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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ChemPlusChem doi.org/10.1002/cplu.202100192
Catalytic olefin metathesis based on the second- and third-row
transition metals has become one of the most powerful
transformations in modern organic chemistry. The shift to first-
row metals to produce fine and commodity chemicals would be
an important achievement to complement existing methods
with inexpensive and greener alternatives. In addition, those
systems can offer unusual reactivity based on the unique
1. Introduction
Olefin metathesis[1] (OM) is a vital reaction both in academia
and industry that utilizes heterogeneous and homogeneous
transition metal catalysts. Olefins Conversion Technology (OCT)
is one of the most important industrial applications of OM that
produces over nine million tons of propylene from ethylene
and 2-butenes each year by utilizing silica-supported tungsten
oxide (WO3/SiO2). WO3/SiO2 has also been employed for the
industrial production of 1-hexene and neohexene.[2] Another
important process, the Shell Higher Olefin Process (SHOP),
produces over a million tons of plasticizers and detergents
annually by utilizing MoO3/Al2O3 or Re2O7/Al2O3.[2,3] Essential
well-defined homogeneous catalysts for OM are based on Ru,
Mo, and W alkylidene complexes and have been applied in the
synthesis of polymers,[4] petrochemicals,[2] agrochemicals,[5] and
conversion of low-molecular-weight alkanes to diesel fuel via
“alkane metathesis.”[6] In addition, some of those catalysts are
applied in the eco-friendly conversion of renewable seed oil
feedstock into biofuel[7] and linear α-olefins,[8] that are utilized
to produce cosmetics, soaps, detergents, polymer additives, and
coatings.[9]
Well-defined homogeneous alkylidene complexes of other
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
and Os are among the rarest elements in the Earth’s crust,[14]
which narrows their use in catalysis. The catalytic activity of Ta
and Nb toward OM is rather limited. Ta and Nb alkylidenes have
been applied to the ring-opening metathesis polymerization
(ROMP) of strained cyclic olefins, often under elevated
temperature.[10,11] Some first-row metals are known to promote
OM, but their applications to produce commodity and fine
chemicals are yet limited. A few challenges preclude the
development of reliable first-row metal-catalyzed OM, such as a
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: kbukhrya@fiu.edu
ChemPlusChem 2021, 86, 924 – 937 www.chempluschem.org
electronic structure of the base metals. In this Minireview, we
summarize the progress of the development of alkylidenes and
metallacycles of first-row transition metals from scandium to
nickel capable of performing cycloaddition and cycloreversion
steps, crucial reactions in olefin metathesis. In addition, we will
discuss systems capable of performing olefin metathesis;
however, the nature of active species is not yet known.
diversify our synthetic tools and may lead to new serendipitous
discoveries in the future.
This Minireview will focus on first-row metal complexes that
can promote OM. We will discuss each metal from scandium to
nickel and provide the latest update on their chemistry relevant
to OM. In general, well-defined catalysts for OM based on first-
row metals are rare. Some of the discussed complexes do not
show catalytic activity; however, they can form key intermedi-
ates (alkylidene and metallacycle) through the cycloaddition
and cycloreversion steps (Scheme 1) that are relevant to OM.
Although first-row transition metal alkylidenes that do not
show OM activity are interested from a fundamental standpoint
and can exhibit other types of reactivity,[15] the discussion of
those complexes is not the focus of this Minireview.
In addition to isolable organometallic compounds, we will
discuss studies where the formation of alkylidene or metalla-
cycle was supported experimentally or theoretically, but they
have not been directly observed. In other reports, the active
species were not elucidated, but described complexes can
promote OM.
2. Scandium
Sc-based catalytic OM is unknown. However, evidence of the
existence of Sc methylidene is reported.[16] Thermolysis of Sc-
PNP complex 1 in benzene-d6 for 3 days at 100 °C resulted in γ-
activation of C H bonds, followed by [2 + 2]-cycloreversion step
to produce isobutylene and methylidene complex (Scheme 2).
The latter quickly formed dimer 4 that was observed by NMR.
Computational and deuterium labeling studies supported this
mechanism. Generation of methylidene 3 from metallacyclobu-
tane 2 through cycloreversion step is analogous to a key step in
the OM reaction.
Scheme 1. Key intermediates and steps in olefin metathesis.
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Scheme 2. Proposed formation of Sc metallacyclobutane and methylidene.
3. Titanium
Ti complexes played an essential role in the discovery and
development of OM.[17] Thus, the first example of OM, ring-
opening metathesis polymerization (ROMP) of norbornene
(NBE), was reported seven decades ago utilizing ill-defined Ti
complexes.[18] In this study, a mixture of TiCl4 and LiAl(n-C7H15)4
slowly polymerized NBE to give polyNBE. Similar systems were
applied to polymerize substituted NBE[19] and cyclobutene.[20]
Tebbe’s reagent (5, Scheme 3, top) prepared from Cp2TiCl2
(Cp = cyclopentadienyl) and AlMe3 is one of the first well-
defined catalysts for OM. This complex forms metallacyclobu-
tane, the key intermediate in OM, in the presence of olefins.[21]
Complex 5 can slowly catalyze the exchange of methylene
groups between two terminal olefins, shown by Tebbe in 1979
(Scheme 3, bottom).[22] This work was the first example of
catalytic OM promoted by a well-defined complex and inspired
a number of chemists to work in the field. Important to note,
Dmitry Belov earned his M.S. degree from
Moscow State University. He started his grad-
uate work in the group of Professor Alexander
Kurkin. During his Ph.D. research at MSU,
Dmitry studied applications of aza-Cope-Man-
nich rearrangement in the synthesis of natural
product analogs. After graduation, he worked
on the synthesis of HIV entry inhibitors in a
collaborative project with the New York Blood
Center under the supervision of Dr. Asim
Kumar Debnath. Dmitry is part of Professor
Konstantin Bukhryakov’s group at FIU to make
new catalysts for olefin metathesis.
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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Scheme 3. The first catalytic OM catalyzed by Tebbe’s reagent 5.
the active catalyst also can be prepared from Cp2TiCl2 and
CH2(MgBr)2.[23]
The following reports from Grubbs and co-workers were
focused on the isolation of Ti metallacyclobutanes from 5 and
olefins in the presence of Lewis bases to remove AlClMe2;[24] and
study their stability,[25] reactivity,[26] and rearrangement
mechanism.[27] Finally, it has been shown that the reaction of 5
with highly strained cyclic olefins leads to metallacycle 8. The
following ring-opening cycloreversion step in the presence of
phosphines releases the cyclopropane ring strain to form
isolable Ti alkylidenes 9 (Scheme 4).[28] Although those studies
were mainly focused on stoichiometric reactions, they were
crucial for understanding cycloaddition and cycloreversion
steps and, therefore, for the development of catalytic reactions.
Konstantin Bukhryakov obtained his B.S. in
2006 from the Tyumen State University and
his Ph.D. in 2012 at Moscow State University,
Russia, where he was working on the synthesis
of enantiopure heterocycles for pharmaceut-
ical applications. Then he joined the group of
Valentin Rodionov at King Abdullah University
of Science and Technology (KAUST), Saudi
Arabia, to work on the synthesis of functional
polymers and their use in catalysis. In 2015, he
joined Richard R. Schrock at MIT as a post-
doctoral fellow to work on Mo alkylidenes. In
2018, he moved to Florida International Uni-
versity as an Assistant Professor.
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Scheme 4. Isolable Ti alkylidenes 9.
The next milestone in OM was the synthesis of the first well-
defined catalysts 10 and 11 for the living ROMP of NBE shown
by Grubbs in 1986 (Scheme 5).[29] The following work explored
substituted NBE and other cyclic olefins for ROMP to produce
several functional polymers.[30]
Alternatively, the Ti alkylidenes 13 can be generated in situ
via α-hydrogen abstraction from dialkyl Ti complexes 12
(Scheme 6). Transient 13 reacts with NBE to form metallacyclo-
butanes 10 and 14, active catalysts for ROMP of NBE.[31] In the
same study, it was shown that coordinating solvents, such as
THF, inhibit polymerization.
It is recognized that the high stability of Ti metallacyclobu-
tanes results in the overall low activity of Ti catalysts and
precludes the development of Ti-based OM. The second
disadvantage of Ti complexes is the limited functional group
tolerance. Ti is an oxophilic metal, and Ti alkylidenes readily
react with carbonyl compounds through “Wittig type” reaction.
Thus, Tebbe’s reagent is used in the methylenation of carbonyl
compounds.[32] However, this reactivity can be coupled with OM
shown by Stille and Grubbs in a reaction of 15 with 5. The
Scheme 5. The first well-defined catalysts for ROMP of NBE.
Scheme 6. Formation of Ti alkylidenes 13 through α-hydrogen abstraction.
Scheme 7. Example of OM coupled with carbonyl olefination.
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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
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
heterocycles and cyclic enol ethers.[34] One recent example
utilizing this method is the synthesis of 20 from 19 in “Takai
conditions” (RCHX2-TiCl4-Zn) to generate Ti-alkylidenes in situ
(Scheme 8).[35] Compound 20 is a precursor for the synthesis of
anti-colon cancer α-pyrone diterpenoid NF00659B1.[36] The use
of readily available and inexpensive reagents makes this
approach an attractive method to produce cyclic compounds.
Due to the disadvantages of Ti-based OM mentioned above
and the discovery of the first well-defined Mo (1987)[37] and Ru
(1992)[38] alkylidenes, the interest in Ti-catalyzed OM decreased.
Although the synthesis of Ti alkylidenes attracted the scientific
community‘s attention, their OM catalytic activity was not
discussed.[39] It is important to note the contribution of Mind-
iola’s group on the synthesis and catalytic reactions of Ti
alkylidene complexes which has made a significant impact on
the development of Ti catalyzed reactions, including dehydro-
genations, dehydrofluorinations, and C H activation.[40] A sig-
nificant milestone was reached in 2014 when the structure of
Tebbe’s reagent 5 was elucidated 35 years after its first
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
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
catalytic activity (Scheme 9).[48] In our study, we selected RCM as
Scheme 8. Tandem carbonyl olefination – ring-closing metathesis in the
synthesis of 20.
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the structure of poly(oxy-1-buten-1,4-ylene) 23-P1 (Scheme 11).

Scheme 9. V alkylidenes for the ring-closing OM.
a model reaction to examine catalysts’ stability toward ethylene
and functional groups tolerance. Products containing a tosylate,
an ether, a tertiary amide, a tertiary amine, or an ester were
accessed. 21 a–e exhibited lower catalytic activity toward
terminal olefins (R=H) compared to internal olefins (R=CH3) due
to the catalyst‘s limited stability in the presence of ethylene.
Therefore, reactions with terminal olefins were conducted in
open vials to allow the escape of ethylene gas from the reaction
mixture. To our knowledge, we reported the first examples of
RCM catalyzed by V-based complexes.
Changes in the imido group have a notable effect on
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.
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-
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).
Cis/trans isomerization was explained by dissociation of
Cr C(OR) single bond in metallacyclobutane followed by free
rotation of σ-bond and reverse reaction to form metallacyclobu-
tane followed by retro [2 + 2] reaction leading to alkene isomer
(Scheme 12).
A few years later, it was discovered that a similar chromium
carbonyl complex (CO)5Cr=C(Me)OEt 25 could catalyze intra-
molecular enyne metathesis reactions.[52] The reactions were
very substrate-dependent and usually gave multiple products.
The reaction of 26 with a stoichiometric amount of 25 resulted
in the mixture of products, including cyclopropane 31 and the
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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Scheme 13. Proposed mechanism of enyne metathesis promoted by 25.
Scheme 14. Enyne metathesis catalyzed by 25.
Scheme 15. Synthesis and reactivity of Cr-alkylidenes.
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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
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
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
benzophenone led to cyclic product 45, which can be isolated
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Scheme 16. Reactivity of Mn alkylidene 41.
Scheme 17. Reactivity of Mn borylene 44.
and characterized. 45 undergoes cycloreversion to yield
carbene complex 46 in solution (Scheme 17).
7. Iron
Fe is the most abundant transition metal in Earth’s crust, and,
therefore, the use of Fe for OM is highly desirable. Despite
extensive theoretical and experimental work, well-defined Fe-
based catalysts for OM are not known to the best of our
knowledge.
Theoretical study of the formation of Fe metallacyclobutene
published by Roald Hoffman in 1981 is one of the early works
relevant to Fe-based OM.[64] In 1985, Freiser showed by ICR
spectroscopy that FeCD2 + reacts with ethylene (CH2 = CH2) in
the gas phase to produce FeCH2 + and CD2 = CH2.[65] Later,
another theoretical work showed the possibility of cyclo-
addition/cycloreversion steps for cationic Fe alkylidene
complexes.[66]
7.1. Theoretical studies and challenges of Fe-catalyzed OM
After the development of well-defined Ru metathesis catalysts,
the syntheses of analogous Fe-alkylidenes, L2Cl2Fe=CR2, were
attempted by Grubbs in 2001 using diazo compounds. How-
ever, only unexpected phosphazine complexes were formed.[67]
Despite the experimental inaccessibility of L2Cl2Fe=CR2, some
earlier calculations showed that those complexes could pro-
mote OM.[68] However, the following theoretical studies revealed
a few challenges that should be taken into account considering
the direct Fe analog of Grubbs catalysts. One of the challenges
is the strength of the bond between Fe and carbon. A
calculation indicates that the bond dissociation energy (BDE) of
Fe=CH2 in (H2Im)(PH3)Cl2Fe=CH2 (H2Im is imidazolinium carbene)
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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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
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-
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
that alkene cyclopropanation reactions are most common for
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.
The third is the step-wise mechanism, where the olefin‘s attack
on the alkylidene implies the formation of biradical or
zwitterion intermediate.[15b]
Complications and side reactions mentioned above arise
because Fe is a first-row metal and commonly possesses a high-
spin ground state, which favors radical reactions. The high-spin
ground state also explains low BDEs for some Fe alkylidenes,[73]
since the bond distance Fe=C in the triplet state is much longer
than in the singlet state (1.749–1.792 Å vs. 1.708–1.726 Å), and
the carbene substituents are not perpendicular to the plane in
which the π-bond is formed. This geometry reveals the differ-
ence between Fe=CRR’ double bond with two unpaired
electrons on the metal center and a structure in which the π-
bond of Fe=CRR’ is not formed and three unpaired electrons
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]
Theoretical calculations propose a few strategies to over-
come the challenges mentioned above. First, increase the BDE
of the Fe-carbene bond by introducing neutral σ-donating
ligands.[70,73] Second, stabilize the singlet-state of both alkyli-
dene and metallacycle using strong field anionic ligands.[70]
However, the use of very strong field ligands, e. g., alkyl and
cyano groups, stabilizes the singlet state for alkylidene but
destabilizes the singlet state for metallacycle.[70,73] Third, use
Fe(IV) complexes because, according to Hückel calculations,
cyclopropanation is forbidden for d4 metal centers.[64] However,
some theoretical studies showed the possibility of low valent
Fe-catalyzed OM.[73,75] Finally, apply rigid chelating ligands to
control the geometry of the alkylidene and metallacycle to
favor singlet states for both.[70,73,76]
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7.2. Experimental evidence of Fe-catalyzed OM
Although isolable Fe-alkylidenes capable of performing OM are
unknown, a few ill-defined Fe-based systems that exhibit OM
activity have been reported.
Historically ROMP of NBE is widely used to test the ability of
a transition-metal complex to catalyze OM.[18] For example,
RuCl3-catalyzed ROMP of NBE was reported in 1965.[77] Note-
worthy, the first well-defined Ru-based catalyst for OM was
reported only in 1992, 27 years later.[38] The high ring strain of
NBE (27.2 kcal/mol) is responsible for its high reactivity.[78]
Notably, the formation of very reactive (and hence prone to
decomposition) metal methylidene intermediates is avoided
during polymerization.[79] Moreover, NBE itself can be respon-
sible for the formation of metal alkylidene species.[80] The last
factor is significant because, in the early stages of research,
synthesis and isolation of metal alkylidene are not always
possible. 1H NMR easily distinguishes signals of olefin protons of
the ROMP polymer from other possible polymers that can form
from NBE (Scheme 18). The tacticity of the resulted polymer
may indicate the nature of the active species.[81] The polymer‘s
molecular weight may indicate what fraction of a transition-
metal complex forms active species.
2,6-bis(arylimino)pyridine Fe complexes 47 a–c (Figure 1) are
known to promote ethylene‘s oligomerization and polymer-
ization. Complex 47 a was employed for polymerization of NBE
to produce polymer through addition (vinylic) polymerization.
However, it was noticed that the final polymer contains a small
fraction of double bonds (122 units per 10,000 insertions, E/Z
76 : 24), which was attributed to the ROMP product.[82]
Noteworthy, when complexes 47 b–c were employed for
the oligomerization of ethylene in the presence of meth-
ylaluminoxane (MAO), unexpected formation of a small amount
Scheme 18. Types of polymerizations of NBE.
Figure 1. Fe-complexes for ethylene oligomerization and polymerization.
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of odd-number olefins was observed along with expected even-
numbers olefins.[83] The overall percentage of odd-numbered
olefins was 29 % and 19 % for catalysts 47 b and 47 c,
respectively. Three hypotheses were suggested to explain the
formation of odd-number olefins. The first is transfer of methyl
group from MAO to the growing chain. The second possibility is
β-alkyl group elimination.[84] The third possibility is the OM
reaction between ethylene and internal olefins. However, the
authors did not suggest any mechanism explaining the
formation of iron alkylidenes.
Recently, we reported an Fe-based system capable of
performing ROMP of NBE. In our study, low-coordinate homo-
leptic complex 48 was tested in the presence of nine carbene
precursors in reaction with NBE.[85] The formation of catalytically
active Fe alkylidene in situ would result in the formation of
polyNBE. Surprisingly, 48 can slowly produce polyNBE in the
absence of carbene precursors. In addition, the resulting
polymer is 99 % cis, syndiotactic (Scheme 19). The content of Ru,
Mo, W, and V in 48 by ICP is negligible and cannot be
responsible for catalytic activity. The addition of perfluoroalco-
hols increases the activity with retained selectivity.
We discussed three possible ROMP mechanisms, including
Fe alkylidene formation, redox-initiated ROMP, and carbonyl-
olefin metathesis. However, we have not confirmed any of the
considered mechanisms and the nature of the active species,
along with the origin of stereoselectivity, remains unclear.
Iluc achieved an important milestone in the development of
Fe-based enyne metathesis in 2021. Thus, it has been shown
that the low-spin diamagnetic Fe alkylidene 49 is capable of
performing cycloaddition reaction with diphenylacetylene to
form diamagnetic vinyl carbene 51, presumably through the
formation of metallacyclobutene 50 (Scheme 20).[86] Further-
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 19. Fe-catalyzed ROMP of NBE.
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Scheme 20. Enyne metathesis by Fe alkylidene 49.
Co complexes are known. Thus, in 1995, it was reported that
0.1 % of Co neodecanoate and Co acetylacetonate combined
with Et3Al or i-Bu3Al could catalyze ROMP of NBE.[87] The
polymer was all-cis polyNBE with high molecular weight (Mw =
720000). The reaction rate is slow (80 % conversion in 3 days),
but it can be increased by adding hexachloroacetone. Later it
was shown that complexes 53–56 (Figure 2) could catalyze the
polymerization of NBE in the presence of MAO.[82,88] The primary
product was vinyl type-polymer, but a small percentage of
ROMP polymer was present in all cases. Interestingly, the
percentage of ROMP product was higher when polymer yield
was lower. No attempts to optimize the catalyst structure were
made. In addition, the authors did not discuss the possibility of
ROMP catalyzed by trace metals, such as Ru, Mo, or W (as well
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
Figure 2. Co-complexes tested for polymerization of NBE.
ChemPlusChem 2021, 86, 924 – 937 www.chempluschem.org
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
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-
butanes were very stable, and cycloreversion was not observed.
In addition to the reaction with TFE, a formation of
metallacyclobutene 60 took place when complex 58 b reacts
with terminal acetylenes (Scheme 22). The 1,4-diradical mecha-
nism was suggested, and the complex was stable at room
temperature.[94]
Similarly, metallacyclobutane complex 62 was found to be
in equilibria with vinyl carbene 63 (Scheme 23). The latter was
not stable enough for isolation but was characterized in
solution.[95] These findings could be the first step to a
productive Co-catalyzed enyne metathesis reaction.
Computational results suggest that an energy minimum
cannot be located for Co metallacyclobutane, and correspond-
ing alkylidenes should be highly reactive.[68c] Although several
Scheme 21. The reaction of Co alkylidenes with tetrafluoroethylene.
Scheme 22. The reaction of Co alkylidene 58 b with phenylacetylene.
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Scheme 23. Cycloreversion of 61.
Co alkylidene complexes have been isolated and
characterized,[96] their reactions with alkenes mainly lead to
cyclopropanation.[97]
9. Nickel
To the best of our knowledge, no well-defined Ni alkylidene
complexes active in OM reaction have been reported. However,
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 24. Proposed formation of catalytically active Ni alkylidene.
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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]
Formation of macrocyclic Ni complex 69 was observed
during metal-vapor synthesis (MVS) experiment with 68
(Scheme 27). However, ethylene formation was not observed,
and, therefore, it is unclear how compound 69 was formed.[102]
The Ni-catalyzed reaction of [1.1.1]propellane 70 as a
carbene precursor with 4-ethynylbiphenyl 71 produced 72,
presumably through enyne metathesis (Scheme 28).[103] Analo-
gous reaction with alkenes led to cyclopropanation.
In 2015 Baker reported the synthesis of Ni difluorocarbene
complex 73, which can react with TFE to produce Ni metal-
lacyclobutane 74 (Scheme 29).[104] Later, it was shown that
fluorinated Ni alkylidene 75 reacts with TFE and 1,1-difluoro-
Scheme 25. Evidence of formation of catalytically active Ni methylidene 65.
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 29. OM of fluorinated alkenes by fluorinated Ni alkylidenes.
ethylene to produce Ni metallacyclobutane 76 and alkylidene
77 along with OM products.[105]
Computational studies suggested two parallel mechanisms
(Scheme 30). The first pathway includes the formation of
unproductive square planar metallocycle 76 through diradical
intermediate 80. The metathesis pathway involves the forma-
tion of unusual strained bicyclic tetrahedral intermediate 78.
The interconversion between 76 and 77 was not observed
because both metallacycle 76 and alkylidene 77 exhibit low
energies relative to the starting materials. The reaction offers
unique reactivity and suggests a novel variant of the Chauvin
mechanism. However, further development is required to make
the reaction synthetically useful.
In 2007 Iwamoto reported that Ni-loaded mesoporous silica
catalysts could catalyze the transformation of ethylene to
propylene with 68 % conversion.[106] It was suggested that
ethylene dimerizes to 1-butene,[107] followed by isomerization to
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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]
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
was observed that a small fraction of double bonds formed (up
to 244 units per 10,000 insertions, E/Z 67 : 33), which was
attributed to ROMP product.[82]
10. Conclusions and Outlook
In this Minireview, the progress of first-row transition metal
promoted OM was summarized starting from the discovery of
ROMP seven decades ago. Although most currently applied
catalysts are primarily based on second- and third-row metals,
the crucial steps of OM: [2 + 2] cycloaddition reaction between
metal carbene and alkene or alkyne, and the cycloreversion of
metallacycle are general reactions that are also attributed to
the first-row metals. Conceptually, OM catalyst development for
the synthesis of commodity and fine olefins based on first-row
metals is possible. It is important to note that the driving force
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of this development is not simply to substitute existing catalysts
with inexpensive alternatives but also to attain new reactivity
based on the unique electronic structure of first-row metals. For
example, Ti and V alkylidenes can promote C H activation that
can be coupled with OM. Co and Ni fluoroalkylidenes offer a
unique reactivity toward perfluoroalkenes. We strongly believe
OM based on first-row metals will offer a complementary
degree of activity and serendipitous discoveries in the near
future.
Acknowledgements
Acknowledgment is made to the Donors of the American Chemical
Society Petroleum Research Fund for support of this research (ACS
PRF# 61343-DNI3). We are also grateful to the Florida Interna-
tional University and the New Faculty Development Grant
provided by the U.S. Nuclear Regulatory Commission for financial
support.
Conflict of Interest
The authors declare no conflict of interest.
Keywords: alkylidenes · first-row transition metals · [31] N. A. Petasis, D. K. Fu, J. Am. Chem. Soc. 1993, 115, 7208–7214.
homogeneous catalysis · metallacycles · metathesis
[1] a) R. R. Schrock, Angew. Chem. Int. Ed. 2006, 45, 3748–3759; Angew.
Chem. 2006, 118, 3832–3844; b) R. H. Grubbs, Angew. Chem. Int. Ed.
2006, 45, 3760–3765; Angew. Chem. 2006, 118, 3845–3850; c) Y.
Chauvin, Angew. Chem. Int. Ed. 2006, 45, 3740–3747; Angew. Chem.
2006, 118, 3824–3831.
[2] J. Mol, J. Mol. Catal. A 2004, 213, 39–45.
[3] a) M. Ghashghaee, Rev. Chem. Eng. 2018, 34, 595–655; b) B. Reuben, H.
Wittcoff, J. Chem. Educ. 1988, 65, 605–607.
[4] D. E. Fogg, H. M. Foucault, D. M. P. Mingos, R. H. Crabtree, in
Comprehensive Organometallic Chemistry III, Elsevier, Oxford, 2007, pp.
623–652.
[5] G. Turczel, E. Kovács, G. Merza, P. Coish, P. T. Anastas, R. Tuba, ACS
Sustainable Chem. Eng. 2019, 7, 33–48.
[6] A. S. Goldman, A. H. Roy, Z. Huang, R. Ahuja, W. Schinski, M. Brookhart,
Science 2006, 312, 257–261.
[7] K. F. Pfister, S. Baader, M. Baader, S. Berndt, L. J. Goossen, Sci. Adv.
2017, 3, e1602624.
[8] a) S. C. Marinescu, R. R. Schrock, P. Müller, A. H. Hoveyda, J. Am. Chem.
Soc. 2009, 131, 10840–10841; b) S. Byun, S. Park, Y. Choi, J. Y. Ryu, J.
Lee, J.-H. Choi, S. Hong, ACS Catal. 2020, 10, 10592–10601.
[9] K. A. Burdett, L. D. Harris, P. Margl, B. R. Maughon, T. Mokhtar-Zadeh,
P. C. Saucier, E. P. Wasserman, Organometallics 2004, 23, 2027–2047.
[10] P. Federmann, T. Richter, H. Wadepohl, J. Ballmann, Organometallics
2019, 38, 4307–4318.
[11] a) K. C. Wallace, R. R. Schrock, Macromolecules 1987, 20, 448–450;
b) M. H. P. Rietveld, W. Teunissen, H. Hagen, L. van de Water, D. M.
Grove, P. A. van der Schaaf, A. Mühlebach, H. Kooijman, W. J. J. Smeets,
N. Veldman, A. L. Spek, G. van Koten, Organometallics 1997, 16, 1674–
1684; c) K. Mashima, M. Kaidzu, Y. Tanaka, Y. Nakayama, A. Nakamura,
J. G. Hamilton, J. J. Rooney, Organometallics 1998, 17, 4183–4195.
[12] a) R. Toreki, R. R. Schrock, J. Am. Chem. Soc. 2002, 112, 2448–2449; b) R.
Toreki, G. A. Vaughan, R. R. Schrock, W. M. Davis, J. Am. Chem. Soc.
1993, 115, 127–137; c) B. T. Flatt, R. H. Grubbs, R. L. Blanski, J. C.
Calabrese, J. Feldman, Organometallics 1994, 13, 2728–2732.
[13] R. Castarlenas, M. A. Esteruelas, E. Oñate, Organometallics 2005, 24,
4343–4346.
ChemPlusChem 2021, 86, 924 – 937 www.chempluschem.org
[14] W. F. McDonough, S. S. Sun, Chem. Geol. 1995, 120, 223–253.
[15] a) R. R. Schrock, Chem. Rev. 2002, 102, 145–180; b) E. de Brito Sá, A.
Rimola, L. Rodríguez-Santiago, M. Sodupe, X. Solans-Monfort, J. Phys.
Chem. A 2018, 122, 1702–1712.
[16] D. S. Levine, T. D. Tilley, R. A. Andersen, Organometallics 2017, 36, 80–
88.
[17] R. H. Grubbs, Handbook of Metathesis 2003, 4–7.
[18] W. L. Truett, D. R. Johnson, I. M. Robinson, B. A. Montague, J. Am.
Chem. Soc. 1960, 82, 2337–2340.
[19] H. G. G. Dekking, J. Polym. Sci. 1961, 55, 525–530.
[20] G. Dall’Asta, G. Mazzanti, G. Natta, L. Porri, Makromol. Chem. 1962, 56,
224–227.
[21] F. N. Tebbe, G. W. Parshall, G. S. Reddy, J. Am. Chem. Soc. 1978, 100,
3611–3613.
[22] F. N. Tebbe, G. W. Parshall, D. W. Ovenall, J. Am. Chem. Soc. 1979, 101,
5074–5075.
[23] a) J. W. Bruin, G. Schat, O. S. Akkerman, F. Bickelhaupt, Tetrahedron
Lett. 1983, 24, 3935–3936; b) B. J. J. van de Heisteeg, G. Schat, O. S.
Akkerman, F. Bickelhaupt, J. Organomet. Chem. 1986, 308, 1–10.
[24] T. R. Howard, J. B. Lee, R. H. Grubbs, J. Am. Chem. Soc. 2002, 102, 6876–
6878.
[25] a) D. A. Straus, R. H. Grubbs, Organometallics 1982, 1, 1658–1661;
b) E. V. Anslyn, R. H. Grubbs, J. Am. Chem. Soc. 1987, 109, 4880–4890.
[26] a) K. A. Brown-Wensley, S. L. Buchwald, L. Cannizzo, L. Clawson, S. Ho,
D. Meinhardt, J. R. Stille, D. Straus, R. H. Grubbs, Pure Appl. Chem. 1983,
55, 1733–1744; b) S. L. Buchwald, R. H. Grubbs, J. Am. Chem. Soc. 1983,
105, 5490–5491; c) D. A. Straus, R. H. Grubbs, J. Mol. Catal. 1985, 28, 9–
25; d) W. C. Finch, E. V. Anslyn, R. H. Grubbs, J. Am. Chem. Soc. 1988,
110, 2406–2413.
[27] T. Ikariya, S. C. H. Ho, R. H. Grubbs, Organometallics 1985, 4, 199–200.
[28] L. R. Gilliom, R. H. Grubbs, Organometallics 1986, 5, 721–724.
[29] L. R. Gilliom, R. H. Grubbs, J. Am. Chem. Soc. 1986, 108, 733–742.
[30] a) T. M. Swager, R. H. Grubbs, J. Am. Chem. Soc. 1987, 109, 894–896;
b) R. H. Grubbs, W. Tumas, Science 1989, 243, 907.
[32] N. A. Petasis, E. I. Bzowej, J. Am. Chem. Soc. 1990, 112, 6392–6394.
[33] a) J. R. Stille, R. H. Grubbs, J. Am. Chem. Soc. 1986, 108, 855–856; b) J. R.
Stille, B. D. Santarsiero, R. H. Grubbs, J. Org. Chem. 1990, 55, 843–862.
[34] a) K. C. Nicolaou, M. H. D. Postema, C. F. Claiborne, J. Am. Chem. Soc.
1996, 118, 1565–1566; b) K. C. Nicolaou, M. H. D. Postema, E. W. Yue, A.
Nadin, J. Am. Chem. Soc. 1996, 118, 10335–10336; c) T. Fujiwara, T.
Takeda, Synlett 1999, 1999, 354–356; d) T. Fujiwara, Y. Kato, T. Takeda,
Tetrahedron 2000, 56, 4859–4869; e) K. C. Nicolaou, C. F. Gelin, J. H.
Seo, Z. Huang, T. Umezawa, J. Am. Chem. Soc. 2010, 132, 9900–9907;
f) Y. Kawashima, A. Toyoshima, H. Fuwa, M. Sasaki, Org. Lett. 2016, 18,
2232–2235; g) G. E. Keck, Y. B. Poudel, T. J. Cummins, A. Rudra, J. A.
Covel, J. Am. Chem. Soc. 2011, 133, 744–747; h) K. Iyer, J. D. Rainier, J.
Am. Chem. Soc. 2007, 129, 12604–12605; i) T. Fujiwara, M. Odaira, T.
Takeda, Tetrahedron Lett. 2001, 42, 3369–3372.
[35] K. Takai, T. Kakiuchi, Y. Kataoka, K. Utimoto, J. Org. Chem. 1994, 59,
2668–2670.
[36] D.-Y. Kwon, K. Lee, H. Park, M. J. Kim, J. Hong, Bioorg. Med. Chem. Lett.
2018, 28, 2746–2750.
[37] J. S. Murdzek, R. R. Schrock, Organometallics 1987, 6, 1373–1374.
[38] S. T. Nguyen, L. K. Johnson, R. H. Grubbs, J. W. Ziller, J. Am. Chem. Soc.
1992, 114, 3974–3975.
[39] a) J. A. van Doorn, H. van der Heijden, A. G. Orpen, Organometallics
1994, 13, 4271–4277; b) J. A. v. Doorn, H. v. d. Heijden, A. G. Orpen,
Organometallics 1995, 14, 1278–1283; c) N. A. Petasis, J. P. Staszewski,
D.-K. Fu, Tetrahedron Lett. 1995, 36, 3619–3622; d) S. Kahlert, H. Görls,
J. Scholz, Angew. Chem. Int. Ed. 1998, 37, 1857–1861; Angew. Chem.
1998, 110, 1958–1962.
[40] a) F. Basuli, B. C. Bailey, J. Tomaszewski, J. C. Huffman, D. J. Mindiola, J.
Am. Chem. Soc. 2003, 125, 6052–6053; b) F. Basuli, J. Tomaszewski, J. C.
Huffman, D. J. Mindiola, J. Am. Chem. Soc. 2003, 125, 10170–10171;
c) F. Basuli, B. C. Bailey, L. A. Watson, J. Tomaszewski, J. C. Huffman,
D. J. Mindiola, Organometallics 2005, 24, 1886–1906; d) F. Basuli, B. C.
Bailey, J. C. Huffman, D. J. Mindiola, Organometallics 2005, 24, 3321–
3334; e) B. C. Bailey, J. C. Huffman, D. J. Mindiola, W. Weng, O. V.
Ozerov, Organometallics 2005, 24, 1390–1393; f) B. C. Bailey, F. Basuli,
J. C. Huffman, D. J. Mindiola, Organometallics 2006, 25, 3963–3968;
g) B. C. Bailey, J. C. Huffman, D. J. Mindiola, J. Am. Chem. Soc. 2007,
129, 5302–5303; h) B. C. Bailey, A. R. Fout, H. Fan, J. Tomaszewski, J. C.
Huffman, J. B. Gary, M. J. A. Johnson, D. J. Mindiola, J. Am. Chem. Soc.
2007, 129, 2234–2235; i) B. C. Bailey, A. R. Fout, H. Fan, J. Tomaszewski,
935 © 2021 Wiley-VCH GmbH
 Minireviews
ChemPlusChem doi.org/10.1002/cplu.202100192
J. C. Huffman, D. J. Mindiola, Angew. Chem. Int. Ed. 2007, 46, 8246–
8249; Angew. Chem. 2007, 119, 8394–8397; j) A. R. Fout, J. Scott, D. L.
Miller, B. C. Bailey, M. Pink, D. J. Mindiola, Organometallics 2009, 28,
331–347; k) M. G. Crestani, A. K. Hickey, X. Gao, B. Pinter, V. N.
Cavaliere, J.-I. Ito, C.-H. Chen, D. J. Mindiola, J. Am. Chem. Soc. 2013,
135, 14754–14767; l) M. Kamitani, B. Pinter, K. Searles, M. G. Crestani, A.
Hickey, B. C. Manor, P. J. Carroll, D. J. Mindiola, J. Am. Chem. Soc. 2015,
137, 11872–11875; m) T. Kurogi, M. E. Miehlich, D. Halter, D. J. Mindiola,
Organometallics 2018, 37, 165–167; n) S.-y. Baek, T. Kurogi, D. Kang, M.
Kamitani, S. Kwon, D. P. Solowey, C.-H. Chen, M. Pink, P. J. Carroll, D. J.
Mindiola, M.-H. Baik, J. Am. Chem. Soc. 2017, 139, 12804–12814; o) T.
Kurogi, P. J. Carroll, D. J. Mindiola, Chem. Commun. 2017, 53, 3412–
3414.
[41] R. Thompson, E. Nakamaru-Ogiso, C.-H. Chen, M. Pink, D. J. Mindiola,
Organometallics 2014, 33, 429–432.
[42] G. Dall’Asta, G. Motroni, Journal of Polymer Science Part A-1: Polymer
Chemistry 1968, 6, 2405–2413.
[43] J. Yamada, M. Fujiki, K. Nomura, Organometallics 2005, 24, 2248–2250.
[44] a) W. Zhang, K. Nomura, Organometallics 2008, 27, 6400–6402; b) K.
Nomura, Y. Onishi, M. Fujiki, J. Yamada, Organometallics 2008, 27,
3818–3824; c) K. Nomura, B. K. Bahuleyan, K. Tsutsumi, A. Igarashi,
Organometallics 2014, 33, 6682–6691; d) K. Nomura, X. Hou, Organo-
metallics 2017, 36, 4103–4106; e) H. Hayashibara, X. Hou, K. Nomura,
Chem. Commun. 2018, 54, 13559–13562; f) S. Chaimongkolkunasin, K.
Nomura, Organometallics 2018, 37, 2064–2074; g) K. Nomura, K. Suzuki,
S. Katao, Y. Matsumoto, Organometallics 2012, 31, 5114–5120; h) K.
Hatagami, K. Nomura, Organometallics 2014, 33, 6585–6592; i) K.
Nomura, X. Hou, Dalton Trans. 2017, 46, 12–24.
[45] a) X. Hou, K. Nomura, J. Am. Chem. Soc. 2015, 137, 4662–4665; b) X.
Hou, K. Nomura, J. Am. Chem. Soc. 2016, 138, 11840–11849.
[46] W. S. Farrell, Z. Anorg. Allg. Chem. 2021, 647, 584–592.
[47] K. M. Dawood, K. Nomura, Adv. Synth. Catal. 2021, 363, 1970–1997.
[48] D. S. Belov, G. Tejeda, C. Tsay, K. V. Bukhryakov, Chem. Eur. J. 2021, 27,
4578–4582.
[49] X. Hou, X. Chen, X. Gao, L. Xu, H. Zou, L. Zhou, Z. Q. Wu, Chin. J. Chem.
2021, 39, 1181–1187.
[50] G. Doyle, J. Catal. 1973, 30, 118–127.
[51] a) C. T. Thu, T. Bastelberger, H. Höcker, Makromol. Chem. Rapid
Commun. 1981, 2, 383–386; b) C. T. Thu, T. Bastelberger, H. Höcker, J.
Mol. Catal. 1985, 28, 279–292.
[52] P. F. Korkowski, T. R. Hoye, D. B. Rydberg, J. Am. Chem. Soc. 1988, 110,
2676–2678.
[53] a) S. Watanuki, M. Mori, Organometallics 1995, 14, 5054–5061; b) S.
Watanuki, N. Ochifuji, M. Mori, Organometallics 1995, 14, 5062–5067.
[54] M. P. Coles, V. C. Gibson, W. Clegg, M. R. J. Elsegood, P. A. Porrelli,
Chem. Commun. 1996, 1963–1964.
[55] P. Wu, G. P. A. Yap, K. H. Theopold, J. Am. Chem. Soc. 2018, 140, 7088–
7091.
[56] M. F. Farona, P. A. Lofgren, P. S. Woon, J. Chem. Soc. Chem. Commun.
1974, 246–247.
[57] M. Miyairi, T. Taniguchi, T. Nishimura, K. Maeda, Angew. Chem. Int. Ed.
2020, 59, 14772–14780; Angew. Chem. 2020, 132, 14882–14890.
[58] D. S. McGuinness, N. W. Davies, J. Horne, I. Ivanov, Organometallics
2010, 29, 6111–6116.
[59] R. H. Grubbs, G. W. Coates, Acc. Chem. Res. 1996, 29, 85–93.
[60] a) A. Fong, Y. Yuan, S. L. Ivry, S. L. Scott, B. Peters, ACS Catal. 2015, 5,
3360–3374; b) A. Fong, B. Peters, S. L. Scott, ACS Catal. 2016, 6, 6073–
6085.
[61] A. E. Stevens, J. L. Beauchamp, J. Am. Chem. Soc. 1979, 101, 6449–6450.
[62] T. R. Hoye, G. M. Rehberg, Organometallics 1990, 9, 3014–3015.
[63] a) H. Braunschweig, M. Burzler, K. Radacki, F. Seeler, Angew. Chem. Int.
Ed. 2007, 46, 8071–8073; Angew. Chem. 2007, 119, 8217–8219; b) J.
Bauer, H. Braunschweig, A. Damme, J. O. C. Jimenez-Halla, T. Kramer, K.
Radacki, R. Shang, E. Siedler, Q. Ye, J. Am. Chem. Soc. 2013, 135, 8726–
8734.
[64] O. Eisenstein, R. Hoffmann, A. R. Rossi, J. Am. Chem. Soc. 1981, 103,
5582–5584.
[65] a) D. B. Jacobson, B. S. Freiser, J. Am. Chem. Soc. 1985, 107, 67–72;
b) D. B. Jacobson, B. S. Freiser, J. Am. Chem. Soc. 1985, 107, 2605–2612.
[66] G. Dazinger, K. Kirchner, Organometallics 2004, 23, 6281–6287.
[67] J. Louie, R. H. Grubbs, Organometallics 2001, 20, 481–484.
[68] a) A. Poater, S. V. C. Vummaleti, E. Pump, L. Cavallo, Dalton Trans. 2014,
43, 11216–11220; b) A. Poater, E. Pump, S. V. C. Vummaleti, L. Cavallo,
Chem. Phys. Lett. 2014, 610–611, 29–32; c) J. A. Luque-Urrutia, M.
Gimferrer, È. Casals-Cruañas, A. Poater, Catalysts 2017, 7, 389.
ChemPlusChem 2021, 86, 924 – 937 www.chempluschem.org
[69] M. Vasiliu, A. J. Arduengo, D. A. Dixon, J. Phys. Chem. C 2014, 118,
13563–13577.
[70] É. De Brito Sá, L. Rodríguez-Santiago, M. Sodupe, X. Solans-Monfort,
Organometallics 2016, 35, 3914–3923.
[71] J. I. du Toit, C. G. C. E. van Sittert, H. C. M. Vosloo, J. Organomet. Chem.
2013, 738, 76–91.
[72] a) Y. Chen, X. P. Zhang, J. Org. Chem. 2007, 72, 5931–5934; b) J. Liu, L.
Hu, L. Wang, H. Chen, L. Deng, J. Am. Chem. Soc. 2017, 139, 3876–3888;
c) M. Brookhart, J. R. Tucker, G. R. Husk, J. Am. Chem. Soc. 1983, 105,
258–264; d) M. Brookhart, W. B. Studabaker, Chem. Rev. 1987, 87, 411–
432; e) Y. Li, J.-S. Huang, Z.-Y. Zhou, C.-M. Che, X.-Z. You, J. Am. Chem.
Soc. 2002, 124, 13185–13193; f) C. G. Hamaker, G. A. Mirafzal, L. K. Woo,
Organometallics 2001, 20, 5171–5176; g) P. Tagliatesta, A. Pastorini, J.
Mol. Catal. A 2003, 198, 57–61.
[73] É. De Brito Sá, L. Rodríguez-Santiago, M. Sodupe, X. Solans-Monfort,
Organometallics 2018, 37, 1229–1241.
[74] S. K. Russell, J. M. Hoyt, S. C. Bart, C. Milsmann, S. C. E. Stieber, S. P.
Semproni, S. DeBeer, P. J. Chirik, Chem. Sci. 2014, 5, 1168–1174.
[75] M. Mauksch, S. B. Tsogoeva, Chem. Eur. J. 2017, 23, 10264–10269.
[76] B. Yang, D. G. Truhlar, Organometallics 2018, 37, 3917–3927.
[77] F. W. Michelotti, W. P. Keaveney, J. Polym. Sci. Part A 1965, 3, 895–905.
[78] R. Walker, R. M. Conrad, R. H. Grubbs, Macromolecules 2009, 42, 599–
605.
[79] C. Xu, X. Shen, A. H. Hoveyda, J. Am. Chem. Soc. 2017, 139, 10919–
10928.
[80] a) A. Mutch, M. Leconte, F. Lefebvre, J.-M. Basset, J. Mol. Catal. A 1998,
133, 191–199; b) G. Floros, N. Saragas, P. Paraskevopoulou, N.
Psaroudakis, S. Koinis, M. Pitsikalis, N. Hadjichristidis, K. Mertis, Polymer
2012, 4, 1657–1673; c) Y. Kong, S. Xu, H. Song, B. Wang, Organo-
metallics 2012, 31, 5527–5532.
[81] R. R. Schrock, Acc. Chem. Res. 2014, 47, 2457–2466.
[82] M. C. Sacchi, M. Sonzogni, S. Losio, F. Forlini, P. Locatelli, I. Tritto, M.
Licchelli, Macromol. Chem. Phys. 2001, 202, 2052–2058.
[83] a) C. Görl, H. G. Alt, J. Mol. Catal. A 2007, 273, 118–132;
b) C. G. W. M. H. G. A. Marcus Seitz, Jordan J. Chem. 2008, 3, 109–145.
[84] M. E. O’Reilly, S. Dutta, A. S. Veige, Chem. Rev. 2016, 116, 8105–8145.
[85] D. S. Belov, L. Mathivathanan, M. J. Beazley, W. B. Martin, K. V.
Bukhryakov, Angew. Chem. Int. Ed. 2021, 60, 2934–2938; Angew. Chem.
2021, 133, 2970–2974.
[86] M. R. Hoffbauer, V. M. Iluc, J. Am. Chem. Soc. 2021, 143, 5592–5597.
[87] B. L. Goodall, L. H. McIntosh, L. F. Rhodes, Macromol. Symp. 1995, 89,
421–432.
[88] F. Bao, X.-Q. Lü, H. Gao, G. Gui, Q. Wu, J. Polym. Sci. Part A 2005, 43,
5535–5544.
[89] Z. Gonda, G. L. Tolnai, Z. Novák, Chem. Eur. J. 2010, 16, 11822–11826.
[90] S. L. Buchwald, C. Bolm, Angew. Chem. Int. Ed. 2009, 48, 5586–5587;
Angew. Chem. 2009, 121, 5694–5695.
[91] D. J. Harrison, S. I. Gorelsky, G. M. Lee, I. Korobkov, R. T. Baker,
Organometallics 2013, 32, 12–15.
[92] D. J. Harrison, G. M. Lee, M. C. Leclerc, I. Korobkov, R. T. Baker, J. Am.
Chem. Soc. 2013, 135, 18296–18299.
[93] J. T. Fuller, D. J. Harrison, M. C. Leclerc, R. T. Baker, D. H. Ess, R. P.
Hughes, Organometallics 2015, 34, 5210–5213.
[94] G. M. Lee, A. S. C. Leung, D. J. Harrison, I. Korobkov, R. P. Hughes, R. T.
Baker, Organometallics 2017, 36, 2853–2860.
[95] J. M. O’Connor, K. K. Baldridge, C. L. Vélez, A. L. Rheingold, C. E. Moore,
J. Am. Chem. Soc. 2013, 135, 8826–8829.
[96] a) J. Foerstner, A. Kakoschke, D. Stellfeldt, H. Butenschön, R. Wartchow,
Organometallics 1998, 17, 893–896; b) S. Sung, Q. Wang, T. Krämer,
R. D. Young, Chem. Sci. 2018, 9, 8234–8241.
[97] a) S. L. Marquard, M. W. Bezpalko, B. M. Foxman, C. M. Thomas, J. Am.
Chem. Soc. 2013, 135, 6018–6021; b) J. A. Bellow, S. A. Stoian, J. van Tol,
A. Ozarowski, R. L. Lord, S. Groysman, J. Am. Chem. Soc. 2016, 138,
5531–5534.
[98] R. H. Grubbs, A. Miyashita, J. Am. Chem. Soc. 1978, 100, 7418–7420.
[99] A. Miyashita, M. Ohyoshi, H. Shitara, H. Nohira, J. Organomet. Chem.
1980, 338, 103–111.
[100] A. Miyashita, R. H. Grubbs, Tetrahedron Lett. 1981, 22, 1255–1256.
[101] L. F. Halle, P. B. Armentrout, J. L. Beauchamp, Organometallics 1983, 2,
1829–1833.
[102] F. G. N. Cloke, P. B. Hitchcock, M. F. Lappert, C. Mac Beath, G. O.
Mepsted, J. Chem. Soc. Chem. Commun. 1995, 87–88.
[103] S. Yu, A. Noble, R. B. Bedford, V. K. Aggarwal, J. Am. Chem. Soc. 2019,
141, 20325–20334.
936 © 2021 Wiley-VCH GmbH
 Minireviews
ChemPlusChem doi.org/10.1002/cplu.202100192
[104] D. J. Harrison, A. L. Daniels, I. Korobkov, R. T. Baker, Organometallics
2015, 34, 5683–5686.
[105] D. J. Harrison, A. L. Daniels, J. Guan, B. M. Gabidullin, M. B. Hall, R. T.
Baker, Angew. Chem. Int. Ed. 2018, 57, 5772–5776; Angew. Chem. 2018,
130, 5874–5878.
[106] M. Iwamoto, Y. Kosugi, J. Phys. Chem. C 2007, 111, 13–15.
[107] F. Speiser, P. Braunstein, L. Saussine, Acc. Chem. Res. 2005, 38, 784–793.
[108] a) M. Iwamoto, Catal. Surv. Asia 2008, 12, 28–37; b) M. Iwamoto,
Molecules 2011, 16, 7844–7863; c) T. Lehmann, T. Wolff, C. Hamel, P.
Veit, B. Garke, A. Seidel-Morgenstern, Microporous Mesoporous Mater.
2012, 151, 113–125; d) L. Alvarado Perea, T. Wolff, P. Veit, L. Hilfert,
F. T. Edelmann, C. Hamel, A. Seidel-Morgenstern, J. Catal. 2013, 305,
154–168.
ChemPlusChem 2021, 86, 924 – 937 www.chempluschem.org
[109] C. Coperet, F. Allouche, K. W. Chan, M. P. Conley, M. F. Delley, A.
Fedorov, I. B. Moroz, V. Mougel, M. Pucino, K. Searles, K. Yamamoto,
P. A. Zhizhko, Angew. Chem. Int. Ed. 2018, 57, 6398–6440; Angew.
Chem. 2018, 130, 6506–6551.
[110] S. V. Zubkevich, V. A. Tuskaev, S. C. Gagieva, A. S. Kayda, V. N.
Khrustalev, A. A. Pavlov, D. N. Zarubin, B. M. Bulychev, Appl. Organo-
met. Chem. 2020, 34, e5873.
Manuscript received: April 26, 2021
Revised manuscript received: June 7, 2021
Accepted manuscript online: June 13, 2021
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