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MINIREVIEW www.rsc.org/chemicalscience | Chemical Science
(Imido)vanadium(V)-alkyl, -alkylidene complexes exhibiting unique
reactivity towards olefins and alcohols
Kotohiro Nomura*a and Wenjuan Zhangb
Received 3rd February 2010, Accepted 20th March 2010
DOI: 10.1039/c0sc00163e
This minireview introduces recent results in the synthesis of a series of (imido)vanadium(V)-alkyl
complexes, and some reactions with alcohols (phenols) that are proposed to proceed via intermediates
involving coordination of the alcohols (phenols). (Imido)vanadium(V)-alkylidene complexes, prepared
by a-hydrogen elimination in the presence of a neutral donor ligand (PMe3, etc.), exhibited high activity
for ring-opening metathesis polymerisation of cyclic olefins (norbornene) even at high temperature;
these are promising for olefin metathesis by vanadium complex catalysts.
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Introduction
Efficient carbon–carbon bond formation is one of the most
important reactions in organic synthesis as well as in polymer
synthesis, and metal-alkyl and metal-alkylidene species are
known to play essential roles. The synthesis and reaction chem-
istry of metal-alkyl complexes have thus been considered to be
important not only for designing efficient catalysts, but also for
a better understanding of the organic reactions, especially in
terms of catalytic cycles or reaction pathways.1 Polyolefins
produced by metal catalysed olefin coordination/insertion poly-
merisation are important synthetic polymers in our daily life, and
the market capacity (even of the conventional polyethylene and
polypropylene) still increases every year. Catalyst development is
a
Department of Chemistry, Tokyo Metropolitan University, 1-1 Minami
Osawa, Hachioji, Tokyo, 192-0397, Japan. E-mail: ktnomura@tmu.ac.jp
b
Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese
Academy of Sciences, Beijing, 100190, People’s Republic of China.
E-mail: zhangwj@iccas.ac.cn
Kotohiro Nomura received his
PhD in 1993 from Osaka
University, before joining the
group of Richard Schrock
(MIT). He then moved to
Sumitomo Chemical Company,
Ltd. and then the NAIST as an
associate professor in 1998.
Recently he moved to Tokyo
Metropolitan University as
a full professor. His research
focuses on the design of molec-
ular catalysts. He received The
Kotohiro Nomura CSJ Award for Young Chemists
in Technical Development from
The Chemical Society of Japan in 1996, and The Society Award
(Chemical & Engineering) from the Catalysis Society of Japan in
2001. He has co-authored over 160 publications and is an editorial
board member for J. Mol. Catal. A: Chem.
This journal is ª The Royal Society of Chemistry 2010
considered as core technology, therefore considerable attention
has been devoted to the design of efficient catalysts that are
highly effective for the synthesis of new polymers which cannot
be prepared using conventional catalysts.2–5
Classical Ziegler-type vanadium catalysts (e.g. VOCl3, VCl4,
VCl3–AlBr3, AlCl3–AlPh3, AliBu3, SnPh4) are known to display
unique characteristics in olefin polymerisation. For example, the
catalyst system afforded (i) high molecular weight linear poly-
ethylene with uniform molecular weight distribution,6 and (ii)
high molecular weight amorphous polymers applied to the
synthesis of ethylene/propylene/diene copolymers (called EPDM,
synthetic rubbers)7,8 as well as ethylene/cyclic olefin copolymers
(COC, as commercialised as ‘APEL’ in Mitsui Chemicals, Inc.,
information and electronic materials). Moreover, (iii) the catalyst
system [V(acac)3 (acac ¼ acetylacetonato)–Et2AlCl] polymerises
propylene to give not only a syndiotactic ‘‘living’’ polymer with
narrow molecular weight distribution (Mw/Mn ¼ 1.05–1.20),9 but
also diblock copolymers of propylene and methyl methacrylate
(MMA).10
Wenjuan Zhang joined the
group of Wen-Hua Sun
(ICCAS) for her PhD in olefin
polymerisation. She then moved
to the group of Kotohiro
Nomura (NAIST) in 2006, as
a JSPS postdoctoral fellow for
two years. She focused on
vanadium(V) chemistry for
olefin coordination insertion and
metathesis polymerisation and
related organometallic chem-
istry. After finishing her fellow-
Wenjuan Zhang ship, she returned to ICCAS as
an associate professor in 2008.
Her recent research has focused on the design of transition metal
catalysts for olefin polymerisation, and related organometallic
chemistry, and ring-opening polymerisation. She received the
Award for Excellent Young Scientists from the Institute of
Chemistry, Chinese Academy of Sciences, both in 2005 and 2009.
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Due to the promising characteristics demonstrated above, the

design and synthesis of new vanadium complex catalysts directed
toward controlled polymerisation has thus been an attractive
target.3a,b,5 Although examples of the synthesis of vanadium
complexes used as catalyst precursors for olefin polymerisation
are known, successful examples which exhibit the above unique
characteristics of vanadium were limited until recently.3a,b,5a,b
Moreover, examples concerning the synthesis and reaction
chemistry of vanadium-alkyls were limited until recently,11–13
probably due to these vanadium-alkyls tending to be reactive
and/or thermally labile, and reductions to lower oxidation states
often occurred in the reactions with organometallic reagents.13
Olefin metathesis [such as ring-opening metathesis polymeri-
sation (ROMP), ring-closing metathesis and cross metathesis
reactions etc.], introduces promising possibilities for the
synthesis of functional polymers as well as valuable organic
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compounds,14 as demonstrated especially by molybdenum15 and

ruthenium.16 Transition metal-alkylidene complexes, especially
high-oxidation-state early transition metal alkylidene complexes, Scheme 1 Selected examples for (imido)vanadium(V) dichloride
attract considerable attention15,17 because they play essential complexes.
roles as catalysts in olefin metathesis and Wittig-type or group
transfer reactions,14,15,17 as demonstrated especially by molyb-
denum (so called Schrock type complexes).14,15 However, as
described below, no examples that promote the olefin metathesis
reaction using vanadium(V)-alkylidene complexes were known
until recently.
In this minireview, our recent efforts concerning (i) the
synthesis of a series of (imido)vanadium(V)-alkyl, and alkylidene
complexes, including recent examples by others, and (ii) some
reactions of these vanadium(V)-alkyl complexes with alcohols
(phenols, ROH) that proceed via coordination of ROH to the
vanadium metal center are discussed.16

1. Synthesis of (imido)vanadium(V)-dichloro
complexes as effective catalyst precursors for olefin
polymerisation
A series of (imido)vanadium(V)-dichloride complexes,
V(NAr)Cl2(X) [Ar ¼ 2,6-Me2C6H3; X ¼ aryloxo (1),18 ketimide
(2),19 phenoxy-imine (3),20 (2-anilidomethyl)pyridine (4)21] or
V(NAd)Cl2(X) [Ad ¼ 1-adamantyl; X ¼ aryloxo (5), ketimide
(6)],22 could be prepared by treating (ArN)VCl3 with the corre-
sponding lithium salts [such as LiN]CtBu2, LiOAr etc.] in
Et2O or toluene (Scheme 1). The crystallographic results
(Fig. 1) revealed that the ketimide-dichloride analogue,
V(NAr)Cl2(N]CtBu2) (2a), folds in a distorted tetrahedral
geometry around V, and the complex (2a) is a 14 electron
species.19 As shown in Scheme 2, complex 2a reacted with one Fig. 1 Structures for V(NAr)Cl2(N]CtBu2) (2a, top left),
equivalent of PMe3 to afford V(NAr)Cl2(N]CtBu2)(PMe3) that V(NAr)Cl2(N]CtBu2)(PMe3) (top right) and V(NAr)Cl2(N]Ct-
folds in a distorted trigonal bipyramidal structure around V; the Bu2)(dmpe) (bottom).19 All hydrogen atoms are omitted for clarity.
reaction of 2a with bis(dimethylphosphino)ethane (dmpe)
afforded V(NAr)Cl2(N]CtBu2)(dmpe), which folds in a dis-
torted octahedral geometry around V.19
As described in the introduction, these complexes were effec- alkyls (Et2AlCl, Me2AlCl, EtAlCl2 etc.), affording high molec-
tive catalyst precursors for ethylene (co)polymerisation in the ular weight polymers with uniform distributions.23 Selected
presence of Al cocatalysts.18,20–24 In particular, the arylimido- results in ethylene polymerisation using V(NAr)Cl2(O-2,6-
aryloxo analogues (1) showed remarkable catalytic activities not Me2C6H3)–Al cocatalyst systems are summarised in Table 1.23b
only for ethylene polymerisation,18,23 but also for ethylene/nor- The catalytic activity in the ethylene polymerisation was highly
bornene copolymerisation in the presence of halogenated Al dependent upon the Al cocatalyst employed, and the activities in

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cocatalyst nuclearity effect26 generated in the two catalyst

systems.

2. Synthesis of (imido)vanadium(V)-alkyl complexes,

and some reactions with alcohols, thiols, borates
2-1. Synthesis of (imido)vanadium(V)-dialkyl, trialkyl
complexes

The reaction of 2a with LiCH2SiMe3 in n-hexane afforded

Scheme 2 Synthesis of (arylimido)vanadium(V)-dichloro complexes
containing a ketimide ligand.19
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V(NAr)(CH2SiMe3)2(N]CtBu2) (7) in high yield (95%, Scheme
3).21 The coordination of PMe3 to 7 was not observed even by
addition of an excess amount (7.0 equiv.) at 25  C, and this
observation might be due to the steric hindrance of the rather
bulky CH2SiMe3 group around the V metal center. The dialkyl
complexes containing (2-anilidomethyl)pyridine ligand 8

toluene increased in the order: iBu2AlCl (52000 kg-PE/mol-V h)
> EtAlCl2 (37400) > Me2AlCl (27500) > Et2AlCl (11700) >
MAO (2930) [ Et2Al(OEt), Me3Al, Et3Al (trace or less). The
activity did not decrease after 30 min. The activity was highly
affected by the solvent employed; the activity of 584000 kg-PE/
mol-V h (TOF 20800000 h1, 5780 s1) was attained in CH2Cl2 in
the presence of EtAlCl2. The resultant polymers prepared in
toluene possessed ultrahigh molecular weights with unimodal
molecular weight distributions (the Mh values in the resultant
polymers prepared in the presence of iBu2AlCl and Me2AlCl
were 9.87–12.5  106 and 8.98  106, respectively). The activity
decreased upon addition of CCl3CO2Et, which can be commonly
used as an effective additive (for restarting the catalytic cycle
from the deactivated catalyst by re-oxidation to a higher oxida-
tion state) in the ethylene polymerisation using vanadium(III)
and/or vanadium(IV) complexes such as V(acac)3 (acac ¼ acety-
lacetonato), V(b-diketonate)3.5,25 The results clearly suggest that
the catalytically active species were thus different from those
prepared from vanadium(III),(IV) complexes. We assumed that
a plausible reason for the observed difference in the catalytic
activities in the presence of MAO and Et2AlCl cocatalysts might
be due to the different catalytically-active species and catalyst/
were also isolated by adopting this approach (yields 60, 73% for
R ¼ Me, iPr, respectively).21 However, attempts at isolating the
dialkyl complexes from the other dichloro analogues (1, 3, 5, 6)
failed due to difficulties in the isolation of the pure, desired
complexes by recrystallisation in most cases. For example,
reaction of V(NAr)Cl2(O-2,6-iPrC6H3) with 2.0 equiv. of
LiCH2SiMe3 in n-hexane afforded the corresponding dialkyl
complex (>90%) containing a tiny amount of unidentified
by-product (in the 1H NMR spectrum) which caused difficulties
for separation.27 As described below, these dialkyl complexes are
key intermediates for the synthesis of the alkylidene complexes
by a-hydrogen elimination, therefore, we had to find another
possibility for the isolation of the dialkyl complexes.
In contrast, the analytically pure trialkyl analogues,
V(NAr)(CH2SiMe3)3 (9) and V(NAd)(CH2SiMe3)3 (10), could be
isolated in high yields (Scheme 4).27,28 Although these complexes
(9, 10) are low coordinate unsaturated vanadium(V) complexes,
the coordination of PMe3 to V was not observed (by 51V NMR
spectroscopy), even by addition of an excess amount (7.0 equiv.)
in C6D6 at 25  C, and this observation would be due to the steric
hindrance of three CH2SiMe3 ligands around the vanadium(V)
metal center. Resonance in the 51V NMR spectrum (d 1070 ppm)
is relatively close to that in V(N-2,6-iPr2C6H3)(CH2Ph)3

Table 1 Selected results for the effect of Al cocatalyst and solvent in ethylene polymerisation by V(N-2,6-Me2C6H3)Cl2(O-2,6-Me2C6H3)–Al cocatalyst
systemsa

Complex/mmol Al cocatalyst Solvent Activityb kg-PE/mol-V h TOFc/h1 Mwd  105 Mw/Mnd Mhe  105

0.05 Me2AlCl Toluene 27500 980000 —f — 89.8

0.05 Et2AlCl Toluene 11700 415000 36.5 1.42 98.7
0.05 i
Bu2AlCl Toluene 52000 1850000 —f — 125
0.01 i
Bu2AlCl Toluene 64800 2310000 —f —
0.05 EtAlCl2 Toluene 37400 1330000 6.02 3.04
1.0 MAO Toluene 2930 104000 28.7 1.64
0.2 (Ti)g MAO Toluene 8400 298000 12.4 1.90
0.05 Et2AlCl C6H5Cl 19000 677000 —f — 38.3
0.05 EtAlCl2 C6H5Cl 64400 2300000 24.4 3.14
0.05 Me2AlCl CH2Cl2 19700 702000 24.2 3.38
0.05 Et2AlCl CH2Cl2 13200 471000 13.4 3.93
0.05 i
Bu2AlCl CH2Cl2 45200 1610000 —f — 58.5
0.01 EtAlCl2 CH2Cl2 584000 20800000 —f —
a
Selected data from ref. 23b. Conditions: solvent + cocatalyst solution ¼ total 30 mL, ethylene 8 atm, 0  C (25  C with MAO), 10 min, Al cocatalyst 250
mmol (MAO 2.5 mmol). b Activity in kg-polymer/mol-V h. c TOF ¼ (molar amount of ethylene consumed)/(mol-V h). d GPC data in o-dichlorobenzene
vs. polystyrene standards. e Molecular weight by viscosity. f Insoluble in o-dichlorobenzene for GPC measurement. g Cp*TiCl2(O-2,6-iPr2C6H3) was
used, ethylene 4 atm, 25  C, 10 min (cited from ref. 3d).

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Scheme 3 Synthesis of dialkyl complexes.19,21,27
Scheme 4 Synthesis of (imido)trialkyl complexes (9, 10).27,28
(1008 ppm),12band the resonances in a series of (imido)vana-
dium(V)-trialkyl complexes are found to be influenced by the
imido substituent employed [ca. V(N-4-MeC6H4)(CH2SiMe3)3
(d 1028),29 V(NAd)(CH2SiMe3)3 (d 895),28 V(NtBu)(CH2SiMe3)3
(d 877)30]. The crystallographic result (Fig. 2)28 revealed that 10
folds in a rather distorted tetrahedral geometry around V. The
V–N–C bond angle is 180.00(17) and the V–N distance is
 and the three V–C bond distances and angles are
1.6317(14) A,
the same [112.55(7) , 2.0267(18) A];  these are in unique
contrast to those for the arylimido-tribenzyl complex,
V(N-2,6-iPr2C6H3)(CH2Ph)3, [ex. V–N–C 169.0(5) and 1.641(6)
 reported by Turner and Murphy.12b As described below, these
A]
complexes are important intermediates for the synthesis of
various dialkyl analogues containing anionic ancillary donor
ligands.
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Fig. 2 ORTEP drawing of 10.28 Thermal ellipsoids are drawn at the 50%
probability level and H atoms are omitted for clarity.
2-2. Reaction of (imido)vanadium-alkyl complexes with various
alcohols, thiols, and borates
In general, metal-alkyls, especially metal-alkyls with early tran-
sition metals, possess a more nucleophilic nature than those with
late transition metals, and are thus highly reactive toward
Brønsted/Lewis acids.1,5,31,32 For instance, cationic alkyl
complexes, which have been proposed to be the catalytically-
active species in olefin coordination polymerisation, are
generated from their dialkyl analogues by reacting them with
cocatalysts via facile protonolysis or alkyl abstraction;31 some
organometallic complexes can be thus grafted onto a silica
surface by reaction of the alkyl compounds with silanol groups
on the surface.33,34
In contrast, some exceptions (that showed remarkable stability
toward alcohols), exemplified by reactions of Zr(CH2Ph)4 or
Zr(CH2tBu)4 with tBu3COH requiring longer hours even under
refluxing conditions, are known.32 Although the reactions of
early transition metal-alkyls with alcohols (phenols) should be
important basic reactions in organometallic chemistry, a detailed
mechanistic study, especially including direct isolation and/or
observation of the intermediates, had not so far been explored.
Reactions of the (arylimido)vanadium(V) trialkyl analogue,
V(N-2,6-iPr2C6H3)(CH2Ph)3, with 2,6-iPr2C6H3OH or (CF3)3COH
in CH2Cl2 or n-hexane afforded the corresponding aryloxide/
alkoxide in high yield.12b The similar reaction of V(NAr)
(CH2SiMe3)3 (9), with 2,6-Me2C6H3OH, 2,6-iPr2C6H3OH,
C6F5OH (in n-hexane at 25  C) cleanly afforded corresponding
vanadium(V)-aryloxide complexes (11a–c) in high yields (90–93%,
Scheme 5).27 The reactions of 9 with 1.0 equiv. of tBuOH,
(CF3)2MeCOH in n-hexane also gave the corresponding alkoxides
(11d,e) in high yields (92–93%).27 Substitution of the alkyl group in
9 with alcohol or phenol leads to upfield chemical shifts (d 406–659
ppm) from the trialkyl complex (9, 1070 pm) in the 51V NMR
spectra, and the degree of the upfield shift in the dialkyl complexes
(11a–e) increased in the order: d 406 (11d, OtBu) > 506–507 (11a,b,
O-2,6-Me2C6H3, O-2,6-iPr2C6H3) > 595 [11e, OCMe(CF3)2] > 659
(11c, OC6F5). These resonances seem to be influenced mostly by
an electronic factor in the anionic donor ligand employed.
Reaction of V(NAd)(CH2SiMe3)3 (10) with 1.0 equiv. of C6F5OH
in n-hexane afforded a mixture of V(NAd)(CH2SiMe3)2(OC6F5)
(62% yield) and [V(NAd)(CH2SiMe3)(OC6F5)(m2-OC6F5)]2
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Scheme 5 Reaction of V(NAr)(CH2SiMe3)3 (9) with phenols, alcohols.27
(4% yield).28 The present route from the trialkyl analogues should
thus be more suited for the synthesis of a series of vanadium(V)
dialkyl derivatives containing aryloxo/alkoxo ligands, because, as
described above, isolations of these complexes were difficult from
the dichloro analogues (1, 5) by alkylation.
Note that the reaction of 9 with 2,6-tBu2-4-MeC6H2OH did
not take place under the same conditions; the reaction did
not occur even if the C2D2Cl4 solution containing 9 was heated
at 50  C in the presence of 2,6-tBu2-4-MeC6H2OH with an
excess amount (2.6 equiv.).27 The above fact is interesting,
because V(NAr)Cl2(O-2,6-tBu2-4-MeC6H2) was prepared from
V(NAr)Cl3 by treatment with 1.0 equiv. of 2,6-tBu2-4-
MeC6H2OH (yield 94%).18 We believe that the observed fact
would be due to the steric bulk of both the phenol and three
CH2SiMe3 ligands in the coordination of oxygen to the vana-
dium(V) metal center, because, as described below, we propose
that the reaction of V(NAr)Me(N]CtBu2)2 with phenols
proceeds via a pentacoordinated trigonal bipyramidal species by
coordination of the phenol to the vanadium.35,36
2-2-1. Reactions of V(NAr)Me(N]CtBu2)2 with various
phenols, alcohols. Reactions of V(NAr)Me(N]CtBu2)2 (12),
which was prepared by treating V(NAr)Cl(N]CtBu2)2 (1a) with
1.0 equiv. of MeMgBr,35 with 1.0 equiv. of phenols exclusively
gave another vanadium(V)-methyl complex of the type,
V(NAr)Me(N]CtBu2)(OAr0 ) [13, Ar0 ¼ 2,6-Me2C6H3 (a), 4-tBu-
2,6-iPr2C6H2 (b), Ph (c), C6F5 (d)], by replacement with the
ketimide ligand (Scheme 6).35,36 Note that the reaction with
the methyl group did not proceed under these conditions, and the
selectivity in the reaction was not dependent upon the kind of
phenol employed. Treatment of 12 with iPrOH, 3-buten-1-ol or
5-hexen-1-ol in n-hexane cleanly afforded V(NAr)Me-
(N]CtBu2)(OiPr) (13e), VMe(NAr)(N]CtBu2)[OCH2(CH2)n-
CH]CH2] [n ¼ 1 (13f), 3 (13g)], respectively.35,36 The reaction of
12 with 2-Me-6-{(2,6-iPr2C6H3)N]CH}C6H3OH (1.1 equiv. to
V) in C6D6 at 25  C reached completion after 3 days, although
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Scheme 6 Reaction of V(NAr)Me(N]CtBu2)2 (12) with various
phenols, alcohols.20,35,36
the above reaction with 2,6-iPr2C6H3OH, 2,6-Me2C6H3OH
completed within 3 h. The product was V(NAr)Me-
(N]C t Bu 2 )[O-2-Me-6-{(2,6- i Pr 2 C 6 H 3 )N]CH}C 6 H 3 ] (13h)
(yield 92%),20 indicating that a unique reactivity toward alcohol
in the vanadium-methyl complex was preserved even in the
reaction with the imino-phenol.
Mechanistic studies for reaction of V(NAr)Me(N]CtBu2)2
(12) with alcohols. Exploration for unique reactivity of the
vanadium-methyl bonds toward alcohols. The reaction of 12 with
1.0 equiv. of 2,6-Me2C6H3OH or 2,6-iPr2-4-tBuC6H2OH at 25  C
afforded a mixture of 13a,b and the corresponding bis(phen-
oxide) (14a,b), and the quantitative conversion of 14a,b could be
achieved by reacting with 2.0 equiv. of Ar0 OH at 25  C after 24 h
(Scheme 7).36 Note that the formation of methane was not
observed even under these conditions.
A rapid scrambling of 13a and 13b was observed when 13a was
treated with 1.0 equiv. of 4-tBu-2,6-iPr2C6H2OH in CDCl3 at
25  C or when 1.0 equiv. of 2,6-Me2C6H3OH was added into
a CDCl3 solution containing 13b (Scheme 8); the resultant
solution eventually gave a ca. 1 : 1 mixture of 13a and 13b within
30 min at 25  C.36 The solution then gave 3 species upon heating
at 60  C for 12 h which were assigned as 14a, 14b, and the mixed
bis(aryloxo) complex, (ArN)VMe(O-4-tBu-2,6-iPr2C6H2)(O-2,6-
Me2C6H3) (14c). These results clearly explain the unique
Chem. Sci., 2010, 1, 161–173 | 165

Scheme 7 Reaction of V(NAr)Me(N]CtBu2)(OAr0 ) (13) with phenol.36
reactivity of both 12 and 13a,b toward alcohols according to
Scheme 8. Both phenol-scrambling and the phenol/ketimide
exchange reaction should be preferred if the phenol approaches
the electrophilic vanadium metal center trans to the Me group
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(NNN face in 12 or NNO face in 13a,b, and not the NNC faces in
12 or 13a,b), to give pentacoordinated trigonal bipyramidal
intermediates (shown in brackets in Scheme 8).36 The reaction
with the Me group would not occur if the reaction takes place via
this proposed intermediate. A similar assumption was also
Scheme 8 Proposed reaction pathways.36
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proposed by Schrock et al.37 in the alkoxide exchange reaction of
Mo(NAr)(CHtBu)(CH2tBu)(OAr) with ROH (OR ¼ OCMe3,
OAd, OC6F5) and the presence of a similar intermediate was
assumed.
Based on our experiments, we propose that the reaction with
alcohols proceeds in the following steps: 1) the alcohols initially
approaches the electron-deficient metal center trans to the methyl
group to give a pentacoordinated trigonal bipyramidal species,
and 2) proton transfer to the aryloxide/ketimide occurs to give
ketimine/phenol dissociation.36
2-2-2. Reaction of V(NAr)Me(N]CtBu2)2 (12) with various
thiols, borates. In contrast, the reaction of 12 with 1.0 equiv. of
2,6-Me2C6H3SH afforded V(NAr)(N]CtBu2)2(S-2,6-Me2C6H3)
(15a) via cleavage of the V–Me bond (Scheme 9).36 The reaction
with n-C6H13SH in n-hexane afforded V(NAr)(N]CtBu2)2(S-n-
C6H13) (15b) as the sole product.36 These facts clearly indicate
that the reaction mechanism should differ between alcohol and
thiol.
The reaction of 12 with 1.0 equiv. of [PhN(H)Me2][B(C6F5)4]
in THF afforded cationic [V(NAr)(N]CtBu)2(THF)][B(C6F5)4]
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Scheme 9 Reactions of V(NAr)Me(N]CtBu)2 (12) with thiols,
borates.36
(16a) (Scheme 9). The crystallographic analysis of 16a (Fig. 3)
indicates that 16a folds in a pseudo-tetrahedral geometry around
the vanadium center with the coordination of one THF molecule,
and the V–N(CtBu2) distances (1.802–1.808 A)  are comparable to
t
those found in V(NAr)Cl(N]C Bu2)2 and somewhat shorter
than those in 12. The position of another THF molecule could
not be defined/determined. The same compound (16a) could also
be cleanly isolated (90%) by the reaction of 12 with 1.0 equiv.
of [Ph3C][B(C6F5)4], and the reaction of 12 with B(C6F5)3 also
gave [V(NAr)(N]CtBu)2(THF)][MeB(C6F5)3] (16b) exclu-
sively.36 Moreover, the reaction of 14a with 1.0 equiv. of
[PhN(H)Me2][B(C6F5)4] also gave the corresponding cationic
species [V(NAr)(N]CtBu2)(O-2,6-Me2C6H3)(THF)2][B(C6F5)4]
Fig. 3 ORTEP drawing (50% probability ellipsoids) for 16a.36 All
hydrogen atoms are omitted for clarity.
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(16c). These results clearly indicate that cleavage of the V–Me
bond was favored in all cases.36
2-2-3. Reactions of (1-adamantylimido)vanadium(V)-alkyl
complexes containing a chelate alkoxo(imino)pyridine ligand with
alcohols (ROH) that proceed via intermediates formed by co-
ordination of ROH. A (1-adamantylimido)vanadium(V)-dialkyl
complex containing a chelate alkoxo(imino)pyridine ligand,
V(NAd)(CH2SiMe3)2(L0 ) [17, L0 ¼ 6-OC(Me)2-2-{(2,6-iPr2C6H3)-
N]CMe}C5H3N] was prepared from V(NAd)(CH2SiMe3)3 (10)
with the corresponding imino-phenol (1.0 equiv. in C6D6 at 50  C
for 3 days).38 The complex (17) folds in a trans (not cis) geometry,
and is thermally stable in C6D6 at 80  C (even after 72 h).
Dissociation of neutral donor(s) in the chelate ligand (L0 ) did not
take place even in the presence of NHC [2.1 equiv. in C6D6 at
80  C, 72 h, NHC ¼ 1,3-bis(2,4,6-trimethylphenyl)imidazol-
2-ylidene].38
The reaction of 17 with 1.0 equiv. of (CF3)2CHOH (in
n-hexane at 25  C) did not take place even after >12 h, and the
reaction with 2.0 equiv. of (CF3)2CHOH did not take place even
after several hours. The fact should be an interesting contrast to
the observed fact that the reaction of the other (imido)vana-
dium(V)-alkyl complexes [such as V(NAr)Me(N]CtBu2)2 (12),
V(NAr)(CH2SiMe3)3 (9), V(NAd)(CH2SiMe)3 (10)] with alco-
hols (phenols) took place cleanly even at room temperature.
Monitoring the reaction mixture by NMR spectroscopy
revealed that the reaction of 17 with (CF3)2CHOH first generated
an intermediate, and was converted to the original complex (17)
when the mixed solution was placed in vacuo (to remove vola-
tiles). On the basis of 1H, 19F, and 51V NMR spectra, the inter-
mediate should be V(NAd)(CH2SiMe3)2(L0 )[(CF3)2CHOH] (T1)
formed by coordination of oxygen in (CF3)2CHOH into the
vanadium in 17, accompanied as well by dissociation of the two
imino groups (Scheme 10). The reaction completed upon heating
or by stirring for a longer time (48 h) to afford the monoalkyl-
alkoxo species, V(NAd)(CH2SiMe3)(L0 )[OCH(CF3)2] (18a). The
structure determined by X-ray crystallography indicates that 18a
folds in a distorted tetrahedral geometry around vanadium, and
that the two neutral nitrogen donors in L0 are dissociated.38
Moreover, a reaction mixture of the dialkyl complex (17) and 2
equiv. of (CF3)2CHOH (25  C after 48 h) afforded two reso-
nances in the 51V NMR spectrum including a resonance ascribed
to the monoalkyl complex (18a). Only one resonance due to 18a
was observed when the reaction mixture was placed in vacuo (to
remove volatiles). The fact also suggests the formation of another
intermediate, assumed to be V(NAd)(CH2SiMe3)(L)[OCH-
(CF3)2][(CF3)2CHOH] (T2), generated by coordination
of (CF3)2CHOH into 18a.38 The reaction of 17 with 2.0 equiv. of
(CF3)2(CH3)COH in place of (CF3)2CHOH did not take place at
25  C, and a similar observation (such as formation of an
intermediate that could be returned to 17 after removal of
volatiles) was made. The reaction completed to afford
V(NAd)(CH2SiMe3)[OC(CH3)(CF3)2] (18b), when the mixture
was heated at 80  C for 22 h.38
On the basis of the above results, we propose that reactions of
the dialkyl complex (17) with ROH [R ¼ CH(CF3)2,
C(CH3)(CF3)2] proceeded via five coordinate intermediates
formed by coordination of the oxygen in ROH (not via addition
of H+) accompanied by dissociation of two neutral nitrogen
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Scheme 10 Proposed scheme for reaction of V(NAd)(CH2SiMe3)2(L0 )
(17) with alcohol.38
donors (imino groups) in the chelate tridentate ligand (Scheme
10). Confirmation of the intermediates, V(NAd)(CH2Si-
Me3)2(L0 )[ROH] (T1), is potentially important not only for better
understanding of the reactions of vanadium(V)-alkyls with
alcohols, but also to explain the observed unique reactivities of
the vanadium(V)-alkyls in V(NAr)(Me)(N]CtBu2)2 (12),35,36
V(NAr)(CH2SiMe3)3 (9),27 V(NAd)(CH2SiMe)3 (10)28 with
various alcohols. We believe that this hypothesis should be
applied to the reactions of early transition metal alkyls (espe-
cially in high oxidation states) with alcohols.
3. Synthesis of vanadium(V)-alkylidene complexes
and their use as olefin metathesis catalysts
As described in the introduction, transition metal-alkylidene
complexes play important key roles in olefin metathesis, which
introduces promising possibilities for the synthesis of functional
polymers as well as valuable organic compounds,14 as demon-
strated especially by molybdenum15 and ruthenium.16 High-
oxidation-state early transition metal alkylidene complexes
attract considerable attention,15,17 because they play essential
roles as catalysts in olefin metathesis and Wittig-type or group
transfer reactions,14,15,17 as demonstrated especially by molyb-
denum (so-called Schrock-type carbene complexes).14,15,17
Although classical Ziegler type vanadium catalysts display
unique characteristics such as use in the synthesis of high
molecular weight polymers with rapid propagation in olefin
168 | Chem. Sci., 2010, 1, 161–173
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coordination insertion polymerisation3a,b,5 and the syntheses of
some vanadium(III),(IV)-alkylidene39,40 as well as vanadium(V)-
alkylidene complexes41 are known, examples for olefin metathesis
with vanadium-alkylidene complexes have been limited. Since no
examples were known until recently concerning the synthesis of
‘olefin metathesis active’ vanadium(V)-alkylidenes,39b their
synthesis and reaction chemistry are thus promising subjects in
terms of the basic understanding of organometallic chemistry as
well in their application in catalysis.
3-1. Approaches for the synthesis of vanadium-alkylidene
complexes: previous reports and selected recent examples
The most common method to prepare high-oxidation state metal
alkylidenes is by promoting a-H abstraction or a-H deprotona-
tion reactions from metal alkyl complexes lacking b-hydogens.17
Some additional assistance (that can stimulate photochemically
and/or sterically, or with a base) is commonly used to promote/
induce the abstraction/deprotonation. Scheme 11 shows selected
reported examples for the synthesis of vanadium-alkylidene
complexes till 2000. Vanadium(III)-alkylidene complex,
CpV(CHtBu)(dmpe), was prepared by a-hydrogen abstraction
upon addition of dmpe (Scheme 11, top equation).39b Reaction of
CpV(CHtBu)(dmpe) with norbornene was attempted but showed
extremely low (catalytic) activity (TON 0.92 after 96 h at
20  C).39b
Transfer of a benzylidene from phosphorus to vanadium(III)
afforded the first vanadium(V)-alkylidene complex (Scheme 11,
middle).41b However, no reaction between CpV(CHPh)-
(N-2,6-iPr2C6H3)(PMe3) and norbornene or acetone was
observed. Reaction of a V(III) borohydride complex with
diphenylacetylene yielded a vanadium(V) complex containing
a V¼C double bond, although the mechanism was not clear
(Scheme 11, bottom).41c No data concerning the reactivity of this
carbene species were given.
Another approach recently employed for the synthesis of
a vanadium(IV)-alkylidene was the so-called oxidatively induced
a-hydrogen abstraction reported by Mindiola et al.39c,e As
shown in Scheme 12, a vanadium(III)-dialkyl complex, (nac-
nac)V(CH2tBu)2 [nacnac ¼ {(Ar0 )NC(Me)CHC(Me)CN(Ar0 )}],
Scheme 11 Selected reported examples for synthesis of vanadium-
alkylidenes.39b,41b,c
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Scheme 12 Synthesis of a vanadium-alkylidene by oxidatively induced
a-hydrogen abstraction.39c–e
was oxidised to afford neutral or cationic vanadium(IV)-alkylidene
complexes, [(nacnac)V(CHtBu)(I)] or [(nacnac)V(CHtBu)(THF)]-
+
[BPh4].39c Reaction of [(nacnac)V(CHtBu)(I)] with LiPR
(R ¼ 2,4,6-iPr3C6H2, 2,4,6-tBu3C6H2) afforded the corresponding
vanadium(IV)-alkyl, phosphinidene complex, [(nacnac)V-
(CH2tBu)(PR)],39d and the vanadium(V)-alkylidyne complex,
[(nacnac)V(CtBu)(L)], was formed via the corresponding vana-
dium(IV)-alkyl,alkylidene complex upon oxidation (Scheme 12).39e
More recently, the synthesis of a series of vanadium(V)-alky-
lidene complexes from a vanadium(III) dialkyl complex con-
taining a monoanionic tridentate chelate ligand (PNP),
[V(CH2tBu)2(PNP)] PNP ¼ N[4-Me-2-(PiPr2)C6H3]2, by treat-
ing with p-acids or two electron oxidants was reported
(Scheme 13).42 The reaction of [V(CH2tBu)2(PNP)] with chal-
cogen sources resulted in the formation of the vanadium(V)-
alkylidene, chalcogenide species, [V(X)(CHtBu)(PNP)] (X ¼ O, S,
Se, Te). The vanadium(III)-alkylidene complex was also formed
upon addition of 2,20 -bipyridine by a-hydrogen abstraction, and
Scheme 13 Synthesis of vanadium(V)-alkylidenes containing a PNP
ligand.42
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a similar reaction with N2CPh2 in Et2O afforded the alkylidene-
hydrazido complex, V(CHtBu)(NNCPh2)(PNP). It has been
proposed that these reactions take place via a transient vana-
dium(III)-alkylidene complex.42
3-2. Generation of catalytically-active species for ring-opening
metathesis polymerisation (ROMP) from (imido)vanadium(V)-
dialkyl complexes containing anionic ancillary donor ligands
Although the initial attempt at reaction of CpV(CHCMe3)-
(dmpe) with norbornene (NBE) afforded polymers with
extremely low (catalytic) activity (TON 0.92 after 96 h at 20  C),
it was revealed that ring-opening metathesis polymerisation
(ROMP) of NBE took place in the presence of V(NAr)Cl2(OAr0 )
(1) and AlMe3.18a Since 1 showed remarkable catalytic activities
for ethylene polymerisation in the presence of halogenated Al
alkyls, is was thus assumed that the aluminium promoters
directly control the olefin coordination insertion or metathesis
pathways (Scheme 14). Moreover, the dibenzyl complex (20)
initiated ROMP of NBE catalytically at 25  C, affording the
ring-opened poly(NBE) with high molecular weight with
uniform molecular weight distribution.18a As far as we know, this
is apparently the first catalytic example of vanadium-initiated
ROMP of NBE, and formation of the alkylidene species was thus
assumed in this catalysis.18a The dibenzyl complex is, however,
not stable and decomposed gradually; an attempted isolation of
the assumed alkylidene was not successful.
Later, we reported that V(NAr)(CH2SiMe3)2(N]CtBu2) (7),
which showed better thermal stability than V(NAr)(CH2Ph)2-
(O-2,6-iPr2C6H3) (20), initiated ROMP of NBE in toluene.19 The
activity increased especially by addition of PMe3 (3 equiv.) at
higher temperature (80  C) but decreased on further addition (5
equiv.); the activity was extremely low in the absence of PMe3
even at 80  C.19 The resultant polymer possessed a ring-opened
structure containing a mixture of cis- and trans-olefinic double
bonds. These results clearly suggest the formation of vana-
dium(V)-alkylidene by a-hydrogen elimination from the dialkyl
species in the presence of PMe3.
Scheme 14 Ring-opening metathesis polymerisation (ROMP) of nor-
bornene (NBE) by (arylimido)vanadium(V) complex catalysts containing
an aryloxo ligand.18a
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3-3. Synthesis of (imido)vanadium(V)-alkylidene complexes

and their use as catalysts for ring-opening metathesis
polymerisation (ROMP)

It was then revealed that the reaction of 7 with PMe3 (7.0 equiv.)
in benzene-d6 at 80  C afforded the alkylidene complex,
V(CHSiMe3)(NAr)(N]CtBu2)(PMe3) (21, a mixture of syn/anti
forms in solution), by a-hydrogen elimination (Scheme 15).19,43
This is the common method to prepare high-oxidation state
metal alkylidenes by promoting a-hydrogen abstraction reac-
tions from metal alkyl complexes lacking b-hydrogens, and
addition of PMe3 was required to promote the abstraction by
steric crowding.17 The crystal structure (Fig. 4) indicates that 21
folds in a distorted tetrahedral geometry around the vanadium
metal center, and the V–CHSiMe3 bond distance (1.860 A)  is
close to that in the bicyclic carbene-amide complex (1.876 A)  41c
 41b
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and is shorter than that in the benzylidene complex (1.922 A).

The 1H and 13C NMR spectra showed resonances corresponding Fig. 4 ORTEP drawing of 21 Thermal ellipsoids are drawn at the 50%
probability level and H atoms are omitted for clarity.19
to V]CHSiMe3 at 14.52, 302.0 ppm, respectively. These results
clearly indicate that 21 is a nucleophilic 16-electron vanadium(V)-
alkylidene complex. Table 2 Ring opening metathesis polymerisation (ROMP) of norbor-
The complex (21) exhibited remarkable catalytic activity for nene (NBE) by V(CHSiMe3)(N-2,6-Me2C6H3)(N]CtBu2)(PMe3) (21),
the ROMP of NBE without a cocatalyst (Table 2).19,43 The Ru(CHPh)Cl2(PCy3)2 (Ru, Cy ¼ cyclohexyl), and Mo(CHCMe2Ph)
(N-2,6-iPr2C6H3)(OtBu)2 (Mo).a
activity (turnover number, TON) was low when the ROMP was
conducted at 25  C, whereas a standard Schrock type initiator, Complex Temperature Time Mwc  Mw/
Mo(CHCMe2Ph)(N-2,6-iPr2C6H3)(OtBu)2 (Mo), exhibited espe- (mmol) Solvent / C /min TONb 104 Mnc
cially remarkable catalytic activity under similar conditions.43,44
The activity of 21 increased at 50  C, whereas the activity of Mo 21 (1.0) Benzene 25 360 267 46 2.3
Ru (1.0) Toluene 25 60 1306 54 1.7
was negligible due to the decomposition of the catalytically active Mo (0.20) Toluene 25 60 8550 160 1.2
species.44 The activity markedly increased at higher temperature 21 (1.0) Benzene 50 180 1275 49 1.6
21 (1.0) Benzene 50 180 166
Mo (0.20) Toluene 50 40 Trace
21 (1.0) Benzene 80 30 967 140 1.3
21 (1.0) Benzene 80 60 1583 133 1.4
21 (1.0) Toluene 80 60 1244 32 2.8
Ru (1.0) Toluene 80 60 350
a
Selected data cited from ref. 43, conditions: catalyst 0.2 or 1.0 mmol,
NBE 2.12 mmol, benzene or toluene 9.6 mL, initial NBE conc. 0.22
mmol mL1. b TON ¼ NBE consumed (mmol)/V (mmol). c GPC data
vs. polystyrene standards.

Scheme 15 Synthesis of vanadium(V)-alkylidene complex (21).19,43
(80  C), and the observed activity was higher than that of
Ru(CHPh)(Cl)2(PCy)2 under the same conditions due to the
improved thermal stability.19,43
The aryloxo-alkylidene analogue (22) was also isolated from
the corresponding dialkyl complex (11b), which also showed
remarkable catalytic activities for ROMP of NBE in the presence
of PMe3, upon heating in C6D6 in the presence of PMe3 (Scheme
16).27 PMe3 was partially dissociated, as expressed in V(CHSi-
Me3)(NAr)(O-2,6-iPr2C6H3)(PMe3)x (22, x ¼ 0.89), from the
metal center during the purification procedure (by placing the
grown microcrystals in vacuo to remove solvent), probably due to
the steric bulk of the two iPr groups on the aryloxo ligand and the
presence of both the PMe3 coordinated and the PMe3 free species
in solution. This can also be confirmed by the observation that
two resonances in both 51V and 1H spectra (corresponding to
V]CHSiMe3) became one resonance on addition of PMe3.
Complex 22 could be prepared from the dichloro analogue
without isolation of the dialkyl analogue (11b).

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carbenes (NHC) have been known to play essential roles as

Scheme 16 Synthesis of (arylimido)vanadium(V)-alkylidene containing
aryloxo ligand (22).27
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ligands in metal complex catalysts as well as organocatalysts,46
and the NHC in VOCl3(IMes) [IMes ¼ 1,3-bis(2,4,6-trimethyl-
phenyl)imidazol-2-ylidene] has shown its utility in stabilising the
high-oxidation-state vanadium(V) complex.47 We thus explored
the reaction of (imido)vanadium(V) trialkyl analogues,
V(NR)(CH2SiMe3)3 [R ¼ Ar (9), Ad (10)], in the presence of
1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (NHC).
Coordination of NHC was not observed if 10 was added with
1.0 equiv. of NHC in C6D6 at 25  C, but a new resonance
ascribed to the alkylidene proton (13.4 ppm) appeared when the
solution was heated at 80  C for 18 h.28 The targeted alkyl-
alkylidene complex, V(CHSiMe3)(NAd)(CH2SiMe3)(NHC) (23),
could be isolated (22% based on NHC, 15% based on V) when 10
was treated with 2/3 equiv. of NHC at 80  C in C6D6 (Scheme
17).28 Similarly, the reaction of the arylimido analogue (9) with

NHC afforded V(CHSiMe3)(NAr)(CH2SiMe3)(NHC) (24) in

better yield (75% based on NHC, 60% based on V, Scheme 17).

Fig. 5 Plots of TON vs Mn, Mw/Mn in the ring-opening metathesis

polymerisation (ROMP) of norbornene by V(NAr)(CHSiMe3)-
(O-2,6-iPr2C6H3)(PMe3)x (22) in benzene (conditions: 22 5.0 mmol, NBE
21.2 mmol, benzene 24 mL at 25  C).27

Other vanadium(V)-dialkyl complexes containing an aryloxo

ligand like V(NAr)(CH2SiMe3)2(O-2,6-Me2C6H3) (11a) and
other complexes containing a (2-anilidomethyl)pyridine ligand (8
in Scheme 3) showed notable catalytic activities for the ROMP of
NBE in the presence of PMe3, but attempts at isolating the
corresponding vanadium(V)-alkylidene were not successful,
although the presence of resonances that may be ascribed to the
assumed alkylidene species was observed in the 1H NMR
spectra.21,27 One probable reason for this difficulty could be
assumed as due to the formed vanadium(V)-alkylidene species
being highly reactive even in C6D6 and affording another species
[such as V[CH(D)SiMe3](C6D5) etc.] by C–H activation.45 Some
reactions with the isolated vanadium(V)-alkylidene are thus in Scheme 17 Reactions of (imido)vanadium(V)-trialkyl complexes.28
progress, and will be introduced soon.
The aryloxo-alkylidene (22) showed higher catalytic activities
at 25  C than the ketimide-alkylidene (21), and the resultant
polymers obtained at 25  C possessed narrow molecular weight
distributions and the Mn value increased over the time course
(Fig. 5). The Mn values increased upon increasing the TON
values (polymer yields) with consistently narrow molecular
weight distributions (Mw/Mn ¼ 1.1–1.2) during the polymerisa-
tion, clearly indicating that the ROMP of NBE by 22 proceeded
in a living manner at 25  C.

Synthesis of (imido)vanadium(V)-alkyl, alkylidene complexes

containing N-heterocyclic carbene ligands from their trialkyl
analogues. As described above, one of the methods commonly
employed for generating metal-alkylidenes is the a-hydrogen Fig. 6 ORTEP drawing of 25. Thermal ellipsoids are drawn at the 50%
abstraction promoted by heat or irradiation.17 N-Heterocyclic probability level and H atoms are omitted for clarity.28

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Fig. 7 ORTEP drawing of 23. Thermal ellipsoids are drawn at the 50%
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probability level and H atoms are omitted for clarity.28
Thermolysis of the (adamantylimido)vanadium(V) trialkyl
analogue, V(NAd)(CH2SiMe3)3 (10), in C6D6 at 80  C afforded
a dimeric species, [V(m2-NAd)(CH2SiMe3)2]2 (25) determined by
X-ray crystallography (Fig. 6). However, the reaction of 10 with
(more bulky and stable) 1,3-di-tert-butylimidazole-2-ylidene did
not show any changes in the 51V NMR spectra even at 80  C for 3
days. The fact would thus suggest that this NHC stabilises 10
probably by weak coordination but did not promote a-hydrogen
elimination under these conditions.
The (adamantylimido)vanadium(V)-alkyl, alkylidene complex
containing NHC (23) folds in a rather distorted tetrahedral
geometry around vanadium (Fig. 7), and the V–C bond distances
for the alkyl, the alkylidene and the NHC are 2.069(3), 1.829(3)
 respectively; these values (alkyl, alkylidene) are
and 2.172(2) A,
similar to those in previous reports.19,47 The V–C(NHC) distance
 the coordination seems
is close to that in VOCl3(IMes) (2.137 A);
likely as neutral carbene and a similar explanation would thus be
possible. Ring-opening metathesis polymerisation of norbornene
by 23 (and 24) took place, but the activities (at 80  C in benzene)
were lower than that of V(CHSiMe3)(NAr)(N]CtBu2)-
(PMe3),19,43 and the activities at 25  C were negligible.
The present approaches should be widely applied for the
preparation of various early transition metal-alkylidene
complexes. Moreover, the present alkyl-alkylidenes would also
be promising intermediates for syntheses of not only the
alkylidynes but also of the cationic alkylidenes or the alkylidene-
containing series of anionic donor ligands. Further studies con-
cerning their application as catalysts, including the effect of the
adamantyl imido ligand are now underway.
Conclusions
In this account, recent examples of the syntheses and reactions of
vanadium(V)-alkyl, and alkylidene complexes containing imido
ligands have been summarised. In particular, unique promising
characteristics, such as the synthesis of ultra high molecular
weight polymers in coordination polymerisation, unique reac-
tivity with alcohols (ROH) that proceed via intermediates formed
by coordination of ROH, and olefin metathesis active vana-
dium(V)-alkylidene complexes that exhibit better thermal
stability, have been introduced. On the basis of these efforts, we
172 | Chem. Sci., 2010, 1, 161–173
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believe this subject will expand the possibilities for the establish-
ment of more efficient/precise catalytic processes as well as the
better understanding of organometallic chemistry with vanadium.
Acknowledgements
K.N. expresses his heartfelt thanks to former/present group
members who contributed to this project as coauthors, and Mr
Shohei Katao (Nara Institute of Science and Technology,
NAIST) for his assistance in the crystallographic analysis. The
research by K.N. was partly supported by a Grant-in-Aid for
Scientific Research on Priority Areas (No. 19028047, ‘‘Chemistry
of Concerto Catalysis’’) from the Ministry of Education, Culture,
Sports, Science and Technology, Japan. W.Z. expresses her
sincere thanks to JSPS for a postdoctoral fellowship (P06349).
The authors also express their thanks to Dr Shu Zhang (NAIST)
for help in the preparation of this manuscript.
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This journal is ª The Royal Society of Chemistry 2010

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12 Selected pioneering examples for structurally characterized V(V)
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M. C. W. Chan, J. M. Cole, V. C. Gibson and J. A. K. Howard,
Published on 28 May 2010. Downloaded on 09/10/2014 09:27:07.
Chem. Commun., 1997, 2345.
14 For examples, see: (a) M. R. Buchmeiser, Chem. Rev., 2000, 100, 1565;
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15 For examples, see: (a) R. R. Schrock, Acc. Chem. Res., 1990, 23, 158;
(b) R. R. Schrock, in Alkene Metathesis in Organic Synthesis, ed. A.
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17 For examples, see: (a) R. R. Schrock, Acc. Chem. Res., 1979, 12, 98;
(b) R. R. Schrock, Chem. Rev., 2002, 102, 145; (c) R. R. Schrock, in
Handbook of Metathesis, ed. R. H. Grubbs, Wiley-VCH, Weinheim,
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18 (a) K. Nomura, A. Sagara and Y. Imanishi, Macromolecules, 2002,
35, 1583; (b) W. Wang, J. Yamada, M. Fujiki and K. Nomura,
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19 J. Yamada, M. Fujiki and K. Nomura, Organometallics, 2005, 24,
2248.
20 Y. Onishi, S. Katao, M. Fujiki and K. Nomura, Organometallics,
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21 S. Zhang, S. Katao, H. W,-Sun and K. Nomura, Organometallics,
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22 W. Zhang and K. Nomura, Inorg. Chem., 2008, 47, 6482.
23 (a) W. Wang and K. Nomura, Macromolecules, 2005, 38, 5905; (b)
W. Wang and K. Nomura, Adv. Synth. Catal., 2006, 348, 743.
24 K. Nomura, W. Wang and J. Yamada, Stud. Surf. Sci. Catal., 2006,
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25 For exampleD. L. Christman, J. Polym. Sci., Part A-1, 1972, 10, 471.
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28 W. Zhang and K. Nomura, Organometallics, 2008, 27, 6400.
29 The data including syntheses of V(N-4-MeC6H4)Cl(CH2SiMe3) and
V(N-4-MeC6H4)Cl2(CH2SiMe3) are shown in ref. 13b. Calculation
chemistry concerning the effect of the imido substituent in
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30 F. Preuss, G. Overhoff, H. Becker, H. J. H€ausler, W. Frank and
G. Reiss, Z. Anorg. Allg. Chem., 1993, 619, 1827.
31 For example (reviews): (a) R. F. Jordan, Adv. Organomet. Chem.,
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32 (a) T. V. Lubben, P. T. Wolczanski and G. D. van Duyne,
Organometallics, 1984, 3, 977. In this report, the reaction with
This journal is ª The Royal Society of Chemistry 2010
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Zr(CH2Ph)4 with 1.14 equiv. of tBu3COH in benzene under reflux
conditions for 7 h afforded Zr(CH2Ph)3(OCtBu3), whereas synthesis
of Zr(CH2Ph)3(OCtBu3) by the reaction of Zr(CH2tBu)4 with
t
Bu3COH in benzene required 30 h at 93–95  C; (b) it is also known
that certain chromium(IV)-tetra(alkyl)s are stable even in alcohols
under reflux conditions.
33 For related reviewing articles, see: (a) C. Coperet, M. Chavanas,
R. P. Saint-Arroman and J. M. Basset, Angew. Chem., Int. Ed.,
2003, 42, 156; (b) J. M. Thomas, R. Raja and D. W. Lewis, Angew.
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34 For recent examples, see: (a) P. Nicholas, H. S. Ahn and T. J. Marks,
J. Am. Chem. Soc., 2003, 125, 4325; (b) M. W. McKittrick and
C. W. Jones, J. Am. Chem. Soc., 2004, 126, 3052; (c) B. Rhers,
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F. Lefebvre, J. -M. Basset, X. Solans-Monfort, O. Eisenstein,
W. W. Lukens, L. P. H. Lopez, A. Sinha and R. R. Schrock,
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C. Coperet, A. Sinha, Z. J. Tonzetich, R. R. Schrock, X. Solans-
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35 J. Yamada and K. Nomura, Organometallics, 2005, 24, 3621.
36 J. Yamada, M. Fujiki and K. Nomura, Organometallics, 2007, 26,
2579.
37 A. Sinha, L. P. H. Lopez, R. R. Schrock, A. S. Hock and P. M€ uller,
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38 W. Zhang, S. Katao, W.-H. Sun and K. Nomura, Organometallics,
2009, 28, 1558.
39 Examples for isolation of terminal vanadium(III),(IV) alkylidenes: (a)
ref. 11c; (b) B. Hessen, J.-K. F. Buijink, A. Meetsma, J. H. Teuben,
G. Helgesson, M. Hakansson, S. Jagner and A. L. Spek,
Organometallics, 1993, 12, 2268. Reaction of CpV(CHCMe3)(dmpe)
with norbornene was attempted but showed extremely low
(catalytic) activity (TON 0.92 after 96 h at 20  C). No GPC data
were described; (c) F. Basuli, U. J. Kilgore, X. Hu, K. Meyer,
M. Pink, J. C. Huffman and D. J. Mindiola, Angew. Chem., Int.
Ed., 2004, 43, 3156; (d) F. Basuli, B. C. Bailey, J. C. Huffman,
M.-H. Baik and D. J. Mindiola, J. Am. Chem. Soc., 2004, 126,
1924; . Synthesis of vanadium(IV)-phosphinidene complex from the
vanadium(IV)-alkylidene; (e) F. Basuli, B. C. Bailey, D. Brown,
J. Tomaszewski, J. C. Huffman, M.-H. Baik and D. J. Mindiola,
J. Am. Chem. Soc., 2004, 126, 10506. Synthesis of vanadium(V)-
alkylidyne via oxidatively induced a-hydrogen abstraction from
vanadium(IV)-alkyl, alkylidene complex.
40 Related isolated examples for vanadium-carbene complexes: (a)
G. Erker, R. Lecht, R. Schlund, K. Angermund and C. Kr€ uger,
Angew. Chem., Int. Ed. Engl., 1987, 26, 666; (b) R. Milczarek,
W. R€ usseler, P. Binger, K. Jonas, K. Angermund, C. Kruger and
M. Regitz, Angew. Chem., Int. Ed. Engl., 1987, 26, 908.
41 (a) B. Hessen, A. Meetsma, F. van Bolhuis and J. H. Teuben,
Organometallics, 1990, 9, 1925; (b) J.-K. F. Buijink, J. H. Teuben,
H. Kooijman and A. L. Spek, Organometallics, 1994, 13, 2922; . No
reaction between CpV(CHPh)(NAr)(PMe3) and norbornene or
acetone was observed(c) M. Moore, S. Gambarotta, G. Yap,
L. M. Liable-Sands and A. L. Rheingold, Chem. Commun., 1997, 643.
42 (a) U. J. Kilgore, C. A. Sengelaub, M. Pink, A. R. Fout and
D. J. Mindiola, Angew. Chem., Int. Ed., 2008, 47, 3769; (b)
U. J. Kilgore, C. A. Sengelaub, H. Fan, J. Tomaszewski, J. A. Karty,
M.-H. Baik and D. J. Mindiola, Organometallics, 2009, 28, 843.
43 W. Zhang, J. Yamada and K. Nomura, Organometallics, 2008, 27,
5353.
44 K. Nomura, T. Atsumi, M. Fujiki and J. Yamada, J. Mol. Catal. A:
Chem., 2007, 275, 1.
45 S. Zhang, K. Nomura, unpublished results. Formation of the phenyl
complex was confirmed by the crystallographic analysis. These results
will be submitted soon.
46 For example: (a) N-Heterocyclic Carbenes in Synthesis, ed. S. P.
Nolan, Wiley-VCH, Weinheim, Germany, 2006; (b) N-Heterocyclic
Carbenes in Transition Metal Catalysis, ed. F. Glorius, Springer,
Berlin, Germany, 2007; (c) D. Bourissou, O. Guerret, F. P. Gabbai
and G. Bertrand, Chem. Rev., 2000, 100, 39; (d) D. Enders,
O. Niemeier and A. Henseler, Chem. Rev., 2007, 107, 5605.
47 C. D. Abernethy, G. M. Codd, M. D. Spicer and M. K. Taylor, J. Am.
Chem. Soc., 2003, 125, 1128.
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