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Structural Elucidation of the Illustrious Tebbe Reagent

Rick Thompson,†,§ Eiko Nakamaru-Ogiso,‡ Chun-Hsing Chen,*,† Maren Pink,*,†
and Daniel J. Mindiola*,†,§
†
Department of Chemistry and the Molecular Structure Center, Indiana University, Bloomington, Indiana 47405, United States
‡
Department of Biochemistry and Biophysics, University of Pennsylvania Perelman School of Medicine, 295 John Morgan Building,
3620 Hamilton Walk, Philadelphia, Pennsylvania 19104, United States
*
S Supporting Information

ABSTRACT: The Tebbe reagent, [Cp2Ti(μ2-Cl)(μ2-CH2)AlMe2] (1), has finally been structurally
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characterized due to the fortuitous formation of cocrystals of 1 and [Cp2Ti(μ2-Cl)2AlMe2] (2). Single
crystals of 1 and 2, despite being extremely reactive and forming an amorphous white coat, can be
mounted and data collected to high resolution, thereby providing for the first time a solid-state
representation of a titanium methylidene adduct with diphilic AlClMe2.

T he Tebbe reagent,1 [Cp2Ti(μ2-Cl)(μ2-CH2)AlMe2] (1),

stands as a historic milestone in the field of organometallic
chemistry. Its ability to transfer a methylene group to organic
with producing single crystals. In this note, we report high-
quality X-ray data of 1 (grown as a cocrystal with an impurity)
and discuss a high-resolution solid-state structure confirming
species via metallo-Wittig chemistry was later extended to other the original geometry proposed by Tebbe.9 For the first time,
methylidene transfer reactions2−5 which proceed through a and nearly 40 years after Tebbe’s ground-breaking experiment,
similar metathesis. This well-known process ultimately we provide here precise geometrical parameters for the
culminated in the 2005 Nobel Prize being awarded to Chauvin, structure of Tebbe’s reagent. Additionally, structural and
Grubbs, and Schrock.6−8 Although reagent 1 was first reported spectroscopic data for a side product in the synthesis is
by Tebbe and co-workers in 1978,9 the original experiments reported.
were performed much earlier in the summer of 1974 at the In 1980, Tebbe and co-workers reported the molecular
DuPont Central Research Division.10 Compound 1 is prepared structure of a close analogue, [Cp2Ti(μ2-Cl)(μ2-CH2)Al-
readily, under an inert atmosphere, by addition of a slight (CH2tBu)2], obtained via alkyl exchange of 1 with [Al-
excess of AlMe3 to Cp2TiCl2 in toluene in yields ranging from (CH2tBu)3].12 Unfortunately, the solid state structure of the
80 to 90% (eq 1).9 In the presence of a suitable Lewis base, 1 neopentyl analogue suffers from occupancy disorder confined
between the bridging chloride and methylidene group.
Consequently, positions were refined for chloride and
methylene, resulting in average distances of 2.494(1) and
2.380(2) Å to the titanium, respectively. The corresponding
distances to the aluminum are reported as 2.258(2) and
2.213(2) Å, although it is possible that the average bridging
can be a source of the transient methylidene [Cp2TiCH2],11 atom positions of a cocrystal could also be refined. Thus, the X-
the species responsible for metallo-ylide group transfer. As ray structure and the NMR results only verify the overall gross
originally noted by Tebbe, compound 1 can be readily isolated geometry, showing the formation of a methylidene species
in pure form by crystallization of the mixture from a toluene/ whereby the CH2 and/or Cl bridge the Cp2Ti and R2Al
pentane solution (the temperature was not specified in the fragments.12 Structural confirmation of 1 has not been
original work).9 Compound 1 slowly degrades in the solid-state documented,10 despite it being the first group 4 alkylidene,
at room temperature, while solids or solutions both rapidly the first alkyl complex with both a transition metal and Al, and
produce methane in the presence of air. Species 1 is well- most notably, one of the first systems to engage in metathesis
known in the context of organic and inorganic chemistry;
however, structural characterization has remained elusive, Received: November 13, 2013
presumably due to its reactive nature or difficulties associated Published: December 27, 2013

© 2013 American Chemical Society 429 dx.doi.org/10.1021/om401108b | Organometallics 2014, 33, 429−432
Organometallics Note

reactions resulting in the formation of many organic molecules,

including natural products.5 Therefore, we tenaciously ex-
plored, under various conditions, structural studies of single
crystals of 1. In this report we discovered that the presence of a
cocrystal allows for reliable diffraction data on a single crystal
and show that an impurity accompanies this reagent.
Following Tebbe’s original protocol,9 complex 1 was
prepared on a smaller scale in toluene using 2.0 g of the
precursor Cp2TiCl2 and a 2 M hexanes solution of AlMe3.
Evaporation of the solvent, extraction of the oily red residue in
neat pentane (as opposed to a toluene/pentane solution), and
cooling of the solution to −25 °C over 19 days resulted in the
formation of large, blood red blocks of what appeared to be
pure 1. The 1H and 13C NMR spectra of a batch of crystals Figure 2. Cocrystallization of complexes 1 and 2 showing the
appear to be consistent with pure 1.9 Because of the highly positions of the modeled methylidene in 1 and chloride in 2.
reactive nature of the crystals, numerous attempts to mount
them on the goniometer resulted in rapid decay of the sample dinuclear species [Cp2Ti(μ2-CH2)(μ2-Cl)TiCp2] (Scheme 1).
and loss of diffraction quality.13 To impede decomposition of Repeating the conditions originally reported,15 a room-
the sample, a slide containing 1 was prepared in a glovebox with
perfluorinated oil and placed in a Teflon-cap-sealed vessel. Scheme 1. Proposed Decomposition Pathway of the Tebbe
During transport and handling, great care was taken to keep the Reagent
sample cold using a secondary container of dry ice. Crystals
were selected from the open slide placed on dry ice. Upon
removal from the original container, the surface of the dark red
crystals began to bubble violently, causing the majority of them
to decompose to a colorless, amorphous solid. A particularly
large crystal was chosen, part of the decomposition product was
quickly removed, and the specimen was capped with a
precooled cryovial and transported to the goniometer and
mounted under a nitrogen cold stream (150 K). In spite of
considerable decomposition on the surface of the crystal
(Figure 1, left) very strong single diffractions were observed
well beyond 60° in 2θ (Figure 1, right).

temperature X-band EPR spectrum of single crystals further

confirmed the presence of 2.16 A 1H NMR spectrum of single
crystals of 1 and 2 reveals approximately 58% of the former
when using a known amount of an internal standard, therefore
suggesting that 2 must be present in significant quantities.
Notably, some of the side product 2 can be separated by careful
fractional crystallization from toluene at −27 °C.13 Therefore,
formation of 2 most likely involves trapping of [Cp2TiCl] by
AlClMe2, and such a process might be catalyzed by a trace
Figure 1. (left) Single crystal of 1 coated with decomposition material. amount of Lewis base. The origin of [Cp2TiCl] is unknown,
(right) Example frame showing excellent diffraction. and such a species could form from 1 or by reduction of the
precursor Cp2TiCl2 (Scheme 1).17
The solid-state structure of 1 (with compound 2 omitted for
For the particular specimen chosen, a standard structure clarity), shown in views from the front and the top (Figure 3),
solution revealed a cocrystal of [Cp2Ti(μ2-Cl)(μ2-CH2)AlMe2] depicts a titanocene motif possessing bridging chloride and
(1) and [Cp2Ti(μ2-Cl)2AlMe2] (2). This cocrystallization methylidene to an AlMe2 fragment. The Cpcent−Ti−Cpcent
manifests itself in a disorder of one of the bridging positions angle (134.0°) is comparable to those in [Cp2Ti(μ2-Cl)(μ2-
with a site occupancy of the major component 1 of 0.62 (Figure CH2)Al(CH2tBu)2] (132.31°)12 and Cp2TiMe2 (134.54°)12
2).14 A single constraint for equal anisotropic displacement However, the most notable feature is the methylidene−Ti
parameters was used for C13 and Cl2. The hydrogen atoms of distance (2.095(5) Å), which is significantly shorter than the
C13 could be located in the Fourier difference map; however, disordered methylidene distance reported for [Cp2Ti(μ2-
they were ultimately refined as “riding atoms” in calculated Cl)(μ2-CH2)Al(CH2tBu)2] (2.3805(5) Å).12 This distance is
positions. slightly longer than that observed for both bridging ethylidene
The formation of 2 is consistent, in part, with the original (1.933(6) Å)18 and terminal alkylidene complexes of titanium
report by Krusic and Tebbe,15 which invoked the transient (1.884(4) Å)19 but akin to that of bridging vinylidene
[Cp2TiCl] being produced en route to the mixed-valent complexes (2.023(5) Å).20
430 dx.doi.org/10.1021/om401108b | Organometallics 2014, 33, 429−432
Organometallics

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Note

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slight modification of Tebbe’s original protocolcrystallizing
(13) See the Supporting Information.
compound 1 directly from pentane instead of tolueneresults (14) Crystallographic details for 1 and 2: a dark red crystal of
in the fortuitous formation of high-quality single cocrystals of 1 approximate dimensions 0.30 × 0.29 × 0.24 mm3 was placed onto the
and 2, therefore allowing us to obtain for the first time a reliable tip of a 0.10 mm diameter MiTeGen pin and mounted on a Bruker
snapshot of the molecular structure of the Tebbe reagent along APEX II Kappa Duo diffractometer equipped with an APEX II
with a side product. The latter is apparently innocuous to the detector at 150(2) K. A total of 33941 reflections (−29 ≤ h ≤ 31, −16
reactivity of the transient methylidene, since it is likely present ≤ k ≤ 16, −21 ≤ l ≤ 21) were collected in the range 2.04−30.05°,
in small amounts when solutions of 1 are prepared in situ.21 4887 of which were unique (Rint = 0.0422); Mo Kα radiation was used
However, the single crystals obtained from our synthesis reveal (λ = 0.71073 Å). A direct-methods solution was calculated, which
species 1 to be present in 58% yield based on mass, therefore provided most non-hydrogen atoms from the E map. Full-matrix least-
squares/difference Fourier cycles were performed to locate the
implying that 2 must be present in the crystals in significant
remaining non-hydrogen atoms. All non-hydrogen atoms were refined
quantities. We have shown that a combination of NMR and with aniosotropic displacement parameters. All hydrogen atoms were
EPR spectroscopic data confirm the formation of 1 (major) and placed in ideal positions and refined as riding atoms with relative
2 (minor) as products composing the crystalline material, isotropic displacement parameters. The residual peak and hole
almost in similar ratios. electron densities were 0.369 and −0.658 e Å−3. The absorption

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*
ASSOCIATED CONTENT
S Supporting Information
coeffiecient was 0.773 mm−1. The least-squares refinement converged
normally with residuals of R1 = 0.0435, wR2 = 0.0965 and GOF =
1.209. Crystal data: C16.12H21.23AlCl1.38Ti, C2/c, a = 22.4504(8) Å, b =
Text, figures, tables, and a CIF file giving detailed experimental 11.9176(4) Å, c = 15.2004(10) Å, α = 90.00°, β = 124.8580(10)°, γ =
procedures, crystallographic data,22 mounting of single crystals 90.00°, V = 3337.2(3) Å3, Z = 8, ρcalcd = 1.349, F(000) = 1411.
(15) Krusic, P. J.; Tebbe, F. N. Inorg. Chem. 1982, 21, 2900.
of cocrystals of 1/2, crystal structure collection, structure (16) Isotropic X-band EPR acquisition parameters: 0.002 M toluene
solution, and refinement data for complex 1, crystallographic solution at −50 °C, g = 1.977, W = 9 G, a(Ti) = 11.7 G, T = 50 °C.
parameters, and an EPR spectrum of complex 2. This material The originally reported Al hyperfine was not resolved.
is available free of charge via the Internet at http://pubs.acs.org.

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(17) Reduction of titanium(IV) with AlMe3 has been reported:
Juppo, M.; Petra Aløn, P.; Ritala, M.; Leskelä, M. Chem. Vap.
AUTHOR INFORMATION Deposition 2001, 7, 211.
Corresponding Author (18) Krueger, C.; Mynott, R.; Siedenbiedel, R.; Stehling, L.; Wilke, G.
*E-mail: [email protected] (D.J.M.); mpink@indiana. Angew. Chem., Int. Ed. Engl. 1991, 30, 1668; Angew. Chem. 1991, 103,
edu (M.P.); [email protected] (C.-H.C.). 1714.
(19) (a) Schrock, R. R. Chem. Rev. 2002, 102, 145. (b) Mindiola, D.
Present Address J.; Bailey, B. C.; Basuli, F. Eur. J. Inorg. Chem. 2006, 3135.
§
Department of Chemistry, University of Pennsylvania, 231 (20) For some examples of Ti−CH2-based derivatives. (a) Beckhaus,
South 34th Street, Philadelphia, PA 19104, United States. R.; Oster, J.; Wang, R.; Böhme, U. Organometallics 1998, 17, 2215.
Notes (b) Bergman, R. G.; et al. J. Am. Chem. Soc. 1998, 120, 6316;(c) J. Am.
The authors declare no competing financial interest. Chem. Soc. 1996, 118, 8737−8738. (d) Park, J. W.; Mackenzie, P. B.;

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Schaefer, W. P.; Grubbs, R. H. J. Am. Chem. Soc. 1986, 108, 6402.
ACKNOWLEDGMENTS (e) Ozawa, F.; Park, J. W.; Mackenzie, P. B.; Schaefer, W. P.; Henling,
L. M.; Grubbs, R. H. J. Am. Chem. Soc. 1989, 111, 1319.
We thank the U.S. National Science Foundation (CHE- (21) Cannizzo, L. F.; Grubbs, R. H. J. Org. Chem. 1985, 50, 2386.
0848248 and CHE-1152123) and the University of Pennsylva- (22) CCDC-955969 contains supplementary crystallographic data for
nia for financial support of this research. this paper. These data can be obtained free of charge via www.ccdc.

431 dx.doi.org/10.1021/om401108b | Organometallics 2014, 33, 429−432

Organometallics Note

cam.ac.uk/conts/retrie-ving.html (or from the Cambridge Crystallo-

graphic Data Centre, 12 Union Road, Cambridge CB21EZ, U.K.; fax,
(+44)1223-336-033; e-mail, [email protected]).

432 dx.doi.org/10.1021/om401108b | Organometallics 2014, 33, 429−432