The comparison of addition of molecules possessing P(V)-H bond to alkynes catalyzed with Pd and Ni complexes

Article abstract of DOI:10.1134/S1070428010090010

Main factors have been analyzed necessary for creation of an efficient catalytic system for alkynes hydrophosphorylation based on nickel complexes, and a valid model system was suggested for the comparison with palladium complexes. It has been discovered for the first time that the insertion of an alkyne into the metal-hydrogen bond occurs with a considerably lower activation barrier than into the metal-phosphorus bond, whereas the variation in the reaction energy corresponds in both cases to an exothermic reaction. Under the optimized conditions the transformation catalyzed by nickel complexes does not require acid addition and may proceed even in the absence of a phosphine ligand.

Full text of DOI:10.1134/S1070428010090010

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 9, pp. 1269−1276. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © V.P. Ananikov, L.L. Khemchyan, I. P. Beletskaya, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 9, pp. 1273−1280.
Dedicated to Full Member of the Russian Academy of Sciences
N.S. Zefirov on occasion of his 75th anniversary
The Comparison of Addition of Molecules Possessing P(V)–H
Bond to Alkynes Catalyzed with Pd and Ni Complexes
V. P. Ananikova, L. L. Khemchyana, and I. P. Beletskayab
aZelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 119991 Russia
e-mail: val@ioc.ac.ru
bLomonosov Moscow State University, Moscow, 119899 Russia
e-mail: beletska@org.chem.msu.ru
Received June 22, 2010
Abstract—Main factors have been analyzed necessary for creation of an efficient catalytic system for alkynes
hydrophosphorylation based on nickel complexes, and a valid model system was suggested for the comparison
with palladium complexes. It has been discovered for the first time that the insertion of an alkyne into the metal–
hydrogen bond occurs with a considerably lower activation barrier than into the metal–phosphorus bond, whereas
the variation in the reaction energy corresponds in both cases to an exothermic reaction. Under the optimized
conditions the transformation catalyzed by nickel complexes does not require acid addition and may proceed even
in the absence of a phosphine ligand.
DOI: 10.1134/S1070428010090010
The hydroheterofunctionalization (the addition of
molecules containing a bond hydrogen–heteroatom) of
unsaturated organic compounds is among the leading
methods of contemporary fine organic synthesis and un-
derlies quite a number of industrial processes [1–3]. The
creation of efficient catalytic systems proceeding from
available complexes of transition metals is the common
strategy in this field. Nowadays a dynamic development
is observed, and in many cases a significant progress is
achieved for catalytic reactions involving quite a number
of heteroatoms and elements (B, Si, O, N, S, Se etc.)
[1–7].
not form a general unambiguous pattern, and in some
cases the results from various studies are contradictory.
The following key problems can be revealed requiring
keen attention and deep comprehension: (1)What is the
efficience of catalysts based on palladium and nickel
complexes in the addition of the P(V)–H bond to alkynes;
(2)What is the reason of the significant difference in the
activity of catalyst precursors containing bivalent and
zero-valent metal compounds, M(II) and M(0); (3)Why
the regioselectivity of addition reactions changes if all of
them occur by the alkyne insertion into the metal–phos-
phorus bond; (4) Ambiguous results exist on the ligand
and acid effect.
Notwithstanding the advances in this field, the
situation in the investigations of addition to alkynes
of molecules containing the phosphorus(V)–hydrogen
bond is not clear. The products of the addition along
Markownikoff rule were shown to be available in the
presence of palladium and nickel catalyst as was reported
by Tanaka [8–12], Han [13, 14], Montchamp [15–17],
Toffano [18] and in our publications [19–21].
In this report we make the first attempt to understand
the reason of some among these contradictions and to sug-
gest the optimum strategy of the studies for their solution.
The investigation of catalytic activity of nickel and
palladium complexes was carried out on a selected model
hydrophosphorylation reaction of 1-heptyne (Scheme 1).
It should be stated that similar model systems involving
a terminal alkyne without substituents (1-hexyne, 1-hep-
The accumulated array of the experimental data does
1269

ANANIKOV et al.
1270
1
Scheme 1.
10% conversion of reagent IIa. The analysis of the H
NMR spectrum showed the absence of the alkyne in the
reaction mixture (conversion of Ia 100%), and a black
insoluble precipitate formed in the course of the reac-
tion. Evidently here the main contribution to the alkyne
conversion originated not from the hydrophosphorylation
but the oligomerization process that was well known for
the nickel complexes [22, 23]. The hydrophosphorylation
in the studied conditions stopped because the lack of the
alkyne.As to the catalytic system based on Pd complexes,
there was no alkyne oligomerization.
O
C5H11
(i-PrO)2P
Catalyst
+
C5H11
(i-PrO)2P H
O
IIIa
Ia
IIa
tyne, or 1-octyne) is a common practice in the studies
of the catalytic addition of molecules possessing P–H
bonds and has been already used in many investigations
[12, 17, 20].
The catalytic transformation was performed in THF
medium at 100°C over 3 h. On completing the reaction
the reaction mixture was analyzed by 1H and 31PNMR. In
contrast to most already published research papers in this
study we determined not only the composition and struc-
ture of the reaction products but the residual amount of
unreacted initial compounds and also the quantity of side
products was estimated. In certain cases just the analysis
of the general picture had the fundamental importance for
the understanding of the nature of the observed processes.
Therefore it is clear that this common model system
cannot provide a valid comparison of the efficiency of
catalytic systems based on palladium and nickel com-
plexes in alkynes hydrophosphorylation.
Inasmuch as in the catalytic system Ni(cod)2/PPh3 the
formation of a small amount of the desired product was
found (Table 1), we carried out a more detailed investiga-
tion of this system for various alkynes (Scheme 2).
Scheme 2.
The hydrophosphorylation of 1-heptyne catalyzed
with palladium complex led to the formation of Mar-
kownikoff product IIIa in 63% yield (Table 1). Nickel
complexes either did not show a considerable catalytic
activity or the yield was negligible.
R1
R2
O
Catalyst
(R3O) P H
2
R1
R +
2
(R3O)2P
O
Ia_Id
IIa_IIc
IIIa_IIId
At the first sight, this result demonstrates the advan-
tage of the palladium over nickel catalyst. However the
more detailed consideration showed that in event of the
nickel acetylacetonate both initial reagents Ia and IIa
remained intact, and the NMR spectra lacked any signals
of new compounds. The color and appearance of the
reaction mixture did not change within 3 h of heating.
Consequently, under these conditions the prfecursor of
the catalyst was not activated, and the catalytically active
metal complexes did not form.
I, R1 = C5H11, R2 = H (a); R1 = Ph, R2 = H (b); R1 = R2 =
Et (c), R1 = R2 = Ph (d); II, R3 = i-Pr (a), Ph (b), C12H25
(c); III, R1 = C5H11, R2 = H, R3 = i-Pr (a); R1 = R2 =
Ph, R3 = i-Pr (b); R1 = R2 = R3 = Ph (c); R1 = R2 = Ph,
R3 = C12H25 (d).
The reaction with phenylacetylene Ib provided only
traces of the Markownikoff product (Table 2). Same
as in the case of 1-heptyne the most of H-phosphonate
remained unreacted, and at the same time the complete
conversion of the alkyne and oligomer formation was
observed.
In the case of bis(cycloctadiene)nickel some product
formed in the system, but the reaction finished at the
Table 1. Conditions and yields of hydrophosphorylation products of 1-heptyne on the complexes of palladium and nickel (100°C,
3 h, metal–ligand ratio 1 : 4, 6 mol% of catalyst, 0.5 ml of THF)
Metala complex and ligand
Pd2dba3, PPh3
Yield of IIIa, %
Residue of IIa, %
Side products, %
63
0
18
100
9
19
0
Ni(acac)2, PPh3
Ni(cod)2, PPh3
6
04
a dba is dibenzylideneacetone, acac is acetylacetone, cod is cyclooctadiene.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 9 2010

THE COMPARISON OF ADDITION OF MOLECULES POSSESSING P(V)–H BOND
1271
The reaction with 3-hexyne Ic required more stringent
conditions (140°C) and gave the addition product in 15%
yield. The distinguishing feature of this process was the
equal conversion of the alkyne and the H-phosphonate
indicating the absence of the side reaction of the alkyne
oligomerization.
The results obtained show that the internal alkynes are
significantly less prone to side oligomerization on the Ni
catalyst than the terminal alkynes.
In the absence of the side oligomerization reaction
the efficiency of catalytic systems based on nickel and
palladium proved to be quite comparable, same as the
selectivity.
Diphenylacetylene Ie reacted already at 120°C, and
olefin IIIc formed in a very high yield, 95%. The com-
plete conversion of H-phosphonate was observed in the
system, and the amount of side products did not exceed
5%. The reaction proved to be of a general character,
and the conversion of other H-phosphonates IIb and
IIc also resulted in the 100% yield of addition products
without any side reactions. The addition to 3-hexyne and
diphenylacetylene occurs with a very high streoselectivity
(E/Z > 99/1) as a syn-addition to the triple bond. The for-
mation of the product corresponding to the anti-addition
of the P–H bond to alkyne (Z-isomer) was not observed,
and the side products found were of another character.
The high efficiency of a simple catalytic system Ni/
PPh3 we discovered for the first time. It was previously
reported that this system was not suitable for synthetic
purposes due to low yields and poor selectivity [13].
Evidently this conclusion originated from the application
of a noninformative model system with 1-octyne prone
to the side reactions involving the alkyne [13].
Since we showed in this study that in the absence of
the side polymerization of alkyne the nickel complexes
catalyze the stereoselective hydrophosphorylation of the
triple bond we regarded as desirable the use of Ni(acac)2
as the precursor of catalyst. The nickel acetylaceto-
nate is stable in air and considerably cheaper than the
bis(cycloctadiene)nickel that is obviously an advantage
for developing synthetic procedures.
The experiments with the palladium catalyst and in-
ternal alkynes Ic and Id showed somewhat lower yields
of the target products and considerably lower selectiv-
ity due to the formation of side products. In this model
system the nickel complexes demonstrated considerable
advantage over palladium.
We found that Ni(acac)2 could be reduced in situ
directly in the reaction mixture by adding a catalytic
quantity of diisobutylaluminum hydride (DIBAL). No
Table 2. Conditions and yields of hydrophosphorylation products of alkynes on the complexes of palladium and nickel, THF,
9 mol% of catalyst
Temperature,
Yield
of III, %
Residue Side products,
Catalytic system
Ni(cod)2, PPh3
Alkyne I
H-phosphonate II
Time, h
19
°C
of II, %
%
100
1
90
9
0
Ph
O
(i-PrO)2P H
Ib
IIa
IIa
Ni(cod)2, PPh3
140
19
15
85
Et
Et
Ic
IIa
Ni(cod)2, PPh3
Ni(cod)2, PPh3
120
120
4
4
95
0
0
5
0
Ph
Ph
Id
Id
100
O
(PhO)2P H
IIb
Id
Ni(cod)2, PPh3
120
4
100
0
0
O
(C12H25O)2P H
IIc
Ic
IIa
Pd2dba3, PPh3
Pd2dba3, PPh3
140
120
19
19
12
70
53
0
35
30
Id
IIa
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 9 2010

ANANIKOV et al.
1272
addition occurred without the reducer (1 ml of THF, 4 h,
120°C, 9 mol% of catalyst). In the presence of DIBAL
olefin IIIb formed in a high yield (96%) and selectivity
(the yield of side products 4%). This result is comparable
with that for bis(cycloctadiene)nickel (Table 2).
Obviously this notable difference between Pd and Ni
catalysts is worth special consideration. The elucidation
of the causes of this dramatic suppression of the catalytic
activity of the nickel complexes will be the object of
further research.
This discovery opens additional prospects for the de-
sign of catalyst of alkynes hydrophosphorylation based
on available Ni(II) salts.
The currently assumed mechanism of the alkynes
hydrophosphorylation catalyzed by palladium and nickel
complexes involves a stage of the oxidative addition
with the formation of complex IV and the subsequent
alkyne insertion into the metal–phosphorus bond to give
complex V (Scheme 3). At the reductive elimination of
the C–H bond from complex V the formation of olefin
III occurs and the regeneration of the compound of the
zero-valent metal.
Note that the use of bivalent nickel salts as catalyst
precursor was described for the addition of (RO)P(O)H2
without reduction [16]. In certain cases the role of reucer
may play one of the reagents or the phosphine ligand. It
was also shown that the stage of activation of the catalyst
precursor was very sensitive to water traces [24].
For the nickel and palladium complexes the alternative
reaction pathway involving the alkyne insertion into the
metal–hydrogen bind was not considered. In this case
intermediate complex VI would form which undergoes
the reductive elimination of the C–Pbond with the forma-
tion of olefin III and the regeneration of the compound
of the zero-valent metal (Scheme 3).
The data obtained unambiguously show that the lack
of reaction not always means the unsuitability of the given
metal compound as a catalyst and that the stage of the
activation of the catalyst precursor for hydrophosphoryla-
tion requires a special attention.
It was previously reported on the strong effect of
the catalytic amounts of Ph2P(O)OH on alkynes hydro-
phosphorylation in the presence of Pd complexes [9,
12, 13]. Our recent study showed that the region- and
stereoselective addition of H-phosphonates to alkynes
was also possible with the catalytic system Pd–PPh3–
CF3COOH [21]. The addition of acid was necessary to
increase the yield of the Markownikoff product and to
improve the chemo- and regioselectivity of the addition.
To our surprise, even small additives of CF3COOH into
the nickel-based catalytic system completely suppressed
the catalytic activity. At the attempt to carry out the reac-
tion of H-phosphonate IIa with diphenylacetylene (Id) in
the presence of 10 mol% of CF3COOH no formation of
olefin IIIb was observed and also no notable conversion
of initial reagents.
The alkyne insertion into the metal–hydrogen bond
was formerly presumed only for the rhodium complexes,
and this reaction resulted in the other product, anti-
Markownikoff isomer in the case of terminal alkynes
[18, 25, 26]. And the explanation of the Markownikoff
regioselectivity in the reactions catalyzed by palladium
and nickel complexes was based just on the suggestion
of the insertion into the metal–phosphorus bond.
Note that depending on the position of substituents R1
and R2 in complexes V and VI both pathways can lead to
the formation of identical reaction products or of regio-
isomers. Strictly speaking, the structure of the reaction
product is not an unambiguous proof of a certain reaction
mechanism in the case of internal alkynes.
Scheme 3.
P(O)(OR3)2
H
III
III
R1
R2
(L)nM
(L)nM
(L)nM
P(O)(OR3)2
R2
R1
H
II
V
VI
P(O)(OR3)2
I
I
(L)nM
H
IV
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 9 2010

THE COMPARISON OF ADDITION OF MOLECULES POSSESSING P(V)–H BOND
1273
The comparative analysis of both routes we performed
by the quantum-chemical calculation using density func-
tional theory B3LYP in the basis Lanl2dz for the metal
and 6-31G(d) for the other atoms. The calculation was
carried out for a model reaction of acetylene insertion in
a complex [Ni(H)(P(O)(OMe)2)(PH3)] (see the figure).
The insertion of acetylene in the nickel–phosphorus bond
from the π-complex VII occurs through the transition
state VIII-TS, and the value of the calculated activation
barrier was 14.5 kcal mol−1. The insertion of acetylene is
an exothermic reaction, and the energy gain at the forma-
tion of complex IX is 26.0 kcal mol−1.
Complexes IX and XI are the model analogs of above
considered compounds V and VI (Scheme 3). The calcu-
lations performed unexpectedly indicate that the alkyne
insertion into the metal–hydrogen bond may occur even
easier than the insertion into the metal–phosphorus bond.
The results obtained prompted us to study the pos-
sibility of the hydrophosphorylation of the triple bond
in alkynes with a catalyst without phosphine ligand. The
reaction proved to be impossible for terminal alkynes Ia
and Ib due to the above mentioned side oligomerization
reaction (Table 3). A little of the hydrophosphorylation
product was found in the reaction of internal alkynes Ic
and Id with H-phosphonate IIa. A considerable amount
of product (20%) formed in the reaction of diphenyl-
acetylene with H-phosphonate IIb, and in the reaction
of H-phosphonate IIc was obtained a good yield (57%).
In the course of attempts to localize the transition
state X-TS for the stage of acetylene insertion into the
metal-hydrogen bond complex XI spontaneously formed.
In come cases its formation occurred already at the stage
of the optimization of the geometry of π-complex VII.
These results evidence the small activation barrier in this
stage (see the figure). The insertion of acetylene into the
Ccязand metal–hydrogen bond is also an exothermic
reaction that leads to the formation of three-coordinate
complex XI with an energy gain of 26.7 kcal mol−1.
It should be stated that the hydrophosphorylation of
alkynes in the absence of a phosphine ligand we are first
to discover. Notwithstanding the low yields and selectiv-
ity compared with the analogous process in the presence
of the ligand (Table 2) this reaction type is promising
for creation of nontoxic and cheap catalytic systems in
keeping with modern trends of the “green” chemistry.
Unlike compound XI the insertion of acetylene into
the metal–phosphorus bond affords a four-coordinate
complex IX due to the interaction with the metal of the
oxygen atom of one of the methoxy groups. The additional
coordination of the oxygen to the metal strbilizes complex
IX and results in comparable values of the reaction ener-
gies 26.0 and 26.7 kcal mol−1. Three-coordinate complex
XI is somewhat higher in energy as expected taking into
account the difference in the activation barriers for the
transition states VIII-TS, X-TS.
It is not excluded that the proper compounds of the
trivalent phosphorus forming as a result of tautomeriza-
tion of H-phosphonate (RO)2PV(O)H ↔ PIII(RO)2(OH)
might coordinate to the metal and act as a ligand. This
assumption is to a certain extent in agreement with the
great difference in the reactivity of the H-phosphonates
(Table 3) that is not observed in the reaction with the
triphenylphosphine as the ligand.
HC CH
ΔE, kcal/mol
H
Ni P(O)(OMe)2
PH3
HC CH
Ni P(O)(OMe)2
HC CH
Ni P(O)(OMe)2
VIII-TS
14.5
H
H
PH3
PH3
VII
X-TS
H
<1.0
0.0
H
H
P(O)OMe
OMe
H
H
H
Ni
Ni P(O)(OMe)2
PH3
PH3
XI
IX
_26.7
_26.0
Calculated potential energy surface for acetylene insertion into the Ni–P and Ni–H bonds.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 9 2010

ANANIKOV et al.
1274
Table 3. Conditions and yields of hydrophosphorylation products of alkynes on Ni(cod)2 in the absence of phosphine ligand
(1 ml of THF, 19 h, 9 mol% of catalyst)
Alkyne
H-phosphonate II
Temperature, °C
Yield of III, %
Residue of II, %
Side products, %
0
100
0
100
C5H11
Ia
O
(i-PrO)2P H
IIa
IIa
100
140
0
100
85
0
3
Ph
Ib
IIa
12
Et
Et
Ic
IIa
120
120
9
80
80
11
0
Ph
Ph
Id
Id
20
O
(PhO)2P H
IIb
Id
120
57
21
22
O
(C12H25O)2P H
IIc
Thus we have shown that the use of an “invalid” model
reaction leads to false results in estimation of relative
catalytic activity of various metal complexes. The neces-
sary conditions of the valid comparison is the absence of
the side reactions involving the chosen reagents and the
necessary activation of the catalyst precursor. We suggest
to use for the comparison of various catalysts based on
the transition metal complexes the diphenylacetylene in
the model reaction of hydrophosphorylation of alkynes.
We suggest as the precursor of the bivalent nickel catalyst
Ni(acac)2/DIBAL.
EXPERIMENTAL
NMR spectra were registered on a spectrometer Bruk-
er Avance (500 MHz) using as internal references TMS
(1H), solvent signals (13C), and aqueous H3PO4 as external
reference (31P). The reaction products were purified by
flash-chromatography on a dry column [27]. Ni(acac)2
before use was dried in a vacuum (0.01– 0.02 mm Hg,
60°C, 30 min).
All reactions were carried out at stirring with a mag-
netic stirrer at temperature-controlled heating on an oil
bath. The reactions were carried out in hermetically
closed test tubes with a screw-top and Teflon gasket. The
manipulations with Ni(cod)2 were performed in the argon
box, the rest of catalysts were charged in air and before
the heating the test tubes were flushed with argon. In
all experiments the THF used was purified and distilled
under argon.
An extremely important result of this research is the
evidence of the alkyne insertion in the metal–hydrogen
bond instead of the traditional concept on the insertion
into the metal–phosphorus bond. The results obtained call
for the reconsideration of the mechanisms of the catalytic
cycles of hydrophosphorylation not only of alkynes but
also of the other unsaturated compounds.
Quantum-chemical calculations. The geometry op-
timization and energy calculation were carried out using
a hybrid potential B3LYP [28–30] in the basis Lanl2dz
[31–34] for metal atoms and the basis 6-31G(d) [35, 36]
for the other atoms. The type of the found stationary
points was controlled by the calculation of the eigenvalues
The found possibility of the “ligandless” hydro-
phosphorylation of alkynes and the exclusion of acid
additives in the reaction catalyzed by nickel complexes
are interesting finds for creation of resource-economical
processes of the selective formation of the carbon–phos-
phorus bond.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 9 2010

THE COMPARISON OF ADDITION OF MOLECULES POSSESSING P(V)–H BOND
1275
of the matrices of the second derivatives of the energy
(the absence of imaginary frequencies for intermediates
and one imaginary frequency for transition states). The
character of the transition states was confirmed by the
calculation of the internal reaction coordinate. The ther-
modynamic functions were calculated in the framework of
the model harmonic oscillator–rigid rotator. All calcula-
tions were carried out applying the software GAUSSIAN
03 [37]. The molecular structures and oscillations were
visualized by the use of the graphic packages MOLDEN
[38] and GABEDIT [39].
alkynes catalyzed by Pd and Ni. Into the test tube was
charged the catalyst, the ligand, and the solvent, the mix-
ture was stirred at room temperature for 3–4 min. To the
obtained solution 1 mmol of H-phosphonate II, 1 mmol
of alkyne I, and 7.7 μl (0.1 mmol) of trifluoroacetic acid
was added. The color of the reaction mixture in the course
of heating did not change (the time and temperature of
the reaction analogous to the experiment without acid).
The catalytic reaction in the absence of phosphine
ligand. A mixture of 214.0 mg (1.2 mmol) of diphenyl-
acetylene and 24.8 mg (0.09 mmol) of Ni(cod)2 in 1 ml
of THF was stirred at room temperature for 3–4 min till
the formation of the homogeneous light-brown solu-
tion. To the obtained solution was added 1 mmol of H-
phosphonate II, then liquid alkynes Ia–Ic. Data on the
time and temperature of the reaction are given in Table 3.
Alkynes hydrophosphorylation catalyzed by Pd
and Ni . A mixture of the catalyst [Pd2dba3 0.03 mmol
(31.1 mg), Ni(acac)2 0.06 mmol (15.4 mg), or Ni(cod)2
0.06 mmol (16.5 mg)], 63 mg (0.24 mmol) of triphe-
nylphosphine, and 0.5 ml of THF was stirred at room
temperature for 3–4 min till the appearance of the yellow-
brown color in the case of Pd2dba3 and Ni(cod)2 and of
the green color in the case of Ni(acac)2. To the solution
obtained was added 1 mmol of H-phosphonate II and
1 mmol of alkyne Ia–Ic. The solid alkyne Id was charged
into the test tube the first (before the catalyst).
The study was carried out under a financial support
of the Russian Foundation for Basic Research (grant no.
07-03-00851) and of the Russian Academy of Sciences
(programs 1, 18).
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nylphosphine, and 1 ml of THF was stirred at room tem-
perature for 3–4 min till the formation of homogeneous
yellow-brown solution, then 1 mmol of H-phosphonate
IIa was added, and the mixture was heated for 4 h at
120°C. On completion of the reaction all compounds
were isolated in pure state by the flash-chromatography,
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obtained compounds were identified by comparison with
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Hydrophosphorylation catalyzed by the system
Ni(acac)2/DIBAL. A mixture of 23.1mg (0.09 mmol)
of Ni(acac)2 and 1 ml of THF was stirred for 5 min, the
obtained homogeneous green solution was cooled to
5°C, afterwards at stirring in the flow of argon was added
0.18 ml of 1 M solution of DIBAL in THF. The solution
from green turned to black. The stirring was continued
for 3 min, then 214 mg (1.2 mmol) of diphenylacetylene,
94.0 mg (0.36 mmol) of triphenylphosphine, 0.167 ml (1
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