Role of paramagnetic Ni(I) and Ni(III) complexes in catalytic reactions of unsaturated hydrocarbons

Article abstract of DOI:10.1134/S0023158412040106

By analyzing experimental data collected by systematic investigation of Ni(I) complex formation conditions, it is demonstrated that, when a system simultaneously contains Ni(0) and Ni(II) complexes, whether cationic or electroneutral, stabilized by olefinic or organoelement ligands, the complexes undergo comproportionation to form Ni(I) complexes. Using individual Ni(II) complexes as examples, it is shown that the spontaneous decomposition of hydrido and organometallic Ni(II) complexes yields Ni(I) complexes. The Ni(I) and Ni(III) complexes are involved in the catalytic cycles of reactions of olefins and acetylenes. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S0023158412040106

ISSN 0023ꢀ1584, Kinetics and Catalysis, 2012, Vol. 53, No. 4, pp. 486–492. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © V.V. Saraev, P.B. Kraikivskii, V.V. Bocharova, D.A. Matveev, 2012, published in Kinetika i Kataliz, 2012, Vol. 53, No. 4, pp. 509–515.
Role of Paramagnetic Ni(I) and Ni(III) Complexes in Catalytic
Reactions of Unsaturated Hydrocarbons
V. V. Saraev, P. B. Kraikivskii*, V. V. Bocharova, and D. A. Matveev
Irkutsk State University, Irkutsk, 664033 Russia
* eꢀmail: peter10@list.ru
Received December 5, 2011
Abstract—By analyzing experimental data collected by systematic investigation of Ni(I) complex formation
conditions, it is demonstrated that, when a system simultaneously contains Ni(0) and Ni(II) complexes,
whether cationic or electroneutral, stabilized by olefinic or organoelement ligands, the complexes undergo
comproportionation to form Ni(I) complexes. Using individual Ni(II) complexes as examples, it is shown
that the spontaneous decomposition of hydrido and organometallic Ni(II) complexes yields Ni(I) complexes.
The Ni(I) and Ni(III) complexes are involved in the catalytic cycles of reactions of olefins and acetylenes.
DOI: 10.1134/S0023158412040106
Progress in presentꢀday industry is impossible tion of cyclic olefins [20, 21], and linear polymerizaꢀ
without introducing hiꢀtech, economically efficient tion and cyclotrimerization of phenylacetylene [22].
catalytic systems. The rapid advances in catalysis by In our opinion, this is primarily due to the fact that
metal complexes and extensive use of modern physical researchers have abandoned the longꢀstanding stereoꢀ
investigation techniques have led to a marked headway type that Ni(I) complexes are intermediates rapidly
in the study of all key metal complexes, including decomposing in the catalytic system and have realized
those appearing during catalyst formation and those that dinuclear diamagnetic Ni(I) complexes mask the
directly involved in the catalytic cycle. An important true valence of nickel in the system.
achievement in this area is the discovery and identifiꢀ
cation of Ni(I) in nickel complex catalysts by in situ
EPR spectroscopy. It was convincingly demonstrated
that Ni(I) complexes at a high concentration compaꢀ
rable with the initial concentration form in catalytic
systems via the reduction of Ni(II) complexes under
the action of organometallic compounds of nontransiꢀ
tion metals [1–3] or via the oxidation of Ni(0) comꢀ
plexes involving Lewis or Brönsted acids [1–4]. After
the EPR identification of Ni(I) compounds in Zieꢀ
glerꢀtype catalytic systems [5], there have been
attempts to elucidate the role of the Ni(I) compounds
in reactions of unsaturated hydrocarbons. Researchers
did not observe symbasis between the intensity of the
EPR signal from Ni(I) and catalytic activity and conꢀ
cluded that the Ni(I) complexes are unstable intermeꢀ
diates undergoing rapid disproportionation via the
reaction
Here, we analyze our and other researchers' data
providing evidence that Ni(I) complexes are thermoꢀ
dynamically stable compared to Ni(II) and Ni(0)
complexes and are directly involved in the catalytic
cycles of reactions of unsaturated hydrocarbons.
EXPERIMENTAL
All experiments were carried out using standard
Schlenk techniques with an argon–vacuum line and
appropriate glassware. All chemicals were stored in
argon in sealed tubes.
The reactants and solvents were purchased from
Merck. Cyclooctaꢀ1,5ꢀdiene (COD), toluene, and
hexane were additionally dried with a sodium–potasꢀ
sium allow and were degassed.
The synthesis of the nickel complexes considered
in this article is described in detail in publications cited
below. Xꢀray structure analysis of the complexes was
carried out on crystals frozen into a drop of silicone
oil.
2Ni(I)
→
Ni(II) + Ni(0)
(I)
and play only an auxiliary role in the formation of
active Ni(II) complexes [6]. At the same time, it was
reliably established that Ni(I) complexes are directly
involved in the catalytic cycles of crossꢀcoupling reacꢀ
tions [7–12] and in biochemical processes [13–16]. In
recent years, it has increasingly frequently been
claimed that Ni(I) complexes participate directly in
various catalytic reactions of unsaturated hydrocarꢀ
RESULTS AND DISCUSSION
Ni(I) Complexes Are Thermodynamically Stable
Compounds
Comproportionation reaction between Ni(II) and
bons: olefin polymerization [17–19], cyclodimerizaꢀ Ni(0) complexes. For the first time, a spontaneous
486

ROLE OF PARAMAGNETIC NI(I) AND NI(III) COMPLEXES
487
change in the oxidation state of nickel in a solution by reacting equimolar amounts of nickel(II) and
containing both Ni(II) and Ni(0) was reported in 1964 nickel(0) triphenylphosphine complexes in diethyl
[23]. A number of nickel(I) complexes were obtained ether:
2Ni(PPh3)4 + X2
Ni(PPh3)2 + Ni(PPh3)2X2
2Ni(PPh3)3X + 2PPh3,
(II)
CH
CH
2
2Ni(PPh3)3X + H2C=CH2,
2
(III)
(XI)
where X = Cl, Br, or I. The yield of nickel(I) comꢀ
plexes resulting from reactions (II) and (III) was close
to 100%.
We discovered that a comproportionation reaction
can also take place between a cationic Ni(II) complex
and a Ni(0) phosphine complex in a toluene + acetoꢀ
nitrile (1 : 1) mixture at room temperature:
Ni(II) + Ni(0)
in solution is almost completely shifted to the rightꢀ
hand side.
2Ni(I),
The following natural question arises here: Why is
there no idea about the chemistry of Ni(I) solutions,
while the chemistry of Ni(II) solutions is developed
well? We think that the rarity of Ni(I) compounds is
due to their low kinetic stability, i.e., their capacity for
readily entering into chemical reactions.
Since the Ni(I) complexes are thermodynamically
more stable than the Ni(II) and Ni(0) complexes, they
can be both identified by in situ EPR spectroscopy and
isolated directly from real catalytic systems. For examꢀ
ple, among the cationic Ni(I) complexes, whose forꢀ
[Ni(CH3CN6)](BF4)2 + Ni(PPh3)4
+PPh
(IV)
3
–CH CN 2[Ni(CN)(PPh3)3]BF4,
3
[Ni(DPPE)2](BF4)2 + Ni(DPPE)2
(V)
2[Ni(DPPE)2]BF4,
where DPPE = bis(diphenylphosphino)ethane.
mation in the catalytic system Ni(PPh3)4/BF4 OEt2
⋅
The quantitative yield of the Ni(I) complexes is
also attained by carrying out a comproportionation
reaction between electroneutral Ni(II) and Ni(0)
complexes, including organometallic ones, in toluene
solution [25, 26]:
was demonstrated for the first time by Tkach et al.
[27], the individual tricoordinated complex
[Ni(PPh3)3]BF4 [28] was isolated from the reaction
system and was comprehensively characterized,
including by Xꢀray structure determination (Fig. 1).
Formation of Ni(I) complexes via the spontaneous
decomposition of hydrido and organometallic Ni(II)
complexes. In 1969, the pentacoordinated nickel(II)
hydrido complex [HNi(P(OEt)3)4]+ was synthesized
by protonation of a nickel(0) phosphite complex in
acid media [29]. Later, reactions of conjugated dienes
[30, 31] and olefins [32] involving this nickel(II) comꢀ
plex were studied by NMR spectroscopy. These studꢀ
ies, which were carried out on a model system, proꢀ
vided a basis for the universally accepted hydride
mechanism of the conversion of unsaturated hydroꢀ
carbons catalyzed by nickel complexes [30, 32]. Howꢀ
ever, an analysis of numerous studies of the mechaꢀ
nisms of reactions catalyzed by real active catalytic
systems suggests that, the higher the activity of the catꢀ
alytic system, the smaller the chance of detecting a
Ni(II) hydrido complex in this system not only during
the functioning of the metal complex catalyst, but also
during its formation [33, 34]. In our opinion, this is due
to the low stability of the coordinatively unsaturated
Ni(II) hydrido complexes in solution. The decomposiꢀ
tion of the Ni(II) hydrido complexes typically yields
Ni(I) complexes [25, 35]. For example, the individual
complex hydrido(2ꢀdiphenylphosphine)thionaphthaꢀ
Ni(P^S)2 + Ni(PMe3)4
NiCp2 + Ni(PPh3)4
2(P^S)Ni(PMe3)2,(VI)
2CpNi(PPh3)2, (VII)
NiCp2 + Ni(P(OEt)3)4
2CpNi(P(OEt)3)2,
(VIII)
NiCp2 + Ni(bipy)2
NiCp2 + Ni(COD)2
2CpNi(bipy),
2CpNi(COD),
(IX)
(X)
where P^S = 2ꢀ(diphenylphosphanyl)thiophenolate,
Cp =
η
5ꢀcyclopentadienyl, bipy = 2,2'ꢀbipyridyl, and
COD = cyclooctaꢀ1,5ꢀdiene.
The Ni(I) complexes synthesized via comproporꢀ
tionation have been isolated in the individual state and
reliably identified by modern methods (EPR, Xꢀray
structure determination). The Ni(I) complexes in
solution remain unchanged at room temperature in an
inert atmosphere for at least 1 month. Note that the
comproportionation reaction practically comes to
completion even when the initial Ni(II) compound is
poorly soluble [24, 25]. It was demonstrated by the
example of the CpNi(COD) complex synthesized via
reaction (X) that Ni(I) can be stabilized in solution by
unsaturated hydrocarbons in the absence of a convenꢀ
tional Pꢀ or Nꢀcontaining donor ligand.
lato[P,S]bis(trimethylphosphine)nickel (I), which is staꢀ
ble in the solid state in an argon atmosphere for a long
time, decomposes spontaneously to yield a nickel(I)
Thus, contrary to common views, the equilibrium
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488
SARAEV et al.
C15
C16
C20
C19
P2
C4
C21
C17
F6
B2
C13
C18
O1
P2
F5
F7
P3
Ni1
P1
Ni1
S1
C2
C1
C3
C4
C6
C5
C7
P1
C12
C11
P3
C23
C24
F4
F3
C8
B1
C10
C22
C9
F1
F2
Fig. 2. Molecular structure of Ni(P^S)(PMe ) (CCDC
3 2
705063) [25]. Bond lengths, Å: Ni–S1 2.241(1), Ni–P1
2.147(9), Ni–P2 2.184(1), Ni–P3 2.199(1). Bond angles,
deg: P1–Ni–P2 123.91(3), P1–Ni–P3 116.02(4), P2–
Ni–P3 118.57(4), P1–Ni–S1 91.08(3), P2–Ni–S1
97.01(4), P3–Ni–S1 94.04(4).
Fig. 1. Molecular structure of the cationic complex
[Ni(PPh ) ]BF (CCDC 682428) [28]. Bond lengths, Å:
P1–Ni1 2.2149(16), P2–Ni1 2.2089(17), P3–Ni1
2.1826(16). Bond angles, deg: P3–Ni1–P2 110.9(6), P3–
Ni1–P1 141.98(7), P2–Ni1–P1 107.00(6).
3 3
4
complex (II) on being dissolved in diethyl ether even at
PPh2
Ni
PPh2
Ni
PMe3
PMe3
CH3
–10°С
[25].
hv
–1/2C H
2
6
PPh2
PPh2
PMe3
PMe3
S
PMe3
S
PMe3
PMe3
–10
°C, Et O
2
III
II
Ni
H
Ni
–1/2H
2
PMe3
S
S
Individual Ni(II) πꢀallyl complexes are also very
I
II
stable [36], but they may decompose in solution in the
course of time to yield Ni(I) complexes as well. For
Complex II was isolated as an individual comꢀ
pound [25] and was comprehensively studied, includꢀ
ing by EPR spectroscopy and Xꢀray crystallography
(Fig. 2). Complex II is stable in solution in an argon
atmosphere at room temperature for more than half a
year.
The same complex II results from the decomposiꢀ
tion of the lightꢀsensitive Ni(II) methyl complex III
[25]:
example, the individual Ni(II) ꢀallyl imine–amido
π
complex IV in the solid state remains unchanged for a
long time ]36]. A solution of complex IV sealed in a
vacuumized tube is table for a few hours, according to
NMR data. Thereafter, line broadening is observed in
the NMR spectrum. After 10–12 h, the EPR spectrum
shows a strong signal from the Ni(I)
complex
πꢀallyl diimine
V:
iꢀPr
H
iꢀPr
iꢀPr
iꢀPr
+ °C, THF
20
N
N
N
N
–1/2H
2
Ni
Ni
iꢀPr
iꢀPr
iꢀPr
iꢀPr
IV
V
Complex
room temperature for over 2 years.
V
is stable in solution in a sealed tube at
Evidently, the above spontaneous decomposition
reactions of the individual Ni(II) hydrido and organoꢀ
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ROLE OF PARAMAGNETIC NI(I) AND NI(III) COMPLEXES
489
×
103, (mol C2H4)(mol Ni)–1 h–1
metallic complexes also occur in catalytic systems
during the formation of a metal complex catalyst.
TOF
30
25
20
15
10
5
Ni(I) Complexes Are Real Active Species in Catalytic
Reactions of Olefins and Acetylenes
The above data suggest that generation of Ni(I)
complexes is very likely to take place in the formation
of various catalytic systems. Although the nonparaꢀ
magnetic species of Ni(I) complexes are difficult to
detect and identify, some data reported in the literaꢀ
ture indicate that Ni(I) complexes are directly
involved in the catalytic cycles of reactions of unsaturꢀ
ated hydrocarbons.
0
1
2
3
4
5
In the formation of the catalytic system
Signal intensity, arb. units
Ni(PPh3)4/BF3
⋅
OEt2, which is among the most active
systems for ꢀalkene oligomerization, the entire Ni(0)
α
Fig. 3. Activity of the Ni(PPh ) /BF · OEt /HBF OEt
3 4
3
2
3
oxidizes to Ni(I), which is then stabilized in the soluꢀ
tion in the form of mononuclear cationic complexes
by triphenylphosphine ligands [37]. After the introꢀ
duction of a substrate (ethylene, propylene, or styꢀ
rene) into the system, the EPR signal from Ni(I) disꢀ
appears immediately and does not reappear until comꢀ
plete oligomerization. However, upon the
introduction of the catalyst poison triethyl phosphite
into the system (P : Ni = 2 : 1), the reaction terminates
immediately and an intense EPR signal from the coorꢀ
system (TOF) as a function of the Ni(I) concentration.
hydroarylation catalyzed by dicationic Pd(II) and
Pt(II) complexes [45, 46].
The formation of the catalytic system
Ni(COD)2/BF3 OEt2, which is among the most effiꢀ
⋅
cient systems for the cycloisomerization and [2 + 2]
cyclodimerization of COD [21] and for the addition
polymerization of norbornene (NB) [19], also involves
the quantitative oxidation of Ni(0) to Ni(I), which is
stabilized in solution by substrate molecules in the
absence of conventional organometallic ligands.
Two types of paramagnetic nickel complex are genꢀ
erated during the formation of this system, namely, a
cationic Ni(I) complex coordinated with COD moleꢀ
cules and a carbocationic Ni(I) complex covalently
bonded with COD [21]. Figure 4 (curves 1, 2) presents
the EPR spectra of these Ni(I) complexes and the corꢀ
responding most likely structures.
As distinct from alkene oligomerization in the
Ni(PPh3)4ꢀbased system, which begins with the conꢀ
version of mononuclear Ni(I) complexes into dinuꢀ
clear diamagnetic structures, the catalytic conversion
of COD or NB in the Ni(COD)2ꢀbased system
involves mononuclear paramagnetic nickel comꢀ
plexes. We demonstrated by in situ EPR spectroscopy
that the [2 + 2] cyclodimerization of COD and the
addition polymerization of NB are accompanied by
the oxidative addition of the substrate (COD or NB) to
a cationic Ni(I) complex with the formation of metalꢀ
dinatively
saturated
complex
[(PPh3)2Ni(P(OEt)3)2]BF4 appears, indicating that
the active form of the Ni(I) complex is dinuclear. The
intensity of this EPR signal is proportional to the
activity of the system at the instant the catalyst poison
was introduced (Fig. 3) [38].
The individual cationic Ni(I) complex
[Ni(PPh3)3]BF4 isolated from the catalytic system
Ni(PPh3)4/BF3
⋅
OEt2 shows, without being additionꢀ
ally activated, approximately the same activity in styꢀ
rene oligomerization as the Ni(PPh3)4/BF3 OEt2 sysꢀ
⋅
tem itself [39, 40].
In order to elucidate the mechanism of the activaꢀ
tion of the multiple bond in the dinuclear Ni(I) comꢀ
plex, we investigated the formation of the
[Ni(PPh3)3]BF4 –styrene complex by NMR and UV
spectroscopy [39, 40]. It was inferred from spectroꢀ
scopic data that, in this Ni(I) styrene complex, posiꢀ
tive charge is transferred from the nickel atom to the
styrene ligand, resulting in the formation of a carbocaꢀ
tionic
Ni(I)
complex,
most
likely
(PPh3)2NiCH2C+HPh, which is dimerized in solution
[39, 40]. The same multiple bond activation mechaꢀ
nism was suggested for explaining experimental data
concerning alkene polymerization catalyzed by catꢀ
ionic Zr(IV) complexes [41, 42], regiospecific and steꢀ
reospecific styrene dimerization catalyzed by cationic
lacyclic lowꢀspin Ni(III) complexes (spectra
3 and 4
and the corresponding structures in Fig. 4) [19]. Takꢀ
ing into account these EPR data and the cyclic strucꢀ
ture of the COD conversion products, we suggested
metallacyclic mechanisms involving Ni(I) and Ni(III)
complexes for the [2 + 2] cyclodimerization of COD
and the addition polymerization of NB [19].
Fe(III) complexes [43], ethylene and
α
ꢀolefin
codimerization catalyzed by cationic Pt(II) complexes
The individual mononuclear nickel(I) complex
[44], vinyl ester polymerization catalyzed by cationic CpNi(PPh3)2, which was synthesized via a comproporꢀ
Pd(II) complexes [45], and olefin hydrovinylation and tionation reaction between Ni(PPh3)4 and NiCp2, is
KINETICS AND CATALYSIS Vol. 53
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490
SARAEV et al.
1
d9
Ni
Ni
d9
2
3
4
F
F
d7
Ni
BF2
d7
F
Ni
2400
2600
2800
3000
, G
3200
3400
3600
H
Fig. 4. EPR spectra and the corresponding most likely structures of Ni(I) and Ni(III) complexes [19, 21].
catalytically very active in the cyclotrimerization and tion of 1,2,4ꢀtriphenylbenzene and a linear polymer
linear polymerization of phenylacetylene in toluene in can be explained in terms of the metallacyclic (A) and
the absence of any activator [22]. The selective formaꢀ alkylidene (B) mechanisms (Fig. 5). These mechaꢀ
Ph
Ph
Ph
Ph
Ph
Ni
H
Ni–H
H
H
Ph
Ph
А
Ni
B
Ph
Ph
H
(H)Ph
Ph(H)
n
Ph
Ph
Ni
Ni–
H
Ph
Ph
H
H
Ph
Ph
(H)Ph
H
Ph(H)
Ph
n
Ph
Fig. 5. Scheme of the selective formation of 1,2,4ꢀtriphenylbenzene (A) and a linear polymer (B) from phenylacetylene in the
CpNi(PPh ) ꢀbased system [22].
3 2
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ROLE OF PARAMAGNETIC NI(I) AND NI(III) COMPLEXES
491
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the oxidative addition of phenylacetylene molecules to
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Thus, the above analysis of the results of systematic
experimental studies suggests the following concluꢀ
sions:
(1) When a system simultaneously contains Ni(0)
and Ni(II) complexes, whether cationic or electroꢀ
neutral, stabilized by olefinic or organoelement
ligands, the complexes undergo comproportionation
to form Ni(I) complexes.
(2) Both the protolytic and spontaneous decompoꢀ
sition of Ni(II) hydrido complexes yields Ni(I) comꢀ
plexes.
(3) The spontaneous decomposition of Ni(II) allyl
imine–amido complexes yields Ni(I) complexes.
(4) The Ni(I) complexes readily get involved in the
oxidative addition of alkenes and alkynes, turning into
Ni(III) complexes. This indicate that they can be
directly involved in the catalytic cycles of reactions of
olefins and acetylenes.
16. Harmer, J., Finazzo, C., Piskorski, R., Ebner, S.,
Duin, E.C., Goenrich, M., Thauer, R.K., Reiher, M.,
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,
19. Kraikivskii, P.B., Saraev, V.V., Bocharova, V.V.,
Matveev, D.A., Petrovskii, S.K., and Gotsko, M.D.,
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ACKNOWLEDGMENTS
21. Saraev, V.V., Kraikivskii, P.B., Matveev, D.A.,
Bocharova, V.V., Petrovskii, S.K., Zelinskii, S.N.,
V.V. Bocharova is grateful to the Irkutsk State Uniꢀ
versity administration for a postgraduate grant.
This work was supported by the Federal Target Proꢀ
gram “Scientific and Scientific–Pedagogical Personnel
of Innovative Russia” (contract no. 14.740.11.0619).
Vilms, A.I., and Klein, H.ꢀF., J. Mol. Catal. A: Chem.
2010, vol. 315, no. 2, p. 231.
,
22. Saraev, V.V., Kraikivskii, P.B., Vil’ms, A.I.,
Zelinskii, S.N., Yunda, A.Yu., Danilovtseva, E.N., and
Kuzakov, A.S., Kinet. Catal., 2007, vol. 48, no. 6, p. 778.
23. Heimbach, P., Angew. Chem., 1964, vol. 76, no. 13,
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