Synthesis of oligoenes that contain up to 15 double bonds from 1,6-heptadiynes

Article abstract of DOI:10.1021/ja0656705

This paper reports the synthesis of polyene oligomers (" oligoenes") that contain up to 15 double bonds that are identical to the "all five-membered ring" species formed through cyclopolymerization of diisopropyldipropargylmalonate. The oligoenes contain

Full text of DOI:10.1021/ja0656705

Published on Web 12/05/2006
Synthesis of Oligoenes that Contain up to 15 Double Bonds
from 1,6-Heptadiynes
†
†
†
,†
Constantin Czekelius, Jillian Hafer, Zachary J. Tonzetich, Richard R. Schrock,*
‡
†
Ronald L. Christensen, and Peter M u¨ ller
Contribution from the Department of Chemistry, Massachusetts Institute of Technology,
Cambridge, Massachusetts 02139, and Department of Chemistry, Bowdoin College, Brunswick,
Maine 04011
Received August 15, 2006; E-mail: rrs@mit.edu
Abstract: This paper reports the synthesis of polyene oligomers (“oligoenes”) that contain up to 15 double
bonds that are identical to the “all five-membered ring” species formed through cyclopolymerization of
diisopropyldipropargylmalonate. The oligoenes contain an isopropylidene unit at each end. The isolated
oligoenes range from the “dimer” (a pentaene, (E)-di-1,2-[1-(2-methyl-propenyl)-4,4-di-iso-propyl-carboxy-
cyclopent-1-enyl]-ethene (3b
and 3b were prepared through Wittig-like reactions between aldehydes and the appropriate monometallic
Mo alkylidene or bimetallic Mo bisalkylidene species whose alkylidene is derived from an identical five-
membered ring monomeric unit. Compounds 3b , 3b , and 3b were prepared through McMurry coupling
reactions of aldehydes. A representative aldehyde (the “monomeric” aldehyde) is diisopropyl-3-formyl-4-
2-methylprop-1-enyl)cyclopent-3-ene-1,1-dicarboxylate (2b), McMurry coupling of which yields 3b . A
2 7 2 3 4 5
)) to the “heptamer” (3b , a pentadecaene). Oligoenes 3b , 3b , 3b , 3b ,
7
2
4
6
(
2
heptaene that contains a six-membered ring in the central unit also was prepared in a Wittig-like reaction
involving a bimetallic Mo alkylidene; this species is a model for oligoenes that contain both six-membered
and five-membered rings. X-ray structures of two bimetallic species that are employed in the synthesis of
the oligoenes are reported.
Introduction
However, substituted polyacetylenes are not necessarily regio-
regular, and regioerrors in the polyene chain can degrade or
Considerable progress has been made in the synthesis and
optical characterization of conjugated polymers such as all-trans
polyacetylene. These studies have been motivated in large part
by the semiconducting properties of these systems and the
advent of rational synthetic approaches toward the design of
molecules for displays, lasers, photovoltaics, and nonlinear
destroy electronic and optical properties. Research into potential
applications of conjugated organic polymers has expanded to
include many other conjugated polymers (or related oligomers)
such as polyparaphenylenevinylenes, polyparaphenyleneethy-
nylenes, polythiophenes, polypyrroles, etc.
In addition to their potential applications in optoelectronic
devices, conjugated polymers are of fundamental interest as
models for understanding the electronic and optical properties
of one-dimensional, conjugated π-electron systems. Short, model
polyenes have received considerable experimental and theoreti-
1
optical materials. Polyacetylene, the simplest π-conjugated
organic polymer, is highly conductive when doped and possesses
(3)
a high third-order susceptibility (ø ), a measure of the change
in refractive index under the action of an electromagnetic field.
Materials that have a high third-order susceptibility are attractive
candidates for photonic switches and other devices. Potential
disadvantages of polyacetylene include its relatively high
sensitivity to oxygen and its insolubility in common organic
solvents. (tert-Butyl-capped polyenes are known to become
relatively insoluble after N ≈ 13, where N is the number of
5
cal attention in recent years. One- and two-photon absorption,
fluorescence, and fluorescence excitation experiments and the
measurement of excited-state decays have led to a deeper
(
3) (a) Masuda, T.; Abdul Karim, S. M.; Nomura, R. J. Mol. Catal. A: Chem.
2
000, 160, 125. (b) Masuda, T.; Higashimura, T. AdV. Polym. Sci. 1986,
2
double bonds. ) Substituted polyacetylenes such as polypheny-
81, 122. (c) Mizumoto, T.; Masuda, T.; Higashimura, T. J. Polym. Sci.,
Part A: Polym. Chem. 1993, 31, 2555. (d) Masuda, T.; Higashimura, T.
Acc. Chem. Res. 1984, 17, 51. (e) Masuda, T.; Fujimori, J. I.; Abrahman,
M. Z.; Higashimura, T. Polym. J. 1993, 25, 535.
3
4
lacetylenes or poly[1,6-heptadiynes] are often more soluble.
(4) (a) Choi, S.-K.; Gal, Y.-S.; Jin, S.-H.; Kim, H. K. Chem. ReV. 2000, 100,
†
Massachusetts Institute of Technology.
Bowdoin College.
1645. (b) Lam, J. W. Y.; Tang, B. Z. J. Polym. Sci. 2003, 41, 2607. (c)
‡
Krause, J. O.; Wang, D.; Anders, U.; Weberskirch, R.; Zarka, M. T.;
Nuyken, O.; Jaeger, C.; Haarer, D.; Buchmeiser, M. R. Macromol. Symp.
2004, 217, 179. (d) Buchmeiser, M. R. Monatsh. Chem. 2003, 134, 327.
(
1) (a) Samuel, I. D. W. Philos. Trans. R. Soc. London, Ser. A 2000, 358, 193.
(
b) Friend, R. H.; Gymer, R. W.; Holmes, A. B.; Burroughes, J. H.; Marks,
R. N.; Taliani, C.; Bradley, D. D. C.; Dos Santos, D. A.; Bredas, J. L.;
Logdlund, M.; Salaneck, W. R. Nature (London) 1999, 397, 121.
(5) Christensen, R. L. The Electronic States of Carotenoids. In The Photo-
chemistry of Carotenoids; Frank, H. A., Young, A. J., Britton, G., Cogdell,
R. J., Eds.; Kluwer Academic Publishers: Dordrecht, 1999; Vol. 8, pp 137-
159.
(
2) Knoll, K.; Krouse, S. A.; Schrock, R. R. J. Am. Chem. Soc. 1988, 110,
4
424.
16664
9
J. AM. CHEM. SOC. 2006, 128, 16664-16675
10.1021/ja0656705 CCC: $33.50 © 2006 American Chemical Society

Synthesis of Oligoenes with up to 15 Double Bonds
A R T I C L E S
Scheme 1. Reaction of Mo(NR′)(CHR′′)(OR)2 with 1,6-Heptadiyne Derivatives (e.g., X ) C(CO2Et)2)
9
understanding of the basic photophysics and photochemistry of
these systems. One important outcome of the work on simple
(N ) 11), lycopene (N ) 11), and astaxanthin (N ) 13). Much
work remains to be done to extend our understanding of the
optical properties of the short polyenes and carotenoids to much
longer oligomers and ultimately polymers. As mentioned earlier,
substituted polyenes tend to suffer from conformational disor-
6
polyenes was the discovery of a low energy, symmetry forbidden
1
-
1
-
(
1 Ag f Ag ) transition (S0 f S1) that lies below the strongly
1
-
1
+
allowed 1 Ag f 1 Bu transition (S0 f S2) associated with
the excitation of an electron from the highest occupied molecular
10
der and in some cases regioerrors, which complicate the
orbital (HOMO) to the lowest unoccupied molecular orbital
interpretation of their optical spectra and other electronic
properties. Investigation of the optical properties of a range of
soluble, planar, regioregular polyenes/oligoenes with known
structures would offer critical advantages in relating their optical
and electronic properties to conjugation length, geometry, and
other variations in molecular structure.
7
(LUMO) in simple versions of molecular orbital theory.
There also is considerable interest in the spectroscopy and
photochemistry of longer polyenes and, in particular, how the
energies and dynamics of polyene excited states change with
increasing π-electron delocalization. Naturally occurring poly-
enes in the form of carotenoids play important roles in
photobiology, e.g., in vision and photosynthesis, and their
strongly allowed S0fS2 transitions provide a broad palette of
colors to plants and animals. Carotenoids function as light-
harvesting pigments in photosynthesis, absorbing light and
transferring energy to other antenna pigments and chlorophylls
Poly[1,6-heptadiynes] such as poly[dialkyldipropargylma-
lonates] are highly conjugated and relatively soluble and appear
to be relatively stable in air. These polymers were first prepared
using “classical” olefin metathesis (alkylidene) catalysts that
are prepared from Mo or W halides or oxyhalides and some
alkylating agent. In general these polymers do not have a
regular structure. As a consequence of addition of the first triple
bond to the alkylidene to give either an R- or a â-substituted
metallacyclobutene, both six-membered rings and five-mem-
bered rings are usually formed (Scheme 1).
4
4
8
in reaction centers. Carotenoids also play crucial protective roles
in these biological systems; their low-energy triplet states quench
chlorophyll triplet states, thus preventing irreversible damage
due to the photosensitization of singlet oxygen. Synthetic
polyenes/oligoenes could play similar roles in artificial photo-
synthetic systems. Understanding how excited-state energies and
lifetimes change with conjugation length and other structural
modifications would allow optimization of light harvesting and
photoprotection in the design of light-driven, synthetic systems.
Systematic study of the optical and electronic properties of
We first explored the polymerization of diethyldipropargyl-
malonate (DEDPM) and related derivatives with well-defined
Mo-based olefin metathesis catalysts, primarily Mo(NAr)-
(CHCMe Ph)(OR ) (Ar ) 2,6-i-Pr C H , OR ) OCMe-
2
F6 2
2
6
3
F6
1
1
(CF ) ), in 1992. These studies confirmed that high oxidation
3
2
“
long” polyenes has been limited to molecules with N e 15 as
state Mo alkylidenes were catalysts for cyclopolymerization
reactions of this general type. The resulting polymer formed
using Mo(NAr)(CHCMe2Ph)(ORF6)2 as the initiator was shown
to contain both five-membered and six-membered rings.
Later we showed that polyenes that contain all six-membered
rings were formed when dicarboxylate catalysts of the type
a consequence of a lack of synthetic routes to longer polyenes
and their limited solubilities. It also is interesting to note that
N e 13 for the longest natural carotenoids such as â-carotene
(
(
6) Pol ´ı vka, T.; Sundstr o¨ m, V. Chem. ReV. 2004, 104, 2021.
7) (a) Hudson, B.; Kohler, B. Ann. ReV. Phys. Chem. 1974, 25, 437. (b)
Hudson, B. S.; Kohler, B. E.; Schulten, K. Linear Polyene Electronic
Structure and Potential Surfaces. In Excited States; Lim, E. D., Ed.;
Academic Press: New York, 1982; Vol. 6, pp 1-95. (c) Christensen, R.
L.; Barney, E. A.; Broene, R. D.; Galinato, M. G. I.; Frank, H. A. Arch.
Biochem. Biophys. 2004, 430, 30.
(9) Zechmeister, L. Cis-trans Isomeric Carotenoids, Vitamins A, and Arylpoly-
enes; Academic Press: New York, 1962.
(10) Wood, P.; Samuel, I. D. W.; Schrock, R. R.; Christensen, R. L. J. Chem.
Phys. 2001, 115, 10955.
(11) (a) Fox, H. H.; Schrock, R. R. Organometallics 1992, 11, 2763. (b) Fox,
H. H.; Wolf, M. O.; O’Dell, R.; Lin, B. L.; Schrock, R. R.; Wrighton, M.
S. J. Am. Chem. Soc. 1994, 116, 2827.
(
8) (a) Frank, H. A.; Cogdell, R. J. Photochem. Photobiol. 1996, 63, 257. (b)
Frank, H. A.; Young, A. J.; Britton, G.; Cogdell, R. J. In AdVances in
Photosynthesis; Govindjee, Ed.; Kluwer Academic Publishers: Dordrecht,
1
999.
J. AM. CHEM. SOC.
9
VOL. 128, NO. 51, 2006 16665

A R T I C L E S
Czekelius et al.
Mo(N-2-t-BuC6H4)(CHCMe3)(O2CCPh3)2 were employed.12
DEDPM polymers that contain only six-membered rings have
λmax values that are lower by 20-30 nm for a given apparent
chain length than those for polymers that contain both five- and
six-membered rings, consistent with a lower effective conjuga-
tion length, presumably as a consequence of twisting of the
polymer chain. Buchmeiser and co-workers have shown that
Mo(NAr)(CHCMe2Ph)(OCMe3)2 catalysts will polymerize
DEDPM to yield polymers that contain >95% five-membered
rings.13 Advantages of poly[1,6-heptadiynes] that contain only
five-membered rings include the single alternating cis,trans
structure and the potentially relatively rigid extended chain if
conjugation is maintained. Since all polymerizations that begin
with neopentylidene or neophylidene initiators have a high rate
of polymerization versus initiation in polymerizations of this
type, we recently prepared initiators that will initiate rapidly
relative to the rate of propagation, including one that contains
the very type of five-membered ring being formed in a
cyclopolymerization reaction, i.e., 1a' in eq 1.14 We also showed
that 1a would react with aldehyde 2a to yield the “dimer”, 3a2,
cleanly and in relatively high yield, in a Wittig-like reaction.
Finally, we showed that upon treatment of 1a′ with 1.5 equiv
of DEDPM, followed by quenching with 2a, it was possible to
isolate from the product mixture the “trimer” 3a3 and “tetramer”
3a4 as pure slightly air-sensitive compounds. We have prepared
relatively short tert-butyl-capped polyenes previously through
stoichiometric Wittig-like reactions related to the reaction shown
in eq 1.15
One might imagine that variations of the reaction shown in
eq 1 could be employed to prepare longer oligomeric polyenes
analogous to 3a3 and 3a4 that have a single structure and chain
length. Spectroscopic studies of a well-defined series of such
compounds are of interest from a theoretical perspective,
1
6
especially if N > 11. Systematic studies of this type are rare.
In this paper we report the synthesis of oligomers analogous to
a3 and 3a4 that contain up to 7 monomer units (N ) 15). These
3
results establish a methodology that could prove useful for
preparing long oligomers of other dialkyldipropargylmalonates,
and possibly also long oligomers of other 1,6-heptadiynes.
Studies of this type we hope will allow us to understand how
variations in molecular structure alter the physical and optical
properties of those materials. We can then return to applications
that involve analogous polymeric materials with some confi-
dence that we understand the fundamental properties of such
materials as a function of structure and chain length.
4a following a protocol published by Trost and co-workers (eq
1
7
2). A Wittig olefination of 5a yielded triene 6a. Triene 6a
could be isolated only in low yield even though different reaction
conditions (DMSO/NaH, THF/NaH, THF/n-BuLi) and various
chromatographic separation techniques were employed. Sig-
nificant decomposition of 6a was observed at room temperature,
even under dinitrogen. Therefore we believe that 6a may be
thermally unstable. Nevertheless, if compound 6a is used
immediately after it is prepared, bimetallic 7 can be isolated in
good yield (eq 3). NMR studies are consistent with 7 having
the syn,syn alkylidene configuration shown. The alkylidene HR
resonance is found at 12.65 ppm in CD2Cl2 with JCH ) 125
Hz. (Such coupling constants are usually routinely obtained
Results and Discussion
Synthesis of Bimetallic 5- and 6-Membered Ring Species.
One strategy for the synthesis of symmetric oligomers of type
3
is to prepare bimetallic species related to 1. Dienal 5a was
prepared employing a ruthenium catalyzed cyclization of diynol
(
12) Schattenmann, F. J.; Schrock, R. R.; Davis, W. M. J. Am. Chem. Soc. 1996,
18, 3295.
1
3
1
through detection of C satellites in high quality proton NMR
spectra.) A JCH value of 125 Hz is a typical syn alkylidene CH
coupling constant in a high oxidation state alkylidene of this
(
13) (a) Anders, U.; Nuyken, O.; Buchmeiser, M. R.; Wurst, K. Angew. Chem.,
Int. Ed. 2002, 41, 4044. (b) Anders, U.; Nuyken, O.; Buchmeiser, M. R.;
Wurst, K. Macromolecules 2002, 35, 9029. (c) Anders, U.; Nuyken, O.;
Buchmeiser, M. R. J. Mol. Catal. A: Chem. 2004, 213, 89.
18
general type.
(
(
(
14) Adamchuk, J.; Schrock, R. R.; Tonzetich, Z. J.; M u¨ ller, P. Organometallics
2
006, 25, 2364.
15) Fox, H. H.; Lee, J.-K.; Park, L. Y.; Schrock, R. R. Organometallics 1993,
(17) (a) Trost, B. M.; Rudd, M. T. J. Am. Chem. Soc. 2005, 127, 4763. (b)
Trost, B. M.; Older, C. M. Organometallics 2002, 21, 2544.
(18) (a) Feldman, J.; Schrock, R. R. Prog. Inorg. Chem. 1991, 39, 1. (b) Schrock,
R. R. Chem. ReV. 2002, 102, 145.
1
2, 759.
16) Christensen, R. L.; Fakash, A.; Meyers, J. A.; Samuel, I. D. W.; Wood, P.;
Schrock, R. R.; Hultzsch, K. C. J. Phys. Chem. 2004, 108, 8229.
16666 J. AM. CHEM. SOC.
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VOL. 128, NO. 51, 2006

Synthesis of Oligoenes with up to 15 Double Bonds
A R T I C L E S
Mo(O)(NR)(OR')2. Such species have never proved isolable and
are believed to be unstable with respect to bimolecular ligand
scrambling reactions; therefore they are left out of equations
that describe reactions in which they presumably are formed
initially.
The reaction between 1-vinyl-3-methylene-5,5-bis(carboxy-
ethyl)cyclohex-1-ene (9) and Mo(NAr)(CHCMe3)(ORF6)2 has
been reported to produce Mo(NAr)[1-methylidene-3-methylen-
5
,5-bis(carboxyethyl)cyclohex-1-ene)](ORF6)2 (10; eq 6) in low
1
1b
yield. An X-ray structure of a compound analogous to 10,
Crystals of 7 suitable for an X-ray crystallographic analysis
could be obtained readily. Its structure (Figure 1 and Table 1)
is unremarkable and, therefore, is not discussed in detail.
Selected distances and angles can be found in Table 2. It should
be noted that the isopropyl groups in the imido ligands are turned
away from the esters slightly, consistent with some steric
crowding.
but lacking the exo methylene group on the six-membered ring,
1
4
has been reported. A reaction analogous to that shown in eq
with a molybdenum complex that contains the less sterically
6
demanding 2-tert-butyl-phenyl-imido ligand yields the bimetallic
species (11) shown in eq 7. Compound 11 is obtained as a brown
The difficulty of preparing and handling 6a prompted us to
explore analogues that contain other esters, in particular,
isopropyl esters. Compounds 5b and 6b (eq 2) proved to be
highly crystalline and readily isolated after minimal workup;
only passage through a silica gel plug is necessary. In contrast
to 6a, 6b showed no signs of decomposition upon storage in
the solid state under dinitrogen. Interestingly, attempts to isolate
the bimetallic isopropyl ester analogue of 7 failed, possibly for
steric reasons that were hinted at in the X-ray structure of 7
(
vide supra). However, a compound related to 7 could be
prepared in good yield by employing the sterically less bulky
,6-dimethylphenylimido ligand (Ar' ) 2,6-Me2C6H3), as shown
in eq 4. NMR data for 8 are analogous to those for 7 (δHR )
2.66 ppm in CD2Cl2, JCH ) 128 Hz, δCR ) 275.3 ppm).
2
1
powder that is significantly more soluble than the other
bimetallic compounds discussed thus far. It can be separated
from traces of the starting neopentylidene complex through
recrystallization from pentane. The spectroscopic features of the
molecule are consistent with the proposed bimetallic structure
shown in eq 7. The primary alkylidene proton resonance is found
as a singlet at 12.38 ppm in benzene-d6 with a JCH value of
1
25 Hz, consistent with formulation of the species as a syn
1
3
alkylidene. The C NMR spectrum shows two alkylidene
resonances at 271.06 and 259.03 ppm. The upfield resonance
is assigned to the primary alkylidene carbon on the basis of an
observed coupling of the alkylidene carbon to one proton.
Also consistent with the proposed formulation of 11 is its
reaction with 2 equiv of aldehyde 2a to yield a “trimer” (12, eq
8) that contains a six-membered ring in the center. Two isomers
of 12 are observed in a ratio of ∼2:1. All NMR data are
consistent with formation of E and Z isomers, as shown in eq
8. This result suggests that oligomers or polymers that contain
both five-membered and six-membered rings are likely to
contain many isomers as a consequence of E and Z isomers
being formed. This may be one reason why polymers that
contain both five-membered and six-membered rings generally
are more soluble than those that contain only five-membered
Upon treatment of 8 with 2b (which was prepared in a Ru-
catalyzed cyclization similar to compound 2a; eq 1), the trimeric
heptaene 3b3 could be obtained in good yield as a pale yellow
solid (eq 5). Compound 3b3 is analogous to the ethyl ester
version (3a3) that was described in the introduction. In all such
Wittig-like reactions the initial Mo product is believed to be
J. AM. CHEM. SOC.
9
VOL. 128, NO. 51, 2006 16667

A R T I C L E S
Czekelius et al.
Figure 1. POV-ray rendering (ellipsoids at 50%) of the molecular structure of 7. Fluorine atoms, hydrogen atoms, and the cocrystallized pentane molecule
are omitted for clarity.
Table 1. Crystal Data and Structure Refinement Parameters for 7 and 17a
compound
7
17
reciprocal net ident.
empirical formula
formula weight
crystal system
05196
C55.50H68F24Mo2N2O8
1539.00
monoclinic
P2(1)/n
05149
C79H110F24Mo2N2O14
1959.57
monoclinic
P2(1)/n
space group
unit cell dimensions
a ) 11.0704(4) Å
b ) 27.1993(10) Å
c ) 22.5569(9) Å
R ) γ ) 90°
â ) 90.8330(10)°
6791.3(4) Å3
4
a ) 10.1034(7) Å
b ) 29.987(2) Å
c ) 14.9740(10) Å
R ) γ ) 90°
â ) 104.099(2)°
4400.0(5) Å3
2
volume
Z
density (calculated)
absorption coefficient
F(000)
3
1.479 g/cm3
1.505 g/cm
-
1
-1
0.484 mm
3116
0.396 mm
2020
theta range for data collection
index ranges
1.75° to 28.70°
-14 e h e 14
1.95° to 22.72°
-10 e h e 10
0 e k e 32
0 e l e 16
57 906
-
36 e k e 36,
30 e l e 30
-
reflections collected
135 769
independent reflections
completeness to theta ) 28.70˚
max. and min. transmission
data/restraints/parameters
17 523 [R(int) ) 0.0699]
5908 [R(int) ) 0.0417]
100.0%
100.0%
0.9623 and 0.9180
17 523/131/913
1.066
0.9615 and 0.9075
5908/1360/863
1.120
2
goodness-of-fit on F
final R indices [I > 2σ(I)]
R1 ) 0.0485, wR2 ) 0.1199
R1 ) 0.0983, wR2 ) 0.2184
R indices (all data)
R1 ) 0.0767, wR2 ) 0.1332
R1 ) 0.1112, wR2 ) 0.2280
-
3
-3
largest diff. peak and hole
1.613 and -0.375 eÅ
1.447 and -1.044 eÅ
a
2
In each case crystal data were recorded at 100 K with λ ) 0.710 73 Å; the refinement method was full-matrix least-squares on F , and the absorption
correction was semiempirical from equivalents.
rings. The λmax value for 12 is 384 nm (in CH2Cl2), 20 nm lower
than λmax for the all five-membered ring trimer in CH2Cl2 (404
nm, vide infra and Table 3). Although more studies of other
oligoenes that contain six-membered ring “errors” are necessary,
it would appear that the presence of one six-membered ring
leads to a significant decrease in λmax.
“Dimeric” and “Trimeric” Aldehydes and Reactions That
Employ Them. We envisioned that the same methodology used
to prepare aldehydes 2a and 2b might be employed to synthesize
longer chain analogues. In order to test this hypothesis, aldehyde
2b was treated with monodeprotonated diisopropyldipropargyl-
malonate (eq 9). The resulting propargylic alcohol (13) proved,
16668 J. AM. CHEM. SOC.
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VOL. 128, NO. 51, 2006

Synthesis of Oligoenes with up to 15 Double Bonds
A R T I C L E S
Table 2. Selected Bond Lengths (Å) and Angles (deg) for 7 and
well as a high catalyst loading was necessary. For example,
with a low catalyst loading (2%) the starting material was
consumed quickly, but only traces of the desired product could
be isolated. Dimeric aldehyde 2b2 is bright yellow, is stable in
air, and can be stored for long periods. The reaction sequence
shown in eqs 11 and 12 produced the “trimeric” aldehyde 2b3
as a deep yellow solid. Like 2b2, aldehyde 2b3 crystallizes
17
7
17
Mo(1)-N(1)
Mo(1)-C(1)
Mo(1)-O(1)
Mo(1)-O(2)
Mo(2)-N(2)
Mo(2)-C(2)
Mo(2)-O(4)
Mo(2)-O(3)
C(1)-C(3)
1.718(3)
1.911(3)
1.918(2)
1.923(2)
1.725(3)
1.914(3)
1.927(2)
1.940(2)
1.434(4)
1.421(4)
1.378(4)
98.98(13)
Mo(1)-N(1)
Mo(1)-C(1)
Mo(1)-O(1)
Mo(1)-O(2)
Mo(1)-O(1E)
C(1)-C(2)
1.697(7)
1.925(8)
1.938(5)
1.927(7)
2.388(11)
1.411(11)
1.354(11)
1.428(11)
1.343(15)
98.6(3)
113.1(3)
119.2(3)
167.7(5)
93.4(5)
120.9(3)
171.8(6)
137.3(6)
127.1(7)
127.0(7)
125.5(9)
C(2)-C(6)
C(6)-C(7)
C(7)-C(7A)
N(1)-Mo(1)-C(1)
N(1)-Mo(1)-O(1)
N(1)-Mo(1)-O(2)
C(2)-C(4)
C(3)-C(4)
N(1)-Mo(1)-C(1)
O(1)-Mo(1)-O(2)
Mo(1)-N(1)-C(11)
Mo(1)-C(1)-C(3)
N(2)-Mo(2)-C(2)
O(3)-Mo(2)-O(4)
Mo(2)-N(2)-C(21)
Mo(2)-C(2)-C(4)
C(4)-C(3)-C(1)
115.38(10) O(1E)-Mo(1)-C(1)
177.4(2)
138.2(2)
98.51(13)
O(1E)-Mo(1)-N(1)
O(1)-Mo(1)-O(2)
Mo(1)-N(1)-C(14)
116.98(10) Mo(1)-C(1)-C(2)
176.7(2)
139.7(2)
126.4(3)
125.7(3)
C(1)-C(2)-C(6)
C(2)-C(6)-C(7)
C(6)-C(7)-C(7A)
C(3)-C(4)-C(2)
readily in pure form after filtering the reaction mixture through
a silica gel plug and evaporating the solvent. This methodology
has not yet been employed to prepare longer polyenals.
With 8, 2b2, and 2b3 in hand, the stage was set to synthesize
longer odd-numbered analogues of 3b3. Reactions between 8
and 2b2 and 2b3 in methylene chloride yielded the “pentameric”
undecaene (eq 13) and the “heptameric” pentadecaene (eq 14),
respectively, in good yields as red microcrystalline solids. The
not unexpectedly, to be sensitive to traces of acid. For example,
when 13 was dissolved in CDCl3, which contained traces of
HCl, clean formation of the cumulene through loss of water
was observed over the course of 1 h. Nevertheless 13 could be
cyclized to the “dimeric” aldehyde 2b2 (eq 10). The reaction
conditions for this cyclization had to be chosen carefully. It
was found that a 9:1 mixture of acetone and water at reflux as
reactions are relatively rapid (minutes), and the products can
be precipitated readily from solution in high purity. They are
J. AM. CHEM. SOC.
9
VOL. 128, NO. 51, 2006 16669

A R T I C L E S
Czekelius et al.
Table 3. Electronic Transitions of Oligoenes in Dichloromethane, Acetonitrile, and Benzenea
oligomer
solvent
E(0−2)
E(0−1)
λ
max(0−1)
E(0−0)
ꢀ(0−
1)/104
dimer (3b2)
trimer (3b3)
tetramer (3b4)
pentamer (3b5)
hexamer (3b6)
heptamer (3b7)
dimer
trimer
tetramer
pentamer
hexamer
heptamer
dimer
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
C6H6
29 411
25 773
24 038
23 041
21 930
21 459
29 762
26 042
24 510
23 256
22 222
21 930
28 090
24 752
23 041
21 739
21 008
20 243
28 409
25 000
23 364
22 026
21 368
20 576
356
404
434
460
476
494
352
400
428
454
468
486
340
388
432
458
492
26 810
23 640
21 978
20 661
19 841
19 157
27 100
23 809
22 371
20 964
20 284
19 455
4.4
9.5
11.0
14.0
6.9
8.2
9.2
10.0
11.0
trimer
tetramer
pentamer
heptamer
C6H6
C6H6
C6H6
C6H6
a
The units of the transition energies are cm-1, the units of λ are nm, and the units of ꢀ are cm-1 M-1
.
analogous to that described for the synthesis of 6b (eq 4) and
added to Mo(NAr)(CH-t-Bu)(ORF6)2 to yield 1b in good yield
(
eq 15). Reaction of 1b with the monomeric aldehyde 2b or
trimeric aldehyde 2b3 yielded the pale yellow, dimeric pentaene
b2 and the deep orange, tetrameric nonaene 3b4, respectively
3
(eqs 16 and 17).
The methodology for synthesizing odd- and even-membered
oligoenes employing Mo complexes as Wittig reagents con-
sumes Mo reagents on a stoichiometric basis, although the
reactions are clean and the yields are high. An alternative
pathway for the synthesis of even-membered oligoenes involves
McMurry coupling of two aldehydes. Initially it was not clear
that highly conjugated oligoenes would tolerate the low valent
titanium species present in a McMurry reaction. We were
pleased to find that reaction of aldehydes 2b, 2b2, or 2b3 with
an excess of a mixture of TiCl4 and Zn afforded dimeric
pentaene 3b2, tetrameric nonaene 3b4, and hexameric tridecaene
3b6, respectively (eq 18). The lower yield of 3b6 is not surprising
in reactions of this type given the likely increasing sensitivity
of longer chain polyenes under the reaction conditions.
Transition energies for the strongly allowed S fS transitions
relatively insoluble in pentane, ether, or benzene but soluble in
dichloromethane. Unfortunately, the oligoenes tend to form
microcrystalline fibrous solids that resemble cotton candy. So
far we have not been able to prepare single crystals that are
suitable for X-ray studies.
0
2
in polyenes have been shown to follow eq 19 where N is the
1
6,19
number of double bonds.
E(N) ) A + B/N
(19)
Reactions of the type shown in eqs 5, 13, and 14 yield
oligoenes that contain an odd number of repeat units. Even-
membered oligoenes are not accessible directly in pure form
using this method. (Of course, mixtures that contain even-
membered oligoenes could be generated in reactions between
Absorption spectra of the isolated oligoenes (3b2, 3b3, 3b4, 3b5,
and 3b7) in dichloromethane are shown in Figure 2. Transition
energies, λmax values (for the 0-1 transition), and selected molar
absorptivities in dichloromethane, acetonitrile, and benzene are
listed in Table 3. Figure 3 shows the correlation of the E(0-0),
E(0-1), and E(0-2) transition energies for the S0 f S2
transition with 1/N. The parameters A and B obtained from fits
8
and a mixture of 2b2 and 2b3, for example.) We envisioned
that reaction of a complex related to 1a bearing a suitably
substituted vinyl-cyclopenten-alkylidene would provide access
to both odd and even oligoenes upon reaction with aldehydes
19a
to eq 19 are in good agreement with results obtained previously.
2
b, 2b2, and 2b3. Triene 15 was prepared readily in a manner
(19) Knoll, K.; Schrock, R. R. J. Am. Chem. Soc. 1989, 111, 7989.
16670 J. AM. CHEM. SOC.
9
VOL. 128, NO. 51, 2006

Synthesis of Oligoenes with up to 15 Double Bonds
A R T I C L E S
Figure 2. Absorption spectra of oligoenes 3b2 (violet), 3b3 (red), 3b4
(brown), 3b5 (blue), and 3b7 (green) in dichloromethane at the same
concentration (N ) 5, 7, 9, 11, and 15, respectively).
shown in Figure 4, and selected bond distances and angles are
listed in Table 2. In contrast to 7 two diethyl ether solvent
molecules are weakly bound to the metal center trans to the
alkylidene, a feature of related bimetallic species that have been
1
4,20
structurally characterized recently.
A projection along the
conjugated system reveals a high degree of planarity of the
oligoene system with the metal centers and R carbons slightly
out of the plane (Figure 5). (Individual deviations are 0.1080
(
0.0033) for Mo(1), -0.1735 (0.0056) for C(1), 0.0225 (0.0051)
for C(2), 0.0187 (0.0053) for C(6), -0.0737 (0.0068) for C(7),
.0737 (0.0068) for C(7A), -0.0187 (0.0053) for C(6A),
0
-
0.0225 (0.0051) for C(2A), 0.1735 (0.0056) for C(1A), and
-0.1080 (0.0033) for Mo(1A).) Although there was little doubt
as to the alternating trans,cis structure of the repeat five-
membered units in oligoenes prepared from DEDPM, to our
knowledge this is the first confirmation of that structure, at least
in a “dimer” with a Mo attached to each end.
Figure 3. Plots of E(0-0), E(0-1), and E(0-2) vs 1/N for oligomers in
CH2Cl2.
Conclusions
We have described a method of preparing oligoenes that
represent portions of polymers obtained by ring-closing me-
tathesis polymerization of dialkyldipropargylmalonates to give
polyenes that contain all five-membered rings. These oligoenes
are accessible through reactions that involve new mono- or
bimetallic Mo alkylidene complexes, although McMurry cou-
pling has also been successful for synthesizing several. The
spectroscopic properties of these compounds are in agreement
with what one would expect for highly conjugated polyenes.
We also were able to show that incorporation of a single six-
membered ring in the center of a “trimer” produces two oligoene
isomers and that λmax in this species is lower than what it is in
the trimer that contains three five-membered rings. We hope to
be able to use this new methodology to synthesize longer
polyenes and 1,6-heptadiyne variations, including those that
incorporate photochemically or electrochemically active func-
tionalities.
Extrapolation of N to infinity yields a limit of E(0-0) ≈ 15 500
-
1
cm (λ ) 650 nm) in dichloromethane.
Synthesis of a Dimeric Bimetallic Species and Its X-ray
Structure. The key to the stoichiometric synthesis of symmetric
oligoenes of some significant length is the bimetallic species
8
. We wanted to know whether bimetallic relatives could be
prepared that contain more than one monomer “repeat” unit.
Therefore we sought to prepare a bimetallic species that contains
two monomer repeat units.
McMurry coupling of 5a produced the pentaene 16 in low
yield (eq 20). As expected, the lack of sterically protecting
methyl groups at the ends of the oligoene and the presence of
ethyl esters instead of isopropyl esters render 16 prone to
decomposition. Therefore, it must be used immediately after it
is prepared and purified. Reaction of 16 with Mo(NAr)(CH-t-
Bu)(ORF6)2 produced the bimetallic species 17, which was
isolated in low yield from diethyl ether as deep purple crystals
Experimental Section
(
eq 21). NMR data suggest that 17 has the same alkylidene
configuration at each end (presumably syn,syn) with δHR )
3.15 ppm in C6D6. Crystals suitable for an X-ray crystal-
lographic analysis were grown from diethyl ether. (See Table
for crystal and structural refinement data.) The structure is
General Comments. All manipulations of air- and moisture-sensitive
materials were performed in oven-dried (200 °C) glassware under an
1
(
20) Schrock, R. R.; Gabert, A. J.; Singh, R.; Hock, A. S. Organometallics 2005,
1
24, 5058.
J. AM. CHEM. SOC.
9
VOL. 128, NO. 51, 2006 16671

A R T I C L E S
Czekelius et al.
Figure 4. POV-ray rendering (ellipsoids at 35%) of the molecular structure of 17. Fluorine atoms, hydrogen atoms, and the cocrystallized pentane molecule
are omitted for clarity. Atoms related by the crystallographic inversion center are not labeled.
,14 and RuCp(NCMe)
PF
17b
were prepared according
, CH[5] ) diethyl
-(2-methylprop-1-enyl)-4-vinylcyclopent-3-ene-1,1-dicarboxylate). 2-(4-
[
5])(NAr)(ORF6
)
2
3
6
3 2
to previously reported methods (ORF6 ) OCMe(CF )
3
17a
Chloro-but-2-ynyloxy)-tetrahydropyran and diethyldipropargyl ma-
lonate23 were prepared as described in the literature. Synthetic details
for all organic compounds (except the symmetric polyenes) can be found
in the Supporting Information.
Crystal Structures. Low-temperature diffraction data were collected
on a Siemens Platform three-circle diffractometer coupled to a Bruker-
AXS Smart Apex CCD detector with graphite-monochromated Mo KR
radiation (λ ) 0.710 73 Å), performing æ- and ω-scans. All structures
Figure 5. Selected view of 17 showing the planarity of the conjugated
ring system.
atmosphere of nitrogen on a dual-manifold Schlenk line or in a Vacuum
Atmospheres glovebox. HPLC grade organic solvents were sparged
with nitrogen and dried by passage through activated alumina (for
diethyl ether, toluene, pentane, THF, and methylene chloride) followed
by passage through Q-5 supported copper catalyst (for benzene) prior
to use and then stored over 4 Å Linde-type molecular sieves. Benzene-
2
were solved by direct methods using SHELXS and refined against F
on all data by full-matrix least-squares with SHELXL-97. All non-
hydrogen atoms were refined anisotropically. All hydrogen atoms were
included into the model at geometrically calculated positions and refined
using a riding model. The isotropic displacement parameters of all
hydrogen atoms were fixed to 1.2 times the U-value of the atoms they
are linked to (1.5 times for methyl groups).
The crystals obtained for compound 17 diffracted only to the
relatively mediocre resolution of 2θmax ) 45.4°, leading to a relatively
low data-to-parameter ratio of about 7:1. In addition the structure
determination was troubled by several complicated disorders, all of
which were refined with the help of similarity restraints on 1-2 and
d
6
and toluene-d
vacuum-distilled. Methylene chloride-d
distilled, and stored over 4 Å Linde-type molecular sieves. Chloroform-
was used as received. NMR spectra were recorded on a Varian 500
8
were dried over sodium/benzophenone ketyl and
2
was dried over CaH , vacuum
2
d
1
1
13
or Varian 300 spectrometer. Chemical shifts for H and C spectra
were referenced to the residual H/ C resonances of the deuterated
solvent ( H: CDCl
2
1
13
1
3
, δ 7.26; C
6
D
6
, δ 7.16; CD
2
Cl
Cl
2
, δ 5.32; C
7 8
D , δ
1
-3 distances. To counteract correlation effects arising from the low
1
3
.09. C: CDCl
3
, δ 77.0; C
6
D
6
, δ 128.39; CD
2
2
, δ 54.00) and are
data-to-parameter ratio, similarity restraints on displacement parameters
as well as rigid bond restraints for anisotropic displacement parameters
were applied to all atoms. In spite of the below-average data quality,
the hydrogen atom bound to C(1) could be located in the difference
Fourier synthesis and was refined semifreely with the help of a distance
restraint, while constraining its U-value to 1.2 times the Ueq value of
C(1).
Compound 7 cocrystallizes with one-half molecule of pentane per
asymmetric unit. The pentane is disordered over four positions that
involve the crystallographic inversion center. The ratio between the
two crystallographically independent components was refined freely,
and similarity restraints on 1-2 and 1-3 distances and displacement
19
reported as parts per million relative to tetramethylsilane. F NMR
spectra were referenced externally to fluorobenzene (δ -113.15 ppm
upfield of CFCl ). UV-vis spectra were recorded using a Hewlett-
3
Packard 8452A diode array spectrophotometer at approximately 22 °C.
High-resolution mass spectrometry measurements were performed at
the MIT Department of Chemistry Instrument Facility, and elemental
analyses were performed by the H. Kolbe Microanalytical Laboratory,
M u¨ lheim an der Ruhr, Germany.
Mo(CHCMe
Me )(ORF6
3
)(N-2,6-i-Pr
2
C
6
H
3
)(ORF6
)
2
,21 Mo(CHCMe
)(ORF6
,22 Mo(CH-
2
Ph)(N-2,6-
2
2
2
C
6
H
3
)
2
,
Mo(CHCMe
3
)(N-2-t-BuC
6
H
4
)
2
(
21) Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.;
O’Regan, M. J. Am. Chem. Soc. 1990, 112, 3875.
(22) Oskam, J. H.; Fox, H. H.; Yap, K. B.; McConville, D. H.; O’Dell, R.;
Lichtenstein, B. J.; Schrock, R. R. J. Organometal. Chem. 1993, 459, 185.
(23) Atkinson, R. S.; Grimshire, M. J. J. Chem. Soc., Perkin Trans. 1 1986,
1215.
16672 J. AM. CHEM. SOC.
9
VOL. 128, NO. 51, 2006

Synthesis of Oligoenes with up to 15 Double Bonds
A R T I C L E S
parameters as well as rigid bond restraints for anisotropic displacement
parameters were applied to all solvent atoms. Nevertheless, mathemati-
cal correlation between coordinates and anisotropic displacement
parameters of the disordered atoms gives rise to unusually shaped
thermal ellipsoids for some of the pentane atoms. This should not affect
the accuracy of the structure of the main molecule, and the low residual
values of the refinement attest to the overall high quality of the structure
of 7. The hydrogen atoms bound to C(1) and C(2) were taken from the
difference Fourier synthesis and refined semifreely with the help of
distance restraints, while constraining their U-values to 1.2 times the
[Mo(NAr)(ORF6
(NAr)(ORF6 ] (17). Activated zinc (1.99 g, 30.4 mmol) was suspended
in degassed DME (20 mL), and the mixture was cooled to 0 °C. TiCl
(2.85 g, 15.0 mmol) was added dropwise. After the mixture was stirred
for 5 min, it was heated to reflux for 2 h. After cooling to 0 °C a
solution of 5a (953 mg, 3.58 mmol) in DME (10 mL) was added
dropwise. The blue suspension was allowed to warm to room temptera-
ture over a period of 18 h and then heated to reflux for 2 h. After
2 2 2 2 2
) ]CH[5](CO Et) CHdCH[5](CO Et) CH[Mo-
)
2
4
cooling to 0 °C a mixture of saturated aqueous NaHCO
CO (5:1) was added along with ether. The gray-blue suspension
was filtered over Celite and washed with Et O. The combined organic
phases were dried over Na SO , and the solvents were evaporated. Flash
column chromatography (silica gel, deactivated with NEt , hexanes/
3
and saturated
K
2
3
Ueq value of the atom to which they are bound. Further details of the
2
data quality and a summary of the residual values of the refinements
are listed in Table 1.
2
4
3
ethyl acetate 25:1) gave pentaene 16 as a colorless oil (120 mg, 0.240
mmol, 13%). The product was used immediately in the next step.
2 2 2
Mo(CH[5](CO -i-Pr) )(NAr)(ORF6) (1b). Triene 15 (1.41 g, 4.60
mmol) was dissolved in pentane (5 mL), and molecular sieves (4 Å)
were added. After 2 h, the solution was decanted and added to a solution
of Mo(CHCMe )(NAr)(ORF6) (3.24 g, 4.60 mmol) in pentane (30 mL),
3 2
and the mixture was stirred for 1 h. The orange precipitate was collected
Pentaene 16 (31.5 mg, 63.0 µmol) was dissolved in diethyl ether (2
mL), and the solution was stored over molecular sieves (4 Å) for 2 h.
Mo(NAr)(CHCMe )(ORF6) (96.5 mg, 0.126 mmol) was dissolved in
3 2
diethyl ether (0.5 mL), and the pentaene solution was added dropwise
at room temperature. The mixture was strirred for 18 h. The solvent
was evaporated, and the residue was triturated with pentane. The dark
on a frit and washed with cold pentane; the yield of 1b was 3.03 g
1
(
3.27 mmol, 71%): H NMR (500 MHz, CD
2
Cl
2
) δ 12.80 (s, 1H, JCH
)
)
130 Hz, ModCHR), 7.27 (t, 1H, J ) 7.5 Hz, p-Ar), 7.18 (d, 2H, J
7.5 Hz, m-Ar), 5.97 (s, 1H, CHdCMe ), 4.86 (sept, 2H, J ) 6.5 Hz,
), 3.70 (s, 2H, CH ), 3.53 (sept, 2H, J ) 6.3 Hz, CHMe ),
.18 (s, 2H, CH ), 1.96 (s, 3H, Me), 1.91 (s, 3H, Me), 1.43 (s, 6H,
C(CF Me), 1.20 (d, 12H, J ) 6.5 Hz, CHMe ), 0.92 (d, 6H, J ) 6.3
Hz, OCHMe ), 1.00 (d, 6H, J ) 6.3 Hz, OCHMe
MHz, CD Cl ) δ 258.9, 171.4, 154.7, 148.6, 143.9, 140.1, 130.1, 126.8,
24.4 (q, JCF ) 288 Hz, CF ), 124.1 (q, JCF ) 288 Hz, CF ), 123.8,
19.2, 81.3 (quin, J ) 29 Hz, C(CF Me), 69.4, 58.0, 45.4, 43.4, 29.1,
8.1, 23.9, 21.7, 20.3, 19.4; F NMR (282 MHz, C ) δ -77.79.
: C, 48.57; H, 5.26; N, 1.49. Found:
solid was recrystallized from Et
(
2
O/pentane to give 17 as purple crystals
14.0 mg, 8.05 µmol, 13%): 1H NMR (300 MHz, C
) δ 13.15 (s,
H, ModCHR), 6.93-6.85 (m, 6H, Ar), 6.64 (s, 2H, CHdCH), 3.77-
.94 (m, 16H, CH and OCH ), 3.62 (septet, J ) 6.9 Hz, 4H, CHMe ),
Me), 1.23 (d, J ) 6.9 Hz, 24H, CHMe ), 0.84 (t,
) δ -78.32
12: C, 45.58; H, 4.52; N, 1.61.
2
6 6
D
OCHMe
3
2
2
2
2
3
2
2
2
2
3
)
2
2
1
3
1.33 (s, 12H, C(CF
J ) 6.9 Hz, 12H, OCH
s). Anal. Calcd for C66
3
)
2
2
2
2
); C NMR (125
1
9
2
CH
3
); F NMR (282 MHz, C
F24Mo O
2 2
6
D
6
2
2
(
H
78
N
1
1
2
3
3
Found: C, 45.46; H, 4.44; N, 1.54.
{Mo(N-2-t-BuC )(ORF6 -µ-(CH[6](CO
was charged with 0.203 g (0.301 mmol) of Mo(N-2-t-BuC
Bu)(ORF6 , and 5 mL of Et O was added. To the stirring solution was
added a solution of 0.0700 g (0.264 mmol) of triene 9 in 10 mL of
Et O. The solution became deep red and was allowed to stir at room
3 2
)
1
9
6
H
4
)
2
}
2
2
Et)
2
C) (11). A flask
)(CH-t-
6
D
6
6
H
4
Anal. Calcd for C38
C, 48.95; H, 5.47; N, 1.49.
Mo(NAr)(ORF6 ]CH[5](CO
a (35.0 mg, 0.132 mmol) was dissolved in pentane (5 mL), and the
solution was treated with molecular sieves (4 Å) for 15 min. Pentane
5 mL) was then used to dissolve Mo(NAr)(CHCMe )(ORF6 (186 mg,
.265 mmol). The solution of 6a was slowly added to the Mo solution,
H49NF12MoO
6
)
2
2
[
)
2
2 2 2
Et) CH[Mo(NAr)(ORF6) ] (7). Triene
2
6
temperature for 18 h. The volatiles were removed in vacuo, and the
residue dissolved in a minimal amount of pentane. The pentane solution
was then set aside at -25 °C for several days during which time the
desired complex precipitated as 0.100 g (45%) of a brown powder.
(
0
3
)
2
and the mixture was stirred for 4 h. The solution was then concentrated
and stored at -40 °C to yield two crops of crystals (124 mg, 82.0
Repeated crystallization from cold pentane removed any traces of Mo-
1
(
(
(
N-2-t-BuC
6
H
4
)(CH-t-Bu)(ORF6
2
) :
H NMR (500 MHz, C
6
6
D ) δ 12.36
µmol, 62%). Crystals suitable for X-ray studies were selected from
s, 1H, JCH ) 125 Hz, ModCHR), 7.74 (d, 1H, J ) 7.5 Hz, Ar), 7.57
d, 1H, J ) 7.5 Hz, Ar), 7.52 (s, 1H, CtCH), 7.04 (t, 2H, J ) 7.5 Hz,
1
this batch: H NMR (500 MHz, CD
2
Cl
2
) δ 12.65 (s, 2H, JCH ) 125
Hz, ModCHR), 7.28 (t, 2H, J ) 7.5 Hz, p-Ar), 7.17 (d, 4H, J ) 7.5
Hz, m-Ar), 3.84 (q, 4H, J ) 7.0 Hz, OCH ), 3.60 (s, 4H, CH ), 3.47
sept, 4H, J ) 7.0 Hz, CHMe ), 1.39 (s, 12H, C(CF Me), 1.17 (d,
4H, J ) 7.0 Hz, CHMe ), 0.93 (t, 6H, J ) 7.0 Hz, OCH
) δ -78.19 (br s), -78.36 (br s).
]CH[5](CO -i-Pr) CH[Mo(NAr′)(ORF6
Ar), 6.86 (m, 4H, Ar), 4.94 (s, 2H, CH
H, CH ), 1.53 (s, 6H, C(CF Me), 1.40 (s, 9H, CMe
CMe ), 1.32 (br s, 3H, C(CF Me), 0.75 (t, 6H, J ) 7.0 Hz, OCH
C NMR (125 MHz, C ) δ 271.1 (MoC ), 259.0 (MoC H), 170.3
CO), 157.6, 156.3, 147.0, 146.7, 134.7, 134.2, 132.1, 130.2, 129.8,
127.5, 127.3, 127.1, 126.8, 124.5 (q, JCF ) 286 Hz, CF ), 124.4 (q, J
2
), 3.69 (m, 4H, OCH
), 1.38 (s, 9H,
CH );
2
), 3.67 (s,
2
2
2
2
3
)
2
3
(
2
2
3 2
)
3
3
)
2
2
3
19
2
2
CH
3
);
F
13
6
D
6
R
R
NMR (282 MHz, C
D
6 6
(
[
Mo(NAr′)(ORF6
)
2
2
2
)
2
] (8). A
Ph)-
(609 mg, 0.858 mmol), which was subsequently dissolved in
3
CF
5
(
0 mL round-bottom flask was charged with Mo(NAr′)(CHCMe
ORF6
2
) 289 Hz, CF ), 124.2 (br q, J ) 286 Hz, CF ), 113.7, 83.0 (br m,
3
CF
3
)
2
C(CF ) Me), 82.75 (sep, J ) 29.9 Hz, C(CF ) Me), 61.78 (OCH ),
3
2
CF
3
2
2
diethyl ether (12 mL). Triene 6b (125 mg, 0.429 mmol) was dissolved
in diethyl ether (8 mL), and the solution was stood over molecular
sieves (4 Å) for 30 min. It was then added slowly to the complex
solution, and the mixture was stirred for 18 h. The solvent was removed
in vacuo, and the residue was redissolved in pentane/diethyl ether (15:
55.02 (Cquat-[6]), 47.22, 36.16, 36.09, 35.84, 30.75, 30.62, 19.59 (br,
19
C(CF
MHz, C
CF ). Anal. Calcd for C49
Found: C, 40.43; H, 3.82; N, 1.93.
3
)
2
Me), 19.08 (C(CF
3
)
2
Me), 14.16 (OCH
), -78.02 (q, 6 CF
54 2 2 8
H F24Mo N O : C, 40.68; H, 3.76; N, 1.94.
2
CH
3
); F NMR (282
6 6
D ) δ -77.66 (q, 6 CF
3
3
), -78.13 (br, 12
3
0
4
2
)
1
.7 mL). Storage at -40 °C yielded pure crystalline material (2 crops,
(E)-Di-1,2-[1-(2-methyl-propenyl)-4,4-di-iso-propyl-carboxy-cy-
1
94 mg, 0.348 mmol, 81%): H NMR (500 MHz, CD
H, JCH ) 128 Hz, ModCHR), 7.13 (m, 6H, Ar), 4.78 (septet, 2H, J
6.5 Hz, OCHMe ), 3.62 (s, 4H, CH ), 2.39 (s, 12H, ArMe), 1.37 (s,
2H, C(CF Me) 0.96 (d, 12H, J ) 6.5 Hz, CHMe
) δ 275.3, 170.9, 157.5, 138.1, 133.1, 129.8, 128.5, 124.1
2
Cl
2
) δ 12.66 (s,
clopent-1-enyl]-ethene (3b ). A solution of 2b (13 mg, 0.043 mmol)
2
in dichloromethane (0.5 mL) was stored over molecular sieves (4 Å)
for 30 min and added to a solution of 1b (41 mg, 0.043 mmol) in
dichloromethane (2 mL). The reaction was stirred vigorously for 3 h.
Solvent was removed in vacuo, and the residue was eluted through an
activated basic alumina plug with diethyl ether. The solvent was
2
2
1
3
3
)
2
2
); C NMR (125
2 2
MHz, CD Cl
(
)
(
q, JCF ) 286 Hz, CF
27 Hz, C(CF
282 MHz, CD Cl
3
), 123.9 (q, JCF ) 288 Hz, CF
3
), 81.9 (sept, JCF
)
2
Me), 69.3, 56.7, 45.1, 30.2, 21.6, 19.4; 9F NMR
1
evaporated, and the residue was triturated with pentane (slightly soluble)
3
1
2
2
) δ -78.06 (br s), -78.39 (br s). Anal. Calcd for
to yield 3b
(500 MHz, C
(sept, 4H, J ) 6.0 Hz, OCHMe
2
(13 mg, 0.021 mmol, 49%) as an off-white solid: H NMR
C
47
50 2
H N F24Mo
2
8
O : C, 39.79; H, 3.55; N, 1.97. Found: C, 39.72; H,
D
6 6
) δ 6.75 (s, 2H, dCH), 6.02 (s, 2H, CHdCMe
2
), 5.01
3
.51; N, 1.96.
2
), 3.65 (s, 8H, CH ), 1.67 (s, 6H, Me),
2
J. AM. CHEM. SOC.
9
VOL. 128, NO. 51, 2006 16673

A R T I C L E S
Czekelius et al.
1
.54 (s, 6H, Me), 0.98 (m, 24H, OCHMe
2
); 13C NMR (125 MHz, C
6
D
6
)
23.9 (m), 20.8; IR (CDCl
1467, 1454, 1376, 1270, 1197, 1105, 1068. HRMS (ESI, [M + Na] ).
3
) cm-1 3041 (w), 2984, 2938 (w), 1722 (s),
+
δ 171.9, 137.1, 136.9, 134.5, 124.5, 120.4, 69.1, 58.7, 45.7, 41.0, 27.6,
-1
21.8 (m), 20.8. IR (CDCl
3
) cm 3141 (w), 2984, 2907, 1724 (s), 1446,
Calcd for C81
nm (C ), 460 nm (CH
and 9.5 × 10 cm
H
112
O
20Na: 1427.7639. Found: 1428.7645. λmax ) 458
+
5
-1
-1
1
C
1
368, 1259 (s), 1192, 1095, 1074, 1011. HRMS (EI, [M] ). Calcd for
H
6 6
2
Cl
2
); ꢀ ) 1.0 × 10 cm
M
in benzene
4
-1
-1
36
4
H
0 cm
52
O
8
-1
: 612.3657. Found: 612.3637. λmax ) 340 nm; ꢀ ) 6.9 ×
M
in dichloromethane.
-1
-6
M
in benzene (9.5 × 10 M).
3 6
McMurry Coupling of 2b to give 3b . A 25 mL two-necked flask
Di-1,2-{1-[(E)-(2-methyl-propenyl)-4,4-di-iso-propyl-carboxy-cy-
with a reflux condensor was charged with activated zinc (217 mg, 3.30
mmol) and dimethoxyethane (10 mL). After cooling to 0 °C titanium
tetrachloride (313 mg, 1.65 mmol) was added dropwise. The blue
suspension was heated to reflux for 2 h. After the suspension cooled
clopent-1-enyl]-vinyl}-4,4-di-iso-propyl-carboxy-cyclopent-1-ene (3b
Aldehyde 2b (35.4 mg, 0.115 mmol) was dissolved in dichloromethane
2 mL). The solution was stored over molecular sieves (4 Å) for 30
3
).
(
min and then added to a solution of 8 (81.4 mg, 57.0 µmol) in
dichloromethane (3 mL). The reaction was stirred vigorously for 3 h
to yield a brownish-yellow solution. The solvent was removed in vacuo,
and the residue was dissolved in diethyl ether and passed through an
activated basic alumina plug. After evaporation of the solvent the
3
to 0 °C, a solution of trimeric aldehyde 2b (330 mg, 0.388 mmol) in
dimethoxyethane (2 mL) was added dropwise and the mixture was
allowed to warm to rt over 12 h. The red-brown suspension was heated
to reflux for 1 h. After the suspension cooled to rt, it was filtered through
celite and the solid was washed with dichloromethane (50 mL). The
solvent was evaporated. The residue was dissolved in a minimum
amount of dichloromethane and excess pentane added. After stirring
for 4 h at rt the red precipitate was filtered off, redissolved in
dichloromethane, and filtered through a neutral aluminum oxide plug
(1 cm × 2 cm) using dichloromethane as eluent. After evaporation of
the solvent the product was obtained as a brick-red powder (81.0 mg,
product was obtained as a yellowish solid (32 mg, 37.0 µmol, 64%):
1
H NMR (500 MHz, C
.76 (d, 2H, J ) 15.5 Hz, CHdCH), 6.00 (s, 2H, CHdCMe
sept, 4H, J ) 6.5 Hz, OCHMe ), 5.01 (sept, 2H, J ) 6.5 Hz, OCHMe
), 3.65 (s, 2H, CH ), 3.57 (s, 2H, CH ), 1.68 (s, 6H,
), 0.97 (d, 12H, J ) 6.0
) δ 171.8, 171.7, 137.7, 137.4,
6
D
6
) δ 6.83 (d, 2H, J ) 15.5 Hz, CHdCH),
), 5.04
),
6
(
3
2
2
2
.71 (s, 2H, CH
2
2
2
Me), 1.55 (s, 6H, Me), 1.01 (m, 24H, OCHMe
Hz, OCHMe
2
13
48.0 µmol, 25%): 1H NMR (300 MHz, CH
CH), 6.59 (d, J ) 15.9 Hz, 2H, CHdCH), 6.50 (d, J ) 15.9 Hz, 2H,
CHdCH), 6.07 (s, 2H, CHdCMe ), 5.03 (m, 12H, OCHMe ), 3.36
(br m, 12H, CH ), 3.30 (br m, 8H, CH ), 3.22 (br s, 4H, CH ), 1.89 (s,
6H, Me), 1.82 (s, 6H, Me), 1.25 (br m, 72H, OCHMe ); C NMR (75
MHz, CH Cl ) δ 171.93, 171.86, 171.86, 138.06, 137.83, 137.75,
137.57, 137.28, 136.28, 134.21, 128.83, 125.49, 123.80, 123.60, 123.23,
2
); C NMR (125 MHz, C
D
6 6
2 2
Cl ) δ 6.72 (br s, 6H, CHd
1
4
1
36.7, 134.6, 125.6, 122.9, 120.5, 69.3, 69.1, 58.7, 58.0, 45.8, 42.3,
-1
0.9, 27.6, 21.8, 20.8; IR (CDCl
3
) cm 2983, 2936(w), 1722(s), 1467,
2
2
+
376, 1262(s), 1196, 1104(s), 1068. HRMS (EI, [M] ) Calcd for
2
2
2
1
3
C
51
H
72
O
12: 876.5018. Found: 876.4996. λmax ) 388 nm (C
6
H
6
4
), 404
2
4
-1
-1
-1
nm (CH
M
2
Cl
2
); ꢀ ) 8.2 × 10 cm
M
in benzene and 4.4 × 10 cm
2
2
-1
in dichloromethane.
1
4
1
22.00, 119.60, 69.75, 69.57, 58.26, 57.51, 57.46, 45.03, 41.87, 41.71,
0.35, 27.88, 21.86, 21.83, 21.81, 20.77; IR (CDCl ) cm 3016, 2984,
3
(
E)-Di-1,2-[1-{(E)-2-[2-(2-methyl-propenyl)-4,4-di-iso-propyl-car-
-1
boxy-cyclopent-1-enyl]-vinyl}-4,4-di-iso-propyl-carboxy-cyclopent-
-enyl]-ethene (3b ). The trimeric aldehyde 2b (21 mg, 0.025 mmol)
722, 1467, 1376, 1271, 1195, 1104, 1068, 949. HRMS (ESI, [M +
1
4
3
+
Na] ). Calcd for C96
H
132
O
24Na: 1691.9001. Found: 1691.9069. λmax
was dissolved in dichloromethane (2 mL). The solution was stored over
molecular sieves (4 Å) for 30 min and added to a solution of 1b (24
mg, 0.025 mmol) in dichloromethane (2 mL). The reaction was stirred
vigorously for 3.5 h. The solvent was removed in vacuo, and the residue
was eluted through an activated basic alumina plug with a mixture of
diethyl ether/tetrahydrofuran (2:1). The solvent was removed from the
5
-1
-1
)
476 nm; ꢀ ) 1.1 × 10 cm
Oligomers 3b and 3b can be prepared similarly from 2b
respectively.
M
in methylene chloride.
2
4
1 2
and 2b ,
Di-1,2-([1-{(E)-[(2-methyl-propenyl)-4,4-di-iso-propyl-carboxy-
cyclopent-1-enyl]-vinyl}-1-{(E)-[(2-methyl-propenyl)-4,4-di-iso-pro-
pyl-carboxy-cyclopent-1-enyl]-vinyl}-1-(E)-4,4-di-iso-propyl-carboxy-
cyclopent-1-enyl]-vinyl)-4,4-di-iso-propyl-carboxy-cyclopent-1-
filtrate, and the residue was washed with pentane to yield 3b
.010 mmol, 42%) as an orange solid: 1H NMR (500 MHz, 54:46
/CDCl ) δ 6.64 (m, 4H, CHdCH), 6.51 (m, 2H, CHdCMe ), 5.94
s, 2H, dCH), 4.95 (m, 8H, OCHMe ), 3.40 (s, 4H, CH ), 3.38 (s, 4H,
CH ), 3.35 (s, 4H, CH ), 3.31 (s, 4H, CH ), 1.68 (s, 6H, Me), 1.66 (s,
H, Me), 1.05 (m, 48H, OCHMe ); C NMR (125 MHz, 54:46 C
CDCl ) δ 172.2, 172.0, 137.8, 137.7, 137.4, 136.4, 134.4, 125.8, 123.7,
22.4, 120.2 (m), 69.5 (m), 58.6, 57.8, 45.4, 42.2, 42.0, 40.7, 27.9,
4
(12 mg,
0
C
(
6
D
6
3
2
7 3
ene (3b ). Trimeric aldehyde 2b (253 mg, 0.297 mmol) was dissolved
2
2
in dichloromethane (7 mL). The solution was stored over molecular
sieves (4 Å) for 45 min and added to a solution of 8 (211 mg, 0.149
mmol) in dichloromethane (3 mL). The reaction was stirred vigorously
for 4 h. The solvent was removed in vacuo, and the residue was eluted
through an activated basic alumina plug with diethyl ether/tetrahydro-
furan (6:1) and benzene to yield 3b
reddish solid: 1H NMR (500 MHz, C
(s, 4H, CHdCH), 6.62 (d, 2H, J ) 15.4 Hz, CHdCH), 6.53 (d, 2H, J
) 15.4 Hz, CHdCH), 6.07 (s, 2H, CHdCMe ), 5.03 (m, 14H,
OCHMe ), 3.30 (m, 28H, CH ), 1.89 (s, 6H, Me), 1.82 (s, 6H, Me),
1.24 (m, 84H, OCHMe ); C NMR (125 MHz, C ) δ 171.9, 171.8,
2
2
2
1
3
6
2
6 6
D /
3
1
2
1
-1
2.0 (m), 21.0; IR (CDCl
454, 1331, 1262 (s), 1165, 1097, 1016. HRMS (ESI, [M + Na]+).
16Na: 1163.6278. Found: 1163.6244. λmax ) 432
3
) cm 3236 (w), 2991, 2913, 1722 (s), 1619,
7
(226 mg, 0.117 mmol, 79%) as a
6 6
D
) δ 6.73 (s, 4H, dCH), 6.72
Calcd for C66
92
H O
4
-1
-1
nm; ꢀ ) 9.2 × 10 cm
M
in benzene.
2
Di-1,2-([1-{(E)-[(2-methyl-propenyl)-4,4-di-iso-propyl-carboxy-
cyclopent-1-enyl]-vinyl}-1-(E)-4,4-di-iso-propyl-carboxy-cyclopent-
2
2
13
2
6 6
D
1
-enyl]-vinyl)-4,4-di-iso-propyl-carboxy-cyclopent-1-ene (3b
dimeric aldehyde, 2b (78 mg, 0.12 mmol), was dissolved in dichlo-
romethane (2 mL), and the solution was stored over molecular sieves
4 Å) for 30 min. It was then added to a solution of 8 (94 mg, 0.066
5
). The
138.0, 137.9, 137.8, 137.7, 137.7, 137.5, 136.7, 134.5, 125.9, 124.2,
124.1, 123.7, 122.6, 120.3, 118.4, 69.5, 69.3, 58.6, 57.9, 45.6, 42.2,
2
42.1, 42.1, 40.8, 27.7, 21.9, 21.9, 21.9, 21.9, 21.9, 20.8; IR (CDCl
3
) ν
(
) 3042 (w), 2984, 2938, 2865 (w), 1723 (s), 1466, 1371, 1262 (s),
-
1
+
mmol) in dichloromethane (4 mL). The reaction was stirred for 3 h.
Solvent was removed in vacuo, and the residue was eluted through an
activated basic alumina plug with diethyl ether/tetrahydrofuran (2:1)
1195, 1105 (s), 1068 cm . HRMS (ESI, [M + Na] ). Calcd for
C
111
H
152
O
28Na: 1956.0362. Found: 1956.0392. λmax ) 492 nm (C
6
H
6
),
5
-1
-1
5
494 nm (CH
cm
2
Cl
2
); ꢀ ) 1.1 × 10 cm
M
in benzene and 1.4 × 10
-
1
-1
and benzene to give pentamer 3b
5
(76 mg, 0.054 mmol, 82%) as an
orange solid: H NMR (500 MHz, CD Cl ) δ 7.00 (s, 4H, dCH), 6.61
d, 2H, J ) 15.5 Hz, CHdCH), 6.49 (d, 2H, J ) 15.5 Hz, CHdCH),
M
in methylene chloride.
1
2
2
Diethyl 5-((4,4-Di(ethoxycarbonyl)-2-(2-methylprop-1-enyl)cy-
clopent-1-enyl)methylene)-3-((1E)-2-(4,4-di(ethoxycarbonyl)-2-(2-
methylprop-1-enyl)cyclopent-1-enyl)vinyl)cyclohex-3-ene-1,1-dicar-
boxylate (12). A flask was charged with 0.113 g (77.8 µmol) of
complex 11 and 8 mL of ether. To the stirring solution was added
0.0569 g (190 µmol) of aldehyde 2a. Upon addition of the aldehyde,
an immediate color change from brown to deep red occurred. The
(
6.05 (s, 2H, CHdCMe
2
), 5.02 (m, 10H, OCHMe
), 1.88 (s, 6H, Me), 1.81 (s, 6H,
); C NMR (125 MHz, CD Cl ) δ 171.9,
71.8, 138.0, 137.8, 137.7, 137.3, 136.3, 134.2, 125.5, 123.7, 123.3,
22.0, 119.6, 69.7, 69.6, 58.3, 57.5, 57.4, 45.0, 41.9, 41.7, 40.3, 27.9,
2 2
), 3.33 (m, 8H, CH ),
3
.29 (m, 8H, CH ), 3.21 (s, 4H, CH
2
2
1
3
Me), 1.23 (m, 60H, OCHMe
1
1
2
2
2
1
6674 J. AM. CHEM. SOC. VOL. 128, NO. 51, 2006
9

Synthesis of Oligoenes with up to 15 Double Bonds
A R T I C L E S
solution was stirred for 24 h at room temperature during which time
the color lightened to yellow-brown. The solvent volume was reduced
in vacuo to ∼5 mL, and 10 mL of pentane was added. The solution
was loaded onto a short silica gel column and eluted with 2:1 hexanes/
38.5, 32.3, 30.8, 30.4, 27.8, 27.4, 20.7, 20.6, 20.5, 14.3, 14.2, 14.2,
+
14.1. HRMS (ESI, [MH] ): Calcd for C45
H
61
O12: 793.4158. Found:
2 2
793.4170. UV-vis: λmax ) 384 nm (CH Cl ).
ethyl acetate. The product fractions (R
solvent was removed in vacuo yielding 0.0500 g (80%) of a bright
f
) 0.45) were pooled, and the
Acknowledgment. R.R.S. thanks the Department of Energy
(DE-FG02-86ER13564) for research support, and Z.J.T. thanks
the National Science Foundation for a predoctoral fellowship
for 3 years. C.C. thanks the German Academic Exchange
Service (DAAD) for partial support through a postdoctoral
fellowship. R.L.C. is supported by the Petroleum Research Fund,
administered by the American Chemical Society, and also was
supported in this work while serving at the National Science
Foundation. We thank Adam Hock for help with X-ray
crystallographic studies.
yellow film. The compound exists as a 2:1 mixture of isomers as
1
determined by NMR: H NMR (500 MHz, CDCl
3
) Major isomer δ
6
1
1
3
.61 (s, 1H), 6.56 (d, 1H, J ) 16.0 Hz, CHdCH), 6.25 (d, 1H, J )
6.0 Hz, CHdCH), 6.02 (s, 1H), 5.97 (s, 1H), 5.84 (s, 1H), 4.20 (m,
2H, OCH ), 3.38 (s, 2H, CH ), 3.34 (s, 2H, CH ), 3.23 (s, 2H, CH ),
.20 (s, 2H, CH ), 2.88 (s, 2H, CH ), 2.86 (s, 2H, CH ), 1.87 (s, 3H,
2
2
2
2
2
2
2
Me), 1.82 (s, 3H, Me), 1.81 (s, 3H, Me), 1.73 (s, 3H, Me), 1.25 (m,
8H, OCH CH ); Minor isomer δ 6.51 (d, 1H, J ) 16.0 Hz, CHd
CH), 6.19 (d, 1H, J ) 16.0 Hz, CHdCH), 6.15 (s, 1H), 6.08 (s, 1H),
1
2
3
6
3
CH
3
.01 (s, 1H), 5.84 (s, 1H), 4.20 (m, 12H, OCH
.32 (s, 2H, CH ), 3.20 (s, 2H, CH ), 3.18 (s, 2H, CH
), 2.85 (s, 2H, CH ), 1.87 (s, 3H, Me), 1.83 (s, 3H, Me), 1.80 (s,
H, Me), 1.71 (s, 3H, Me), 1.25 (m, 18H, OCH
MHz, CDCl ) Both isomers δ 172.3, 172.2, 172.2, 171.2, 171.1, 138.4,
37.9, 137.6, 137.5, 137.2, 137.1, 136.4, 136.1, 136.0, 134.4, 133.8,
2
), 3.40 (s, 2H, CH
2
),
), 3.07 (s, 2H,
Supporting Information Available: Experimental details for
all organic compounds except the polyene oligomers. Fully
labeled thermal ellipsoid drawings for 7 and 17. Data for the
structures are available to the public at http://www.reciprocal-
net.org (numbers 05149 for 17 and 05196 for 7). This material
is available free of charge via the Internet at http://pubs.acs.org.
2
2
2
2
2
1
3
2 3
CH ); C NMR (125
3
1
1
1
5
33.7, 133.2, 132.8, 132.7, 132.4, 131.9, 131.4, 130.8, 126.8, 125.4,
23.3, 122.5, 121.8, 120.1, 120.0, 119.5, 61.9, 61.8, 61.8, 61.7, 59.0,
8.9, 58.0, 57.9, 54.4, 54.2, 44.7, 44.6, 43.7, 43.4, 42.7, 40.3, 40.2,
JA0656705
J. AM. CHEM. SOC.
9
VOL. 128, NO. 51, 2006 16675