Minireviews

ChemPlusChem doi.org/10.1002/cplu.202100192

Very Important Paper

Olefin Metathesis by First-Row Transition Metals
Dmitry S. Belov, Gabriela Tejeda, and Konstantin V. Bukhryakov*[a]

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Catalytic olefin metathesis based on the second- and third-row electronic structure of the base metals. In this Minireview, we
transition metals has become one of the most powerful summarize the progress of the development of alkylidenes and
transformations in modern organic chemistry. The shift to first- metallacycles of first-row transition metals from scandium to
row metals to produce fine and commodity chemicals would be nickel capable of performing cycloaddition and cycloreversion
an important achievement to complement existing methods steps, crucial reactions in olefin metathesis. In addition, we will
with inexpensive and greener alternatives. In addition, those discuss systems capable of performing olefin metathesis;
systems can offer unusual reactivity based on the unique however, the nature of active species is not yet known.

1. Introduction diversify our synthetic tools and may lead to new serendipitous
discoveries in the future.
Olefin metathesis[1] (OM) is a vital reaction both in academia This Minireview will focus on first-row metal complexes that
and industry that utilizes heterogeneous and homogeneous can promote OM. We will discuss each metal from scandium to
transition metal catalysts. Olefins Conversion Technology (OCT) nickel and provide the latest update on their chemistry relevant
is one of the most important industrial applications of OM that to OM. In general, well-defined catalysts for OM based on first-
produces over nine million tons of propylene from ethylene row metals are rare. Some of the discussed complexes do not
and 2-butenes each year by utilizing silica-supported tungsten show catalytic activity; however, they can form key intermedi-
oxide (WO3/SiO2). WO3/SiO2 has also been employed for the ates (alkylidene and metallacycle) through the cycloaddition
industrial production of 1-hexene and neohexene.[2] Another and cycloreversion steps (Scheme 1) that are relevant to OM.
important process, the Shell Higher Olefin Process (SHOP), Although first-row transition metal alkylidenes that do not
produces over a million tons of plasticizers and detergents show OM activity are interested from a fundamental standpoint
annually by utilizing MoO3/Al2O3 or Re2O7/Al2O3.[2,3] Essential and can exhibit other types of reactivity,[15] the discussion of
well-defined homogeneous catalysts for OM are based on Ru, those complexes is not the focus of this Minireview.
Mo, and W alkylidene complexes and have been applied in the In addition to isolable organometallic compounds, we will
synthesis of polymers,[4] petrochemicals,[2] agrochemicals,[5] and discuss studies where the formation of alkylidene or metalla-
conversion of low-molecular-weight alkanes to diesel fuel via cycle was supported experimentally or theoretically, but they
“alkane metathesis.”[6] In addition, some of those catalysts are have not been directly observed. In other reports, the active
applied in the eco-friendly conversion of renewable seed oil species were not elucidated, but described complexes can
feedstock into biofuel[7] and linear α-olefins,[8] that are utilized promote OM.
to produce cosmetics, soaps, detergents, polymer additives, and
coatings.[9]
Well-defined homogeneous alkylidene complexes of other 2. Scandium
second- and third-row transition metals, such as Nb,[10] Ta,[10,11]
Re,[12] and Os,[13] are also capable of performing OM. Both Re Sc-based catalytic OM is unknown. However, evidence of the
and Os are among the rarest elements in the Earth’s crust,[14] existence of Sc methylidene is reported.[16] Thermolysis of Sc-
which narrows their use in catalysis. The catalytic activity of Ta PNP complex 1 in benzene-d6 for 3 days at 100 °C resulted in γ-
and Nb toward OM is rather limited. Ta and Nb alkylidenes have activation of C H bonds, followed by [2 + 2]-cycloreversion step
been applied to the ring-opening metathesis polymerization to produce isobutylene and methylidene complex (Scheme 2).
(ROMP) of strained cyclic olefins, often under elevated The latter quickly formed dimer 4 that was observed by NMR.
temperature.[10,11] Some first-row metals are known to promote Computational and deuterium labeling studies supported this
OM, but their applications to produce commodity and fine mechanism. Generation of methylidene 3 from metallacyclobu-
chemicals are yet limited. A few challenges preclude the tane 2 through cycloreversion step is analogous to a key step in
development of reliable first-row metal-catalyzed OM, such as a the OM reaction.
relatively weak metal-carbon bond, preference for high-spin
complexes, and easily attainable variety of oxidation states.
However, first-row metals can offer advantages. The high
abundance of first-row metals provides an opportunity to
develop inexpensive catalysts, decrease the environmental
footprint, and allow for non-toxic alternatives to the currently
used catalysts. In addition, the development of catalysts based
on metals that have not yet been widely applied for OM will

[a] Dr. D. S. Belov, G. Tejeda, Dr. K. V. Bukhryakov

Chemistry and Biochemistry
Florida International University
11200 SW 8th St., Miami, FL, 33199 (USA)
E-mail: [email protected] Scheme 1. Key intermediates and steps in olefin metathesis.

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Scheme 2. Proposed formation of Sc metallacyclobutane and methylidene.

Scheme 3. The first catalytic OM catalyzed by Tebbe’s reagent 5.

3. Titanium

Ti complexes played an essential role in the discovery and

development of OM.[17] Thus, the first example of OM, ring- the active catalyst also can be prepared from Cp2TiCl2 and
opening metathesis polymerization (ROMP) of norbornene CH2(MgBr)2.[23]
(NBE), was reported seven decades ago utilizing ill-defined Ti The following reports from Grubbs and co-workers were
complexes.[18] In this study, a mixture of TiCl4 and LiAl(n-C7H15)4 focused on the isolation of Ti metallacyclobutanes from 5 and
slowly polymerized NBE to give polyNBE. Similar systems were olefins in the presence of Lewis bases to remove AlClMe2;[24] and
applied to polymerize substituted NBE[19] and cyclobutene.[20] study their stability,[25] reactivity,[26] and rearrangement
Tebbe’s reagent (5, Scheme 3, top) prepared from Cp2TiCl2 mechanism.[27] Finally, it has been shown that the reaction of 5
(Cp = cyclopentadienyl) and AlMe3 is one of the first well- with highly strained cyclic olefins leads to metallacycle 8. The
defined catalysts for OM. This complex forms metallacyclobu- following ring-opening cycloreversion step in the presence of
tane, the key intermediate in OM, in the presence of olefins.[21] phosphines releases the cyclopropane ring strain to form
Complex 5 can slowly catalyze the exchange of methylene isolable Ti alkylidenes 9 (Scheme 4).[28] Although those studies
groups between two terminal olefins, shown by Tebbe in 1979 were mainly focused on stoichiometric reactions, they were
(Scheme 3, bottom).[22] This work was the first example of crucial for understanding cycloaddition and cycloreversion
catalytic OM promoted by a well-defined complex and inspired steps and, therefore, for the development of catalytic reactions.
a number of chemists to work in the field. Important to note,

Dmitry Belov earned his M.S. degree from Konstantin Bukhryakov obtained his B.S. in
Moscow State University. He started his grad- 2006 from the Tyumen State University and
uate work in the group of Professor Alexander his Ph.D. in 2012 at Moscow State University,
Kurkin. During his Ph.D. research at MSU, Russia, where he was working on the synthesis
Dmitry studied applications of aza-Cope-Man- of enantiopure heterocycles for pharmaceut-
nich rearrangement in the synthesis of natural ical applications. Then he joined the group of
product analogs. After graduation, he worked Valentin Rodionov at King Abdullah University
on the synthesis of HIV entry inhibitors in a of Science and Technology (KAUST), Saudi
collaborative project with the New York Blood Arabia, to work on the synthesis of functional
Center under the supervision of Dr. Asim polymers and their use in catalysis. In 2015, he
Kumar Debnath. Dmitry is part of Professor joined Richard R. Schrock at MIT as a post-
Konstantin Bukhryakov’s group at FIU to make doctoral fellow to work on Mo alkylidenes. In
new catalysts for olefin metathesis. 2018, he moved to Florida International Uni-
versity as an Assistant Professor.
Gabriela Tejeda earned her B.S. in 2017 from
Florida International University (FIU). As an
undergraduate student, she worked with sin-
glet oxygen as a method of degradation of
organic pollutants from water as part of Dr.
O’Shea’s group. She then worked for a year as
a precious metal assayer at Republic Metals
Corporation. In 2018, she decided to return to
FIU to obtain her Ph.D. She is now a Ph.D.
candidate working on the synthesis of vana-
dium catalysts used for olefin metathesis
reactions under Dr. Bukhryakov’s supervision.

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cycloreversion step produces alkylidene 17 from 16, and the

following olefination leads to the cyclic enol 18 (Scheme 7), an
important precursor in the synthesis of natural product
capnellane. Noteworthy, stoichiometric amounts of 5 are
Scheme 4. Isolable Ti alkylidenes 9. required.[33]
Tandem carbonyl olefination – ring-closing metathesis
(RCM) promoted by stoichiometric amounts of Ti complexes has
been applied for the total synthesis of a large number of
The next milestone in OM was the synthesis of the first well- heterocycles and cyclic enol ethers.[34] One recent example
defined catalysts 10 and 11 for the living ROMP of NBE shown utilizing this method is the synthesis of 20 from 19 in “Takai
by Grubbs in 1986 (Scheme 5).[29] The following work explored conditions” (RCHX2-TiCl4-Zn) to generate Ti-alkylidenes in situ
substituted NBE and other cyclic olefins for ROMP to produce (Scheme 8).[35] Compound 20 is a precursor for the synthesis of
several functional polymers.[30] anti-colon cancer α-pyrone diterpenoid NF00659B1.[36] The use
Alternatively, the Ti alkylidenes 13 can be generated in situ of readily available and inexpensive reagents makes this
via α-hydrogen abstraction from dialkyl Ti complexes 12 approach an attractive method to produce cyclic compounds.
(Scheme 6). Transient 13 reacts with NBE to form metallacyclo- Due to the disadvantages of Ti-based OM mentioned above
butanes 10 and 14, active catalysts for ROMP of NBE.[31] In the and the discovery of the first well-defined Mo (1987)[37] and Ru
same study, it was shown that coordinating solvents, such as (1992)[38] alkylidenes, the interest in Ti-catalyzed OM decreased.
THF, inhibit polymerization. Although the synthesis of Ti alkylidenes attracted the scientific
It is recognized that the high stability of Ti metallacyclobu- community‘s attention, their OM catalytic activity was not
tanes results in the overall low activity of Ti catalysts and discussed.[39] It is important to note the contribution of Mind-
precludes the development of Ti-based OM. The second iola’s group on the synthesis and catalytic reactions of Ti
disadvantage of Ti complexes is the limited functional group alkylidene complexes which has made a significant impact on
tolerance. Ti is an oxophilic metal, and Ti alkylidenes readily the development of Ti catalyzed reactions, including dehydro-
react with carbonyl compounds through “Wittig type” reaction. genations, dehydrofluorinations, and C H activation.[40] A sig-
Thus, Tebbe’s reagent is used in the methylenation of carbonyl nificant milestone was reached in 2014 when the structure of
compounds.[32] However, this reactivity can be coupled with OM Tebbe’s reagent 5 was elucidated 35 years after its first
shown by Stille and Grubbs in a reaction of 15 with 5. The appearance.[41]

4. Vanadium

The first V-based OM, ROMP of substituted cyclobutenes, was

reported in 1968 utilizing ill-defined V catalysts produced in the
reaction of VCl4 and AlEt3.[42] However, the first well-defined V
alkylidene that can polymerize highly-strained cyclic olefins was
discovered 37 years later by the Nomura group in 2005.[43] Since
then, this group has been extensively explored high-oxidation-
state V alkylidene alkoxide complexes for the ROMP of various
Scheme 5. The first well-defined catalysts for ROMP of NBE.
cyclic alkenes.[44,45] Some of those complexes exhibit high
activity and selectivity toward ROMP of norbornene.[45] A
comprehensive review of the development of V alkylidene
chemistry appeared recently and covered V-based OM from
2005 to 2020.[46] Other reviews have also been published.[47]
Recently, our group has developed the synthesis of
complexes 21 a–e, a new class of compounds, and tested their
Scheme 6. Formation of Ti alkylidenes 13 through α-hydrogen abstraction.
catalytic activity (Scheme 9).[48] In our study, we selected RCM as

Scheme 8. Tandem carbonyl olefination – ring-closing metathesis in the

Scheme 7. Example of OM coupled with carbonyl olefination. synthesis of 20.

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the structure of poly(oxy-1-buten-1,4-ylene) 23-P1 (Scheme 11).

Catalyst 22 a resulted in a polymer with higher molecular
weight (~ 30 000 g/mol) than catalyst 22 b. Surprisingly, a
related complex (CO)5W=C(OCH3)Ph 22 W leads to addition
polymerization. 2,3,4,5-tetrahydrooxepin-2-yl acetate 24 was
also shown to produce a polymer. Both polymers have a fully
head-to-tail structure, an indication that only Fischer-type
alkylidenes were formed during the reaction.
A mixture of butyl vinyl ether and ethyl propenyl ether (cis-
Scheme 9. V alkylidenes for the ring-closing OM.
isomer) was treated with 22 a as a catalyst to support the OM
mechanism. Rapid formation of ethyl vinyl ether and butyl
propenyl ether (cis/trans ~ 1) was observed along with both
starting materials (propenyl ether as a mixture of cis/trans ~ 1).
a model reaction to examine catalysts’ stability toward ethylene Cis/trans isomerization was explained by dissociation of
and functional groups tolerance. Products containing a tosylate, Cr C(OR) single bond in metallacyclobutane followed by free
an ether, a tertiary amide, a tertiary amine, or an ester were rotation of σ-bond and reverse reaction to form metallacyclobu-
accessed. 21 a–e exhibited lower catalytic activity toward tane followed by retro [2 + 2] reaction leading to alkene isomer
terminal olefins (R=H) compared to internal olefins (R=CH3) due (Scheme 12).
to the catalyst‘s limited stability in the presence of ethylene. A few years later, it was discovered that a similar chromium
Therefore, reactions with terminal olefins were conducted in carbonyl complex (CO)5Cr=C(Me)OEt 25 could catalyze intra-
open vials to allow the escape of ethylene gas from the reaction molecular enyne metathesis reactions.[52] The reactions were
mixture. To our knowledge, we reported the first examples of very substrate-dependent and usually gave multiple products.
RCM catalyzed by V-based complexes. The reaction of 26 with a stoichiometric amount of 25 resulted
Changes in the imido group have a notable effect on in the mixture of products, including cyclopropane 31 and the
catalytic activity. An increase in imido group size and electron-
donating properties (21 a–21 d) leads to an improved turnover
number (TON) in most tested reactions. Phosphine size
increasing has an even more noticeable impact on the catalytic
activity, as 21 b and 21 e are the most active of the five
catalysts. Generally, catalyst 21 b displays the highest (or similar
to other complexes) activity toward tested substrates. The
possible strategies to develop reliable V-based catalysts for OM
include increasing the electrophilicity of the imido group and
the donating properties and size of the neutral ligand.
Also, ring expansion metathesis polymerization was recently
reported by the Wu group.[49] A series of different binuclear V
complexes were synthesized and determined to have high
activity in the formation of cyclic polymers.
Scheme 11. Cr-catalyzed ROMP.

5. Chromium

The first successful chromium catalyzed OM reaction dated

back to 1973 when Doyle reported chromium carbonyl
catalyzed conversion of 1-pentene to 4-octene and ethylene
(Scheme 10).[50] The conversion was low, and a co-catalyst was
required for the reaction to proceed.
Later (CO)5Cr=CRPh (22 a, R=OCH3 and 22 b, R=Ph) were
used to promote ROMP of cyclic vinyl ethers.[51] 2,3-dihydrofuran
23 was treated with Cr-complex 22 a to yield a polymer with

Scheme 10. The first Cr-catalyzed OM. Scheme 12. Proposed mechanism of isomerization in Cr-catalyzed OM.

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enyne metathesis product 30. The proposed mechanism is

shown in Scheme 13.
The catalytic process could be achieved if the substrate
contains vinyl ether to regenerate Fisher carbene. Although, in
some cases, 7 turnover numbers (TON) can be achieved
(Scheme 14), the reaction remains poorly developed.[53] Overall,
the reactivity of Cr Fischer-type alkylidenes in the metathesis of
vinyl ethers is unique and could be exploited in the develop-
ment of olefin/vinyl ethers cross-metathesis reaction method-
ology.
Remarkable progress in the synthesis of Schrock-type Cr
alkylidenes was achieved by Gibson and later by Theopold
groups. Cr(NAr)2Cl2 was alkylated with neopentylmagnesium
chloride to give compound 34 a, which upon standing in THF at
room temperature resulted in alkylidene complex 37
(Scheme 15). THF could be easily substituted with PMe3 to give
Scheme 13. Proposed mechanism of enyne metathesis promoted by 25.
39.[54] Running a similar reaction in THF in the presence of PPh3
led to the isolation of alkylidenes 36 a and 36 b.[55] The highly
reactive alkylidene 35 a reacts with C6D6 to give compound 40
in the absence of coordinating ligands. A similar process is
described for compound 34 a. Solution of 34 a in SiMe4 slowly
gave compound 34 c (3 days) and later compound 34 b (17 days
at 45 °C). Both dialkyl compounds 34 a–b do not catalyze ROM
Scheme 14. Enyne metathesis catalyzed by 25. of NBE even when heated at 60 °C. In contrast, compound 34 a,
when dissolved in cyclopentene, slowly produces alkylidene 35,
which undergoes cycloaddition to produce Cr metallacyclobu-
tane 38. Compound 38 was found to be surprisingly stable, and
the cycloreversion step was not observed.
ArCr(CO)3 was reported to catalyze the polymerization of
alkynes.[56] Initially, metallacyclobutene was suggested as a
possible intermediate, but later an alternative explanation was
suggested based on the insertion mechanism.[57]
There has been much debate around the mechanism of
ethylene polymerization on a Phillips catalyst.[58] The Green-
Rooney mechanistic proposal involved the formation of Cr
alkylidenes and [2 + 2] reaction with ethylene.[59] However, later
computational results suggested that this mechanism should
have very high activation energies and is thus unlikely.[60]

6. Manganese

Several Mn Fischer and Schrock type alkylidenes, alkylidynes,

and vinylidene complexes have been prepared and character-
ized. But to the best of our knowledge, Mn-catalyzed OM has
not been reported. However, it has been shown by ion
cyclotron resonance (ICR) spectroscopy that MnCH2 + can react
with ethylene in the gas phase through OM.[61]
In contrast to the Cr-catalyzed process (Schemes 13 and 14),
the reaction of Fischer-type Mn alkylidene 41 with 42 resulted
in the exclusive formation of cyclopropane 43 (Scheme 16).[62]
There was no evidence for metathesis products. However, the
formation of cyclopropane might implicate Mn cyclobutene
intermediate.
The only process that resembles OM mechanism was
reported in 2013.[63] Treatment of Mn borylene complex 44 with
Scheme 15. Synthesis and reactivity of Cr-alkylidenes. benzophenone led to cyclic product 45, which can be isolated

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Cl2Ru=CH2 and concluded that Fe-based catalysts would not

perform well.[69] Furthermore, other calculations indicated that
complexes LCl2Fe=CRR’ should mainly favor alkene cyclopropa-
nation over OM both thermodynamically and kinetically.[70]
Finally, it was shown theoretically for the direct analog of
Grubbs second-generation catalyst (NHC)Cl2Fe=CHPh that this
Scheme 16. Reactivity of Mn alkylidene 41. complex has an open-shell triplet ground state at the metal
center and could be prone to radical chemistry rather than to
OM.[15b]
Generally, Fe complexes possess several spin states similar
in energy, including high-spin and open-shell complexes, which
tend to favor free radical reactions such as cyclopropanation,
hydrogen-atom transfer, radical C C coupling, and
cyclopropanation.[70] Coordination of an olefin, the essential
step of OM, is achieved by overlapping a doubly occupied π-
Scheme 17. Reactivity of Mn borylene 44.
bond orbital of the olefin with the metal‘s empty d-orbitals.
Unpaired electrons partially occupy these orbitals in high-spin
systems, which is weakening the stabilization.[71] It is noteworthy
and characterized. 45 undergoes cycloreversion to yield that alkene cyclopropanation reactions are most common for
carbene complex 46 in solution (Scheme 17). Fe alkylidenes[72] and can proceed through a few pathways. The
first one is the direct carbene transfer to an alkene. The second
is the reductive elimination of cyclopropane from metallacycle.
7. Iron The third is the step-wise mechanism, where the olefin‘s attack
on the alkylidene implies the formation of biradical or
Fe is the most abundant transition metal in Earth’s crust, and, zwitterion intermediate.[15b]
therefore, the use of Fe for OM is highly desirable. Despite Complications and side reactions mentioned above arise
extensive theoretical and experimental work, well-defined Fe- because Fe is a first-row metal and commonly possesses a high-
based catalysts for OM are not known to the best of our spin ground state, which favors radical reactions. The high-spin
knowledge. ground state also explains low BDEs for some Fe alkylidenes,[73]
Theoretical study of the formation of Fe metallacyclobutene since the bond distance Fe=C in the triplet state is much longer
published by Roald Hoffman in 1981 is one of the early works than in the singlet state (1.749–1.792 Å vs. 1.708–1.726 Å), and
relevant to Fe-based OM.[64] In 1985, Freiser showed by ICR the carbene substituents are not perpendicular to the plane in
spectroscopy that FeCD2 + reacts with ethylene (CH2 = CH2) in which the π-bond is formed. This geometry reveals the differ-
the gas phase to produce FeCH2 + and CD2 = CH2.[65] Later, ence between Fe=CRR’ double bond with two unpaired
another theoretical work showed the possibility of cyclo- electrons on the metal center and a structure in which the π-
addition/cycloreversion steps for cationic Fe alkylidene bond of Fe=CRR’ is not formed and three unpaired electrons
complexes.[66] localized on the metal center and one (with an opposite spin)
on the carbene carbon.[73] This configuration is described for the
complex synthesized previously.[74]
7.1. Theoretical studies and challenges of Fe-catalyzed OM Theoretical calculations propose a few strategies to over-
come the challenges mentioned above. First, increase the BDE
After the development of well-defined Ru metathesis catalysts, of the Fe-carbene bond by introducing neutral σ-donating
the syntheses of analogous Fe-alkylidenes, L2Cl2Fe=CR2, were ligands.[70,73] Second, stabilize the singlet-state of both alkyli-
attempted by Grubbs in 2001 using diazo compounds. How- dene and metallacycle using strong field anionic ligands.[70]
ever, only unexpected phosphazine complexes were formed.[67] However, the use of very strong field ligands, e. g., alkyl and
Despite the experimental inaccessibility of L2Cl2Fe=CR2, some cyano groups, stabilizes the singlet state for alkylidene but
earlier calculations showed that those complexes could pro- destabilizes the singlet state for metallacycle.[70,73] Third, use
mote OM.[68] However, the following theoretical studies revealed Fe(IV) complexes because, according to Hückel calculations,
a few challenges that should be taken into account considering cyclopropanation is forbidden for d4 metal centers.[64] However,
the direct Fe analog of Grubbs catalysts. One of the challenges some theoretical studies showed the possibility of low valent
is the strength of the bond between Fe and carbon. A Fe-catalyzed OM.[73,75] Finally, apply rigid chelating ligands to
calculation indicates that the bond dissociation energy (BDE) of control the geometry of the alkylidene and metallacycle to
Fe=CH2 in (H2Im)(PH3)Cl2Fe=CH2 (H2Im is imidazolinium carbene) favor singlet states for both.[70,73,76]
is approximately one-half of BDE of Ru=CH2 in (H2Im)(PH3)
Cl2Ru=CH2 (44.5 vs. 87.7 kcal/mol).[69] In addition, Dixon has
shown that the cycloaddition step in the case of (H2Im)(PH3)
Cl2Fe=CH2 is an endothermic process unlike for (H2Im)(PH3)

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7.2. Experimental evidence of Fe-catalyzed OM of odd-number olefins was observed along with expected even-
numbers olefins.[83] The overall percentage of odd-numbered
Although isolable Fe-alkylidenes capable of performing OM are olefins was 29 % and 19 % for catalysts 47 b and 47 c,
unknown, a few ill-defined Fe-based systems that exhibit OM respectively. Three hypotheses were suggested to explain the
activity have been reported. formation of odd-number olefins. The first is transfer of methyl
Historically ROMP of NBE is widely used to test the ability of group from MAO to the growing chain. The second possibility is
a transition-metal complex to catalyze OM.[18] For example, β-alkyl group elimination.[84] The third possibility is the OM
RuCl3-catalyzed ROMP of NBE was reported in 1965.[77] Note- reaction between ethylene and internal olefins. However, the
worthy, the first well-defined Ru-based catalyst for OM was authors did not suggest any mechanism explaining the
reported only in 1992, 27 years later.[38] The high ring strain of formation of iron alkylidenes.
NBE (27.2 kcal/mol) is responsible for its high reactivity.[78] Recently, we reported an Fe-based system capable of
Notably, the formation of very reactive (and hence prone to performing ROMP of NBE. In our study, low-coordinate homo-
decomposition) metal methylidene intermediates is avoided leptic complex 48 was tested in the presence of nine carbene
during polymerization.[79] Moreover, NBE itself can be respon- precursors in reaction with NBE.[85] The formation of catalytically
sible for the formation of metal alkylidene species.[80] The last active Fe alkylidene in situ would result in the formation of
factor is significant because, in the early stages of research, polyNBE. Surprisingly, 48 can slowly produce polyNBE in the
synthesis and isolation of metal alkylidene are not always absence of carbene precursors. In addition, the resulting
possible. 1H NMR easily distinguishes signals of olefin protons of polymer is 99 % cis, syndiotactic (Scheme 19). The content of Ru,
the ROMP polymer from other possible polymers that can form Mo, W, and V in 48 by ICP is negligible and cannot be
from NBE (Scheme 18). The tacticity of the resulted polymer responsible for catalytic activity. The addition of perfluoroalco-
may indicate the nature of the active species.[81] The polymer‘s hols increases the activity with retained selectivity.
molecular weight may indicate what fraction of a transition- We discussed three possible ROMP mechanisms, including
metal complex forms active species. Fe alkylidene formation, redox-initiated ROMP, and carbonyl-
2,6-bis(arylimino)pyridine Fe complexes 47 a–c (Figure 1) are olefin metathesis. However, we have not confirmed any of the
known to promote ethylene‘s oligomerization and polymer- considered mechanisms and the nature of the active species,
ization. Complex 47 a was employed for polymerization of NBE along with the origin of stereoselectivity, remains unclear.
to produce polymer through addition (vinylic) polymerization. Iluc achieved an important milestone in the development of
However, it was noticed that the final polymer contains a small Fe-based enyne metathesis in 2021. Thus, it has been shown
fraction of double bonds (122 units per 10,000 insertions, E/Z that the low-spin diamagnetic Fe alkylidene 49 is capable of
76 : 24), which was attributed to the ROMP product.[82] performing cycloaddition reaction with diphenylacetylene to
Noteworthy, when complexes 47 b–c were employed for form diamagnetic vinyl carbene 51, presumably through the
the oligomerization of ethylene in the presence of meth- formation of metallacyclobutene 50 (Scheme 20).[86] Further-
ylaluminoxane (MAO), unexpected formation of a small amount more, 51 can react with alkynes to produce the second
insertion product 52. Although the reaction requires elevated
temperature and extended time, this is the first example of a
well-defined Fe alkylidene capable of performing cycloaddition/
cycloreversion transformations.

8. Cobalt

Along with cationic Fe alkylidenes, Freiser studied cycloaddi-

tion/cycloreversion transformations of CoCD2 + by ICR spectro-
scopy in 1985.[65] A few examples of ROMP of NBE catalyzed by

Scheme 18. Types of polymerizations of NBE.

Figure 1. Fe-complexes for ethylene oligomerization and polymerization. Scheme 19. Fe-catalyzed ROMP of NBE.

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thought to be Cu-catalyzed.[89] Ppm levels of Cu were able to

catalyze C N coupling, which initially was thought to be Fe-
catalyzed.[90] Careful control experiments are necessary to claim
a new reactivity. It is possible that after careful reexamination,
some of the reported discoveries will find a more straightfor-
ward explanation.
In 2013 Baker reported the preparation of the formally d8
Co(I) difluoro and fluoro(perfluoroalkyl)carbenes 58 a–b (car-
bene is a neutral ligand).[91] The carbene complex was prepared
by oxidative addition followed by a two-electron reduction
process starting from commercially available CpCo(CO)2
(Scheme 21). Later it was discovered that cobalt fluorocarbenes
58 a–b react with tetrafluoroethylene (TFE) to give the perfluor-
ometallacyclobutanes 59 a–b via formal [2 + 2] cycloaddition
(Scheme 21).[92] Computational studies suggested that the
Scheme 20. Enyne metathesis by Fe alkylidene 49. concerted [2 + 2] pathway is energetically unfavorable, and the
reaction proceeds through the formation of 1,4-singlet diradical
intermediate.[93] For the reported system, perfluorometallacyclo-
Co complexes are known. Thus, in 1995, it was reported that butanes were very stable, and cycloreversion was not observed.
0.1 % of Co neodecanoate and Co acetylacetonate combined In addition to the reaction with TFE, a formation of
with Et3Al or i-Bu3Al could catalyze ROMP of NBE.[87] The metallacyclobutene 60 took place when complex 58 b reacts
polymer was all-cis polyNBE with high molecular weight (Mw = with terminal acetylenes (Scheme 22). The 1,4-diradical mecha-
720000). The reaction rate is slow (80 % conversion in 3 days), nism was suggested, and the complex was stable at room
but it can be increased by adding hexachloroacetone. Later it temperature.[94]
was shown that complexes 53–56 (Figure 2) could catalyze the Similarly, metallacyclobutane complex 62 was found to be
polymerization of NBE in the presence of MAO.[82,88] The primary in equilibria with vinyl carbene 63 (Scheme 23). The latter was
product was vinyl type-polymer, but a small percentage of not stable enough for isolation but was characterized in
ROMP polymer was present in all cases. Interestingly, the solution.[95] These findings could be the first step to a
percentage of ROMP product was higher when polymer yield productive Co-catalyzed enyne metathesis reaction.
was lower. No attempts to optimize the catalyst structure were Computational results suggest that an energy minimum
made. In addition, the authors did not discuss the possibility of cannot be located for Co metallacyclobutane, and correspond-
ROMP catalyzed by trace metals, such as Ru, Mo, or W (as well ing alkylidenes should be highly reactive.[68c] Although several
as other metals known to be active in OM) that can be present
in the reaction mixture. Such precedents are well-documented
for cross-coupling chemistry. For example, it is known that ppb
levels of Pd can catalyze the Sonogashira reaction, which was

Scheme 21. The reaction of Co alkylidenes with tetrafluoroethylene.

Figure 2. Co-complexes tested for polymerization of NBE. Scheme 22. The reaction of Co alkylidene 58 b with phenylacetylene.

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produced characteristic products of OM: 2-butene, ethylene,

and propylene-1,1-d2 (TON ~ 2, Scheme 25).
Later in 1980, Miyashita reported the preparation of Ni
metallacyclobutanes 67 a–b by γ-H abstraction reaction of Ni
bis dineopentylnickel complexes 66 a–b (Scheme 26).[99] Thermal
decomposition of 67 a produced Ni methylidene intermediate,
which was confirmed by several experiments.[100] The complex
67 a is capable of RCM of 1,7-octadiene, but activity was low. In
addition to metathesis activity, complex 67 a can perform a
cyclopropanation reaction. Thus, thermal decomposition of 67 a
in neat cyclohexene gave norcarane (8–10 % per Ni).
The study of cationic NiCH2 + in the gas-phase showed that
it reacts with tetrafluoroethylene (CF2 = CF2) to produce NiCF2 +
and CF2 = CH2.[101]
Scheme 23. Cycloreversion of 61.
Formation of macrocyclic Ni complex 69 was observed
during metal-vapor synthesis (MVS) experiment with 68
(Scheme 27). However, ethylene formation was not observed,
Co alkylidene complexes have been isolated and and, therefore, it is unclear how compound 69 was formed.[102]
characterized,[96] their reactions with alkenes mainly lead to The Ni-catalyzed reaction of [1.1.1]propellane 70 as a
cyclopropanation.[97] carbene precursor with 4-ethynylbiphenyl 71 produced 72,
presumably through enyne metathesis (Scheme 28).[103] Analo-
gous reaction with alkenes led to cyclopropanation.
9. Nickel In 2015 Baker reported the synthesis of Ni difluorocarbene
complex 73, which can react with TFE to produce Ni metal-
To the best of our knowledge, no well-defined Ni alkylidene lacyclobutane 74 (Scheme 29).[104] Later, it was shown that
complexes active in OM reaction have been reported. However, fluorinated Ni alkylidene 75 reacts with TFE and 1,1-difluoro-
significant progress was made in this direction.
Grubbs reported the first evidence of Ni-based OM in 1978.
Ni metallacyclohexane 64 was prepared by alkylation of Ni-
(PPh3)2Cl2 with 1,5-dilithiopentane (Scheme 24).[98] Thermal
decomposition of 64 through α- and β- alkyl elimination
reactions led to catalytically active species. Catalytic RCM
reaction of 1,7-octadiene and 64 produced cyclohexene and
ethylene.
Further evidence for Ni methylidene 65 intermediate was
observed when 64 b was treated with propylene. The reaction

Scheme 25. Evidence of formation of catalytically active Ni methylidene 65.

Scheme 24. Proposed formation of catalytically active Ni alkylidene. Scheme 26. Catalytically active Ni metallacyclobutane 67 a.

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Scheme 27. Formation of complex 69.

Scheme 28. Enyne metathesis catalyzed by Ni complex.

Scheme 30. Proposed mechanism of Ni-promoted OM.

a mixture of cis- and trans-2-butenes, and subsequent OM of 2-

butenes with an excess of ethylene. The hypothesis was further
confirmed by the fact that the same catalyst can catalyze the
formation of propene from butenes and ethylene and the
reverse reaction. This reactivity was unique for Ni and other
tested metals, such as Al, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Zr, Mo, W,
showed no or little conversion. However, due to ill-defined
active sites, no conclusive evidence about the mechanism of
ethylene to propylene transformation was reported.[108] Note-
worthy, an alternative mechanism that does not include OM
has been suggested.[109]
The formation of a small amount of odd-number olefins was
observed during Ni catalyzed ethylene polymerization when
Et2AlCl was used instead of MAO for catalyst activation.[110]
Scheme 29. OM of fluorinated alkenes by fluorinated Ni alkylidenes. However, the mechanism for the formation of Ni alkylidene was
not suggested. 2,6-bis(arylimino)pyridine Ni complexes similar
to 47 a–c (Figure 1) were tested for polymerization of NBE to
produce polymer through addition (vinylic) polymerization. It
ethylene to produce Ni metallacyclobutane 76 and alkylidene was observed that a small fraction of double bonds formed (up
77 along with OM products.[105] to 244 units per 10,000 insertions, E/Z 67 : 33), which was
Computational studies suggested two parallel mechanisms attributed to ROMP product.[82]
(Scheme 30). The first pathway includes the formation of
unproductive square planar metallocycle 76 through diradical
intermediate 80. The metathesis pathway involves the forma- 10. Conclusions and Outlook
tion of unusual strained bicyclic tetrahedral intermediate 78.
The interconversion between 76 and 77 was not observed In this Minireview, the progress of first-row transition metal
because both metallacycle 76 and alkylidene 77 exhibit low promoted OM was summarized starting from the discovery of
energies relative to the starting materials. The reaction offers ROMP seven decades ago. Although most currently applied
unique reactivity and suggests a novel variant of the Chauvin catalysts are primarily based on second- and third-row metals,
mechanism. However, further development is required to make the crucial steps of OM: [2 + 2] cycloaddition reaction between
the reaction synthetically useful. metal carbene and alkene or alkyne, and the cycloreversion of
In 2007 Iwamoto reported that Ni-loaded mesoporous silica metallacycle are general reactions that are also attributed to
catalysts could catalyze the transformation of ethylene to the first-row metals. Conceptually, OM catalyst development for
propylene with 68 % conversion.[106] It was suggested that the synthesis of commodity and fine olefins based on first-row
ethylene dimerizes to 1-butene,[107] followed by isomerization to metals is possible. It is important to note that the driving force

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ChemPlusChem doi.org/10.1002/cplu.202100192

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