C[Mn(CO)(L)Cp](CO)-
CHPh}Fe(CO)3 (2, 4) has been studied.
The equilibrium between TMM form 2 and two dinuclear
m-vin-
ylidene forms Cp(CO)2MnFe( -C]CHPh)(CO)4 (2a-Z and 2a-E) has
m
been ascertained by VT NMR spectroscopy. The data obtained allow
us to conclude that the cleavage of the benzylideneketene [PhCH]
C]C]O] fragment into the vinylidene PhCH]C and CO groups and
reversible formation of dinuclear m-vinylidene complexes 2a-Z and
2a-E from complex 2 occur in solution.
In contrast to 2, complex 4 containing the PPh3 ligand at the Mn
atom was shown to exist in solution only as TMM form by the NMR
and IR spectroscopy.
h
4-{C[Mn(CO)2Cp](CO)CHPh}Fe(CO)3 (2) were isolated (0.386 g,
43% yield).
IR (C6H12),
1928m, 1854vw cmꢀ1. Ref.: (CH2Cl2),
n
(SP) 2087w, 2060s, 2034w, 2001vs,1987sh, 1977vs,
n
(SP) 2086, 2055, 2029sh,
2000, 1970, 1918 (C^O), 1844 (C]O) cmꢀ1 [16].
1O NMR (CD2Cl2, ꢀ60 ꢁC):
7.14e7.34 (m, 5H, S6O5).
d
4.25 (s, 1O, S2O); 4.99 (s, 5O, S5O5);
4. Experimental
13S NMR (CD2Cl2, þ22 ꢁC):
d
76.30 (s, S2); 89.45 (s, C5H5); 95.84
4.1. General considerations
(s, S1); 125.00e128.40 (m, C6H5); 145.59 (s, Cipso of C2HC6H5);
198.17 (s, C3]O3); 211.11 (s, br, Fe(CO)3); 230.30 (s, br, Mn(CO)2).
All operations were carried out in an argon atmosphere. Absolute
solvents saturated with argon were used. Complexes Cp(CO)2Mn]
C]CHPh (1) and Cp(CO)(PPh3)Mn]C]CHPh (3) were prepared as
described in Ref. [13]. The course of reaction was followed by means
of TLC on Silufol plates and IR spectroscopy. Physico-chemical
characteristics were obtained in the Krasnoyarsk Regional Centre of
Research Equipment, Siberian Branch of the Russian Academy of
Science. The IR spectra were recorded on the Vector 22 Infrared
Fourier spectrometer (Bruker, Germany). The 1H, 13C{1H} and 31P
{1H} NMR spectra were obtained using NMR spectrometer AVANCE
III 600 DPX (Bruker, Germany). The X-ray data were obtained with
the SMART APEX II autodiffractometer (Bruker, Germany).
Isomer Cp(CO)2MnFe(m-C]CHPh)(CO)4 (2a-Z):
1O NMR (CD2Cl2, þ22 ꢁC):
d 4.94 (s, S5O5); 7.14e7.34 (m, 5H,
S6O5); 8.23 (s, ]S2O).
13S NMR (CD2Cl2, þ22 ꢁC):
d 88.28 (s, C5H5); 125.00e128.40 (m,
C6H5); 142.62 (s, ]C2HPh); 146.87 (s, Cipso of ]C2HC6H5); 204.52
and 208.43 (s, Fe(CO)4); 234.08 (s, br, Mn(CO)2); 249.02 (s, br, C1).
Isomer Cp(CO)2MnFe(m-C]CHPh)(CO)4 (2a-E):
1O NMR (CD2Cl2, þ22 ꢁC):
d 4.79 (s, C5H5); 7.41 (tr, 2H, Hmeta of ]
C2HC6H5, JHH ¼ 7.61); 7.53 (d, 2H, Horto of ]C2HC6H5, JHH ¼ 6,93);
Hpara of ]C2HC6H5 overlapping with C6H5 signals of 2 and isomer
2a-Z; 8.29 (s, ]S2O).
H
H
(Et3P)(CO)3Fe
2
H
H
2
1
C
C
C
solv.
C
1
C
O
Fe
PEt3
(Et3P)(CO)3Fe
Fe(CO)3(PEt3)
C
C
O
O
Scheme 4.

A.B. Antonova et al. / Journal of Organometallic Chemistry 696 (2011) 963e970
969
4.3. X-ray diffraction studies of (h
5-cyclopentadienyl)-(carbonyl)-
R
R
(triphenylphosphine)-[
2,2,2,2-
4-{[(1- 5-cyclopentadienyl)-(1-carbonyl)-(1-
triphenylphosphine)-2-
1-manganese]-(2- 1-phenylmethylene)-(2-
1-carbo)-(1,2-h1 1-methane)}-(2,2,2-tricarbonyl)-iron(MneFe) (4)
h
1-(phenyl)ethenylidene]-manganese (3) and
R
R
C
C
h
h
LM
L + M C
h
h
C
h
,h
O
O
The intensity data were collected with Bruker SMART APEX II
X-ray area-detector diffractometer, MoK eradiation, for single
Scheme 5.
a
crystals of complexes 3 and 4. The sample of 4 was cooled to obtain
the sufficient number of data. Absorption corrections have been
introduced via multi-scan method [43]. The structures were solved
and refined in the anisotropic approximation of non-hydrogen
atoms using [44]. All hydrogen atoms were placed in geometrically
idealized locations and refined as riding. All phenyl cycles were
preserved in the idealized form during the refinement procedure.
The Cp cycle also was idealized in both cases with MneC distance of
average value and the distance was preserved with the esd of
0.002 Å.
There are the solvent molecules (hexane) in the crystal of 4.
These molecules are arranged in the inversion centers in the middle
of the c-axis, what indicates the presence of alone hexane molecule
in the crystal cell. The molecule was also idealized over interatomic
distances and angles, but the torsion angles were free for some
variations during the refinement.
H
Ph
2
C
3
O
3
O
1
C
C
C
Mn
Fe
CO
O
C
C
C
C
O
O
C
O
O
Mn
H
2
1
(2a-
Z)
C
C
3
Ph
C
3
O
Fe
Ph
H
C
2
O
C
C
C
3
O
O
O
O
1
3
C
C
C
(2)
Mn
Fe
CO
C
C
C
O
O
O
(2a-
E)
Acknowledgements
Scheme 6.
This work was partially supported by the Presidium of the
Russian Academy of Sciences (Program for Basic Research, Project
No. 7.18) and Russian Foundation for Basic Research (Grant No. 09-
03-90745-mob_st). Authors are grateful to Prof. N.A. Ustynyuk for
useful discussions, Dr. E.A. Shor and Dr. A.M. Shor for giving the data
of quantum chemical study.
13S NMR (CD2Cl2, þ22 ꢁC):
d 88.72 (s, C5H5); 125.59, 127.16 and
128.22 (s, Cpara, Cmeta, Corto of ]C2HC6H5); 141.29 (s, ]C2HPh);
148.23 (s, Cipso of ]C2HC6H5); 204.62 and 208.17 (s, Fe(CO)4);
229.05 and 235.23 (s, Mn(CO)2); 253.91 (s, C1).
4.1.2. Preparation of
mixture of Cp(CO)(PPh3)Mn]C]CHPh (3) (0.050 g,
h
4-{C[Mn(CO)(PPh3)Cp](CO)CHPh}Fe(CO)3 (4)
Appendix. A. Supplementary material
A
The supplementary crystallographic data for compounds 3 and 4
have been deposited with the Cambridge Crystallographic Data
Centre, CCDC Nos. 781985 and 781984, correspondingly. The data
can be obtained free of charge via http://www.ccdc.cam.ac.uk or e-
mail: deposit@ccdc.cam.ac.uk.
0.098 mmol) and Fe2(CO)9 (0.073 g, 0.200 mmol) in benzene (10 ml)
wasstirredfor3 h. The solutionwas filtered throughalumina pad and
the solvent was evaporated in vacuum. The residue was dissolved in
5 ml of hexaneebenzene (4:1) mixture and chromatographed on an
alumina column (l ¼ 80 mm, d ¼ 15 mm). Pale-yellow zone was
eluted with hexaneebenzene (4:1) mixture and wide brown zone
was eluted with hexaneebenzene (2:1) mixture sequentially.
Removal of solvents from the first fraction gave pale-yellow crystals
References
[1] A.B. Antonova, O.S. Chudin, N.I. Pavlenko, W.A. Sokolenko, A.I. Rubaylo,
A.D. Vasiliev, V.V. Verpekin, O.V. Semeikin, Izv. Akad. Nauk. Ser. Khim. (2009)
933; Russ. Chem. Bull. Int. Ed., 58 (2009) 955.
[2] A.B. Antonova, A.A. Ioganson, Usp. Khim. 58 (1989) 1197; Russ. Chem. Rev. 58
(1989) 693 (Engl. Transl.).
[3] A.B. Antonova, Coord. Chem. Rev. 251 (2007) 1521.
[4] M.I. Bruce, Chem. Rev. 91 (1991) 197.
[5] M.I. Bruce, in: C. Bruneau, P.H. Dixneuf (Eds.), Metal Vinylidenes and Alleny-
lidenes in Catalysis, Wiley-VCH, Weinheim, Germany, 2008, pp. 1e60.
[6] (a) H. Werner, Angew. Chem. Int. Ed. Engl. 29 (1990) 1077;
(b) H. Werner, Coord. Chem. Rev. 248 (2004) 1693.
[7] A.G.M. Barrett, M.A. Sturgess, Tetrahedron 44 (1988) 5615.
[8] I.I. Moiseev, Usp. Khim. 58 (1989) 1175; Russ. Chem. Rev. 58 (1989) 682 (Engl.
Transl.).
[9] M.C. Puerta, P. Valerga, Coord. Chem. Rev. 193e195 (1999) 977.
[10] I. Omae, Applications of Organometallic Compounds. J. Wiley & Sons Ltd.,
Chichester, 1999, 518 pp.
[11] J.P. Selegue, Coord. Chem. Rev. 248 (2004) 1543.
[12] (a) C. Bruneau, P.H. Dixneuf, Acc. Chem. Res. 32 (1999) 311;
(b) C. Bruneau, P.H. Dixneuf, Angew. Chem. Int. Ed. 45 (2006) 2176.
[13] A.B. Antonova, N.E. Kolobova, P.V. Petrovsky, B.V. Lokshin, N.S. Obezyuk,
J. Organomet. Chem. 137 (1977) 55.
of Fe(CO)4(PPh3) (0.013 g). (IR (CH2Cl2),
1941 cmꢀ1). After removal of solvent from the second fraction and
crystallization from hexane, 0.048 (70%) of black crystals
4-{C[Mn(CO)(PPh3)Cp](CO)CHPh}Fe(CO)3 (4) were isolated.
Anal. Found: S, 72.32; O, 3.80; Mn, 8.15; Fe, 8.27%.
C36H26PMnFeO5. Anal. Calc: S, 72.35; O, 3.82; Mn, 8.20; Fe, 8.23%.
n (SP): 2054, 1974,
g
h
IR (C6H12) n .
(SP), 2042s, 1989s, 1965m, 1885w, 1835w br cmꢀ1
Mass spectrum (EI, 70 eV) m/z: 438 [C5H5(CO)MnP(C6H5)3]þ,
382 [C5H5MnP(C6H5)3]þ, 262 [P(C6H5)3]þ, 148 [C5H5MnCO]þ, 130
[C6H5CHCCO]þ, 120 [C5H5Mn]þ, 102 [C6H5C2H]þ, 55 [Mn]þ.
1O NMR (d6-acetone):
d
3.27 (s, O, S2O); 4.57 (d, 5O, S5O5
3JPH ¼ 2.05); 6.85e7.13 [m, 5H, C2HC6H5]; 7.49e7.79 [m, 15H, P(C6H5)3].
13S{1H} NMR (d6-acetone):
d
73.51 (d, C2, 3JPC ¼ 2.77 Hz); 90.14
(s, C5H5); 101.60 (d, C1, JPC ¼ 34.04 Hz); 124.52 (s, Cmeta of
2
C2HC6H5); 125.56 (s, Cpara of C2HC6H5); 128.05 (s, Corhto of C2HC6H5);
3
128.42 (d, Cmeta of PPh3, JPC ¼ 9.39 Hz); 130.17 (d, Cpara of PPh3,
4JPC ¼ 2.05 Hz); 133.48 (d, Cortho of PPh3, 2JPC ¼ 8.71 Hz); 136.19 (d,
Cipso of PPh3, JPC ¼ 42.20 Hz); 147.36 (s, Cipso of C2HC6H5); 204.03 (s,
C3]O3); 211.16 (m, Fe(CO)3); 241.51 (d, Mn(CO), 2JPC ¼ 39.59 Hz).
[14] N.E. Kolobova, L.L. Ivanov, O.S. Zhvanko, G.G. Aleksandrov, Yu.T. Struchkov,
J. Organomet. Chem. 228 (1982) 265.
[15] H. Werner, F.J. Garcia Alonso, H. Otto, K. Peters, H.G. von Schnering, Chem. Ber.
121 (1988) 1565.
31P{1H} NMR (d6-acetone):
d 87.56 (s, Mn-PPh3).

970
A.B. Antonova et al. / Journal of Organometallic Chemistry 696 (2011) 963e970
[16] V.G. Andrianov, Yu.T. Struchkov, N.E. Kolobova, A.B. Antonova, N.S. Obezyuk,
J. Organomet. Chem. 122 (1976) C33.
[17] N.E. Kolobova, V.V. Derunov, O.M. Khitrova, M.A. Lusenkova, A.S. Batsanov,
Yu.T. Struchkov, P.V. Petrovskii, Metalloorg. Khim. 1 (1988) 400; Organomet.
Chem. USSR 1(2) (1988) 220 (Engl. Transl.).
[29] J. Chen, R. Wang, Coord. Chem. Rev. 231 (2002) 109.
[30] D.B. Grotjahn, G.A. Bikzhanova, L.S.B. Collins, T. Concolino, K.-C. Lam,
A.L. Rheingold, J. Am. Chem. Soc. 122 (2000) 5222.
[31] (a) Y. Ortin, Y. Coppel, N. Lugan, R. Mathieu, M.J. McGlinchey, J. Chem. Soc.
Chem. Commun. (2001) 2636;
[18] A.B. Antonova, S.V. Kovalenko, A.A. Ioganson, N.A. Deikhina, E.D. Korniets,
Yu.T. Struchkov, A.I. Yanovskii, Metalloorg. Khim. 2 (1989) 1014; Organomet.
Chem. USSR 2 (1989) 530 (Engl. Trans.).
(b) Y. Ortin, N. Lugan, R. Mathieu, Dalton Trans. (2005) 1620.
[32] C. Masters, Homogeneous Transition-metal Catalysis. A Gentle Art. Chapman
and Hall, LondoneNew York, 1981.
[19] D.A. Pogrebnyakov, Z.A. Starikova, N.I. Pavlenko, A.I. Rubailo, V.A. Sokolenko,
O.S. Chudin, A.B. Antonova, Izv. Akad. Nauk. Ser. Khim. (2002) 1235; Russ.
Chem. Bull. Int. Ed. 51 (2002) 1339.
[20] R. Birk, H. Berke, G. Huttner, L. Zsolnai, Chem. Ber. 121 (1988) 471.
[21] R.D. Adams, G. Chen, L. Chen, W. Wu, J. Yin, Organometallics 12 (1993) 3431.
[22] C. Kelley, N. Lugan, M.R. Terry, G.L. Geoffroy, B.S. Haggerty, A.L. Rheingold,
J. Am. Chem. Soc. 114 (1992) 6735.
[33] G. Henrici-Olivé, S. Olivé, The Chemistry of the Catalyzed Hydrogenation of
Carbon Monoxide. Springer-Verlag, Berlin, 1984.
[34] A.B. Antonova, O.S. Chudin, W.A. Sokolenko, A.I. Rubaylo, N.I. Pavlenko, V.V.
Verpekin, A.D. Vasiliev, O.V. Semeikin. In: Zing Carbene Chemistry Conference.
Mexico. 2009. Programme and Abstract Book. p. 39.
[35] L.N. Novikova, M.G. Peterleitner, K.A. Sevumyan, O.V. Semeikin, D.A. Valyaev,
N.A. Ustynyuk, Appl. Organomet. Chem. 16 (2002) 530.
[23] I. Ara, J.R. Berenguer, J. Fornies, E. Lalinde, M. Tomas, Organometallics 15
(1996) 1014.
[24] (a) K.H. Dötz, Angew. Chem. Int. Ed. Engl. 23 (1984) 587;
(b) K.H. Dötz, H.C. Jahr, in: G. Bertrand (Ed.), Carbene Chemistry: From Fleeting
Intermediates to Powerful Reagents, Fontis Media S.A.: Lausanne and Marcel
Dekker, Inc., New York, Basel, 2002, pp. 231e270;
(c) A. Minatti, K.H. Dötz, Chromium-templated benzannulation reaction. in:
K.H. Dötz (Ed.), Topics in Organometallic Chemistry, Metal Carbenes in
Organic Synthesis, vol. 13. Springer, Heidelberg, Germany, 2004, pp. 123e156.
[25] F.R. Kreißl, P. Friedrich, G. Huttner, Angew. Chem. Int. Ed. Engl. 16 (1977) 102.
[26] J. Martin-Gil, J.A.K. Howard, R. Navarro, F.G.A. Stone, J. Chem. Soc. Chem.
Commun. (1979) 1168.
[36] (a) A.N. Nesmeyanov, G.G. Aleksandrov, A.B. Antonova, K.N. Anisimov,
N.E. Kolobova, Yu. T. Struchkov, J. Organomet. Chem. 110 (1976) C36;
(b) G.G. Aleksandrov, A.B. Antonova, N.E. Kolobova, Yu.T. Struchkov, Koord.
Khim. (Coord. Chem.) 2 (1976) 1684.
[37] (a) E.A. Shor, A.M. Shor, personal communication;
(b) E.A. Ivanova Shor, V.A. Nasluzov, A.M. Shor, A.B. Antonova, N. Rösch,
J. Organomet. Chem., prepared for publication
[38] A. Almenningen, A. Haaland, K. Wahl, Acta Chem. Scand. 23 (1969) 1145.
[39] M.R. Churchill, K. Gold, Inorg. Chem. 8 (1969) 401.
[40] K. Ehrlich, G.F. Emerson, J. Am. Chem. Soc. 94 (1972) 2464.
[41] M. Franck-Neumann, P. Stöber, G. Passmore, Tetrahedron: Asymmetry
(1996) 3193.
7
[27] (a) W.A. Herrmann, J. Plank, M.L. Ziegler, K. Weidenhammer, J. Am. Chem. Soc.
101 (1979) 3133;
[42] W.A. Donaldson, C.D. Cushnie, S. Guo, M.J. Kramer, D.W. Bennett, Transit. Met.
Chem. 22 (1997) 592.
(b) W.A. Herrmann, Adv. Organomet. Chem. 20 (1982) 159.
[28] G.L. Geoffroy, S.L. Bassner, Adv. Organomet. Chem. 28 (1988) 1.
[43] G.M. Sheldrick, SADABS. University of Göttingen, Germany, 2004.
[44] G.M. Sheldrick, Acta Cryst. A64 (2008) 112e122.