Palladium(II)-acetylacetonate complexes containing phosphine and diphosphine ligands and their catalytic activities in telomerization of 1,3-dienes with diethylamine

Article abstract of DOI:10.1016/j.jorganchem.2013.11.017

A series of novel [Pd(acac-O,O′)(P?P)]BF₄ and known complexes [Pd(acac-O,O′)(PR₃)₂]BF₄ (P?P = dppm (1), dppp (2), dppb (3), dppf (4); R = Ph (5), p-Tol (6), i-Pr (7); acac = 2,4-pentanedionato) were prepared by the reaction of [Pd(acac-O,O′)(MeCN)₂]BF₄ (1) with appropriate ligands. Complex 2 was characterized by single-crystal X-ray analysis. Models of the structure and IR wavenumbers assignments of the cations of 1-4 were obtained by DFT calculations. Synthesized complexes were tested as catalysts in the telomerization of isoprene and butadiene with diethylamine. In the case of telomerization of butadiene with diethylamine high catalyst activity (e.g. TOF_av = 1940 h^-1 and TON up to 17,480 for complex 5) was obtained.

Full text of DOI:10.1016/j.jorganchem.2013.11.017

Accepted Manuscript
Palladium(II)-Acetylacetonate Complexes Containing Phosphine and Diphosphine
Ligands and Their Catalytic Activities in Telomerization of 1,3-Dienes with
Diethylamine
Dmitry S. Suslov, Mikhail V. Bykov, Marina V. Belova, Pavel A. Abramov, Vitaly S.
Tkach
PII:
S0022-328X(13)00815-2
10.1016/j.jorganchem.2013.11.017
JOM 18362
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 14 June 2013
Revised Date: 17 October 2013
Accepted Date: 11 November 2013
Please cite this article as: D.S. Suslov, M.V. Bykov, M.V. Belova, P.A. Abramov, V.S. Tkach,
Palladium(II)-Acetylacetonate Complexes Containing Phosphine and Diphosphine Ligands and Their
Catalytic Activities in Telomerization of 1,3-Dienes with Diethylamine, Journal of Organometallic
Chemistry (2013), doi: 10.1016/j.jorganchem.2013.11.017.
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•
A series of novel [Pd(acac-O,O′)(P^P)]BF4 and known complexes [Pd(acac-
O,O′)(PR3)2]BF4 (P^P = dppm (1), dppp (2), dppb (3), dppf (4); R = Ph (5), p-Tol (6), i-
Pr (7); acac = 2,4-pentanedionato) were prepared by the reaction of [Pd(acac-
O,O′)(MeCN)2]BF4 (8) with appropriate ligands
•
•
Models of the structure and IR wavenumbers assignments of the cations of 1-4 were
obtained by DFT calculations.
Synthesized complexes were tested as catalysts in the telomerization of isoprene and
butadiene with diethylamine. In the case of telomerization of butadiene with
diethylamine high catalyst activity was obtained.

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Palladium(II)-Acetylacetonate Complexes Containing Phosphine
and Diphosphine Ligands and Their Catalytic Activities in
Telomerization of 1,3-Dienes with Diethylamine
Dmitry S. Suslov*,†, Mikhail V. Bykov†, Marina V. Belova†, Pavel A. Abramov‡, Vitaly S. Tkach†
† Irkutsk State University, 664003, K. Marks str., 1, Irkutsk, Russia
‡ Nikolaev Institute of Inorganic Chemistry SB RAS, 630090, pr-kt Akad. Lavrentieva, 3,
Novosibirsk, Russia
Keywords: palladium, acetylacetonate, telomerization, isoprene, butadiene, diethylamine,
phosphines
Abstract:
A series of novel [Pd(acac-O,O′)(P^P)]BF4 and known complexes [Pd(acac-O,O′)(PR3)2]BF4
(P^P = dppm (1), dppp (2), dppb (3), dppf (4); R = Ph (5), p-Tol (6), i-Pr (7); acac = 2,4-
pentanedionato) were prepared by the reaction of [Pd(acac-O,O′)(MeCN)2]BF4 (1) with
appropriate ligands. Complex 2 was characterized by single-crystal X-ray analysis. Models of the
structure and IR wavenumbers assignments of the cations of 1-4 were obtained by DFT
calculations. Synthesized complexes were tested as catalysts in the telomerization of isoprene
and butadiene with diethylamine. In the case of telomerization of butadiene with diethylamine
high catalyst activity (e.g. TOFav = 1940 h–1 and TON up to 17480 for complex 5) was obtained.

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INTRODUCTION
Telomerization, linear dimerization of 1,3-dienes with simultaneous addition of a nucleophile
in a catalytic reaction, is a very efficient “green” organic transformation with an overall atom
economy of 100%. Since its discovery 45 years ago [1,2], telomerization has attracted significant
interest due to its robustness and versatility in the production of a wide variety of valuable
products. Easily available starting materials are converted in the presence of a catalyst in a 100%
atom efficient manner to give functionalized octa-2,7-dienes. The resulting products have been
used as intermediates in the total synthesis of several natural products, as well as precursors for
plasticizer alcohols, industrial monomers, solvents, corrosion inhibitors, and non-volatile
herbicides [3–12]. Complexes of palladium are known to effectively catalyze the reaction of
dienes with a variety of nucleophiles. It is also known that the palladium catalyzed dimerization
of butadiene-type substrates can take place, leading to linear or cyclic products, with
chemoselectivity depending on nature of nucleophiles and ligands appended to the reactive
palladium center [13–15].
The telomerization process has been intensively studied by many industrial and academic
laboratories [1,2,16–27]. Studies of the mechanism by Jolly et al. have led to the generally
accepted basic catalytic cycle (for methanol), which has been crucial for further development
[28–31]. Very recently, a detailed DFT studies of Pd -catalyzed 1,3-butadiene (BD)
telomerization of methanol was reported [13,15]
A series of palladium complexes with phosphines, diphospines and NHC (NHC = N-
heterocyclic carbene) ligands were reported for the telomerization of dienes with amines, water
and alcohols [7,12,14,32–34]. Beller and co-workers [35–43] reported the most selective, active,
and productive catalyst, an (NHC)Pd0 complex. In particular, the best-known Pd-catalyst for

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butadiene telomerization of diethylamine gives TON of 17800 molBD/molPd, and TOF of 890 h–1
[36,37].
We reported that acetylacetonate-based cationic palladium complexes with triarylphosphine
ligands, [Pd(acac)(PAr3)2]BF4, can be used as very efficient precursors for the selective
dimerization of styrene (to the best of our knowledge the highest catalyst turnover number ever
reported for this reaction was achieved) [44]. Complexes of such type can be obtained in
different manner: a) by acetylacetonate ligand abstraction from Pd(acac)2 with [CPh3]BF4,
NaBPh4, HBF4·OEt2, CF3SO3H followed by further phosphine-ligand addition[45–48],b) by
reaction of Pd(0) complexes with acetylacetone followed by addition of [CPh3]BF4 [49], c) by
consecutive haloids displacement from starting palladium complex using Tl(acac) and AgClO4
[50], or d) by acetonitrile displacement [51,52]. Only one example of use of
[Pd(acac)(PPh3)2]BF4 in the telomerization of isoprene with amines was reported [53b].
Here we report the results of synthesis of the novel palladium complexes [Pd(acac)(P^P)]BF4
(P^P = dppm, dppp, dppb, dppf) as well as results of [Pd(acac)(PR3)2]BF4 or
[(acac)Pd(P^P)]BF4-catalyzed telomerization of isoprene and butadiene with diethylamine.

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RESULTS AND DISCUSSION
Scheme 1
Complex Synthesis. The synthetic procedures followed for the preparation of complexes 1-7
are summarized in Scheme 1. Methodology requires complex 8, which can be prepared starting
from Pd(acac)2, MeCN and HBF4·OEt2 [47]. The cationic complexes were prepared in near
quantitative yields. The structures of compounds 1-4 have been confirmed by the usual
techniques (1H, 13C, 31P, and 11B NMR, FTIR, and elemental analysis). Due to the insolubility in
available solvents complex 1 was characterized only by means of FTIR and elemental analysis.
Structural details and Gibbs free energy for the cations of complexes 1-4 were obtained by our
ZORA-BP86 calculations (Table 1, Figure 1). Comparison between observed and DFT-
calculated IR wavenumbers for complexes 1-4 is presented in Table 2. In addition, the structure
of compound 2 was also confirmed by single-crystal X-ray diffraction analysis.
Table 1. DFT-calculated (ZORA-BP86) structural parameters (bond lengths, Å; angles, °) and
Gibbs free energy (kcal/mol) of reactions (see Scheme 1) for the cations of 1-4.

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1
2
3
4
[Pd-O]av
[Pd-P]av
P-Pd-P
O-Pd-O
G
2,06
2,29
74,4
92,5
-34,8
2,07
2,30
94,4
91,3
-44,7
2,07
2,31
94,4
91,2
-44,3
2,07
2,33
98,8
90,8
-40,7
Figure 1. Optimized structure for cation of complex 4, hydrogen atoms are ommited for clarity.
Complex [Pd(acac)(dppp)]BF4 (4) crystallizes from CH2Cl2/Et2O as light-yellow
conglomerates of crystals. It possesses C2/c space group with a = 28.8084(6) Å,
b = 14.2418(3) Å, c = 15.7720(3) Å, and β = 94.919(1) Å. In the crystal structure there are
cations [Pd(acac)(dppp)]+ with Pd(II) in a square planar coordination (Figure 2) and highly
-
disordered BF4 anions. The DFT calculated structure (Table 1) agrees well with the
experimental data (Figure 2). The Pd-O and Pd-P distances in the complexes described in
literature are given in Table 3. As can be seen, all calculated and observed distances are in a
good agreement with the corresponding values of known phosphine-acetylacetonate Pd
complexes.

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Table 2. Comparison between observed and DFT-calculated (ZORA-BP86) IR spectra
(wavenumbers ,cm-1) for the cations of palladium complexes 1-4.
Assignment
ν(C=O and C=C)
δ(C–H in CH3)
IR
Calcd, unscaled
1559, 1529
1426, 1343
1260
1553, 1518
1437, 1366
1270
1
ν(C–CH3, C=O and C=C)
δ(C–H in CH)
1190, 777
762, 738, 716, 687
1559, 1516
1435, 1343
1269
1184, 780
744, 721, 713, 686
1560, 1529
1424, 1343
1260
δ(CH in Ph and CH2)
ν(C=O and C=C)
δ(C–H in CH3)
2
ν(C–CH3, C=O and C=C)
δ(C–H in CH)
1189
1185
δ(C–H in CH2)
1157, 835, 793
1421, 745, 690
1571, 1517
1438, 1368
1276
1144, 819, 768
1400, 730, 686
1563, 1530
1426, 1343
1261
δ(CH from Ph)
ν(C=O and C=C)
δ(C–H in CH3)
ν(C–CH3, C=O and C=C)
δ(C–H in CH)
3
1189
1184
δ(C–H in CH2)
1165, 906, 844, 797
1422, 742, 692
1555, 1514
1434, 1366,
1261
1110, 896, 844, 775
1403, 726, 682
1562, 1529
1426, 1343
1261
δ(CH in Ph)
ν(C=O and C=C)
δ(C–H in CH3)
ν(C–CH3, C=O and C=C)
ν(C–C in Cp)
δ(C–H from CH and Cp)
δ(CH from Ph)
4
1171
1160
1197, 826
749, 690
1180, 814
730, 684

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Figure 2. ORTEP plot (50% thermal ellipsoids) of the X-ray crystal structure of cation of
compound 2. BF4 was omitted for clarity. Selected bond lengths [Å] and angles [°]: [Pd-O]av,
2.052(3), [Pd-P]av, 2.2466(12), P-Pd-P, 90.90(4),O-Pd-O, 90.54(13).
Table 3. Average Pd-O and Pd-P distances in the palladium(II)-acetylacetonate complexes
containing phosphine ligands described in literature.
Complex
[Pd-O]av [Pd-P]av
ref.
2.082
2.065
2.034
2.046
2.019
2.111
2.031
2.026
2.022
2.053
2.246
2.252
2.265
2.268
2.281
2.237
2.251
2.259
2.259
2.266
[55]
[55]
[56]
[57]
[57]
[58]
[59]
[59]
[50]
[54]
(NBu4)[(acac)Pd(µ-PPh2)2Pt(C6F5)2]·(CH3)CO
[(acac)Pd(µ3-PPh2)2Pt2(C6F5)2AgPh]·CH2Cl2
[Pd(acac)(PPh3)2]BF4·H2O
[Pd(CH3COCHCOCH2PhNO2)(PPh3)2]BF4
[Pd(CH3COC(Ph(NO2)2)COCH3)(PPh3)2]BF4
[(hfa)Pd(µ-PPh2)2Pd(hfa)]·CHCl3
[Pd(acac)((Ph2P)2binaphthyl)]BF4
[Pd(acac)((Ph2P)2binaphthyl)]BF4·CH2Cl2
[Pd(acac)(PPh3)2]ClO4
[Pd(acac)((MePhP)2Fc)]BF4

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Synthesis of the complex [Pd(acac)(dppe)]BPh4 was reported by Basato et al [46,60]. In spite
of DFT-calculated Gibbs free energy of acetonitrile exchange reaction by dppe was of the same
value (-45.4 kcal/mol) as for other diphosphines, our attempts to prepare complex with the
similar cation [Pd(acac)(dppe)]BF4 failed. The reaction of 8 with dppe were performed initially
in CH2Cl2, but the complex generated was unstable and decomposed upon workup. 31P NMR
spectrum of the reaction mixture showed signals at 25.8, 58.0, and 63.5 ppm which we assigned
to the complex cations with following formal fragments: dppe-bridged [Pd(ꢀ-dppe)Pd]2+,
dicationic [Pd(dppe)]2+ and monocationic [Pd(dppe)]+ respectively. For comparison 31P NMR
chemical shifts for [Pd2(ꢀ-dppe){PPh(C6H4S)2}2] is 20.9 ppm [61], for [Pd(dppe)2](OAc)2 is 58.7
ppm, and for (OAc)2Pd(dppe) is 63.4 ppm [62]. We assume that this is due to the transformation
of [(acac)Pd(dppe)]BF4 to ½Pd(acac)2 and ½[Pd(dppe)2](BF4)2 with formation of dppe-bridged
by-product by analogy with data reported for Pd(OAc)2 [62–64] and Pd(dppe)Cl2 [65]. The
nature of this phenomenon is the subject of special study.
Telomerization of 1,3-butadiene with diethylamine. In exploratory experiments using
individual complex 5 as catalyst we discovered that addition of boron trifluoride etherate as co-
catalyst is not required to obtain active catalyst, opposite to the results for dimerization of styrene
[44]. Optimum temperature was found to be 70°C, at higher temperature catalyst decomposition
occurs. Palladium complexes 1-8 were tested in the model reaction of diethylamine with 1,3-
butadiene (Scheme 2, Table 4). Even at very low catalyst concentration conversions up to 91.0%
and excellent selectivity (99.9%) were observed with complex 7. To our delight whatever the
ligand present on the palladium, only the linear telomerization product is formed.
Telomerizations of butadiene with secondary amines show considerably higher selectivity
compared to much more studied the telomerization in the presence of alcohol [12]. The ligand

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structure is known to influence the product ratio in the telomerization reaction, but factors
explaining the changes in chemo- and regioselectivity remained unraveled. Subtle changes in
concentration of reagents, solvent, promoter, and reaction progress influence the selectivity of
the telomerization reaction [33]. As it was shown by Drent [26], raising the temperature up to
135°C lead to formation of by-product octatriene up to 8% along with N,N-diethyl-2,7-
octadienylamine. Similar temperature dependence of dimerization side-reaction in telomerization
of butadiene with methanol was analyzed in details in recent review by van Leeuwen et al. [33]
We also performed catalyst activity studies in which conversion, product yield and selectivity
were continuously measured. In Figure 3 selected runs using complex 5 formed in situ at 70°C
are shown at different BD:Pd ratio. The conversion of ~50% of butadiene was observed after
0.5h with selectivity of >99% toward the linear telomerization product and reaction nearly
complete after 3 h.
100
90
80
70
60
1
2
50
40
30
20
10
0
0
1
2
3
t / h
Figure 3. Activity, expressed as yields of octa-2,7-dienyldiethylamine as a function of reaction
time. (Complex 5 was formed in situ by reaction of 8 with 2PPh3 in dichloromethane. Reaction
conditions: (1) BD:Pd = 6000, Et2NH:Pd = 3000, 1.3·10-5 mol Pd, 70ºC, 3 h, 0.5 ml CH2Cl2 (2)
BD:Pd = 3000, Et2NH:Pd = 6000, 0.65·10-5 mol Pd, 70ºC, 3 h, 0.5 ml CH2Cl2)

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For complex 1 with dppm ligand, the methylene group in the diphosphine backbone led to
dramatically reduced yield (Table 4). This could be simply explained by the poor solubilization
of the complex 1, since dppm based Pd catalyst showed comparable activity in telomerization
with long-chained homologues [24]. Complex 8 showed almost no activity. Comparing results
for telomerization of butadiene with diethylamine in terms of TOF and TON (up to 17480) with
literature data shows that 2,3 and 5-7 should be regarded as highly efficient catalysts [12,36].
Scheme 2
Table 4. Telomerization of 1,3-butadiene with diethylamine
TOFc,
TONc,
Entry Catalyst Yielda, % Selectivityb, %
molBD/(molPd·h) molBD/molPd
1
2
3
4
5
6d
7
8
9
10.6
79.4
76.6
49.0
71.1
87.4
73.8
91.0
0.3
99.9
99.9
99.9
99.9
99.9
99.9
99.9
99.9
-
210
640
1
2
3
4
5
5
6
7
8
1590
1530
980
4760
4600
2940
4270
17480
4430
5460
~20
1420
1940
1480
1820
~6
Reaction conditions: 1,3-butadiene:Pd = 6000, Et2NH:Pd = 3270, 1.3·10-5 mol Pd (0.016 mol%
with respect to 1,3-butadiene), 70ºC, 3 h.
aYield of octa-2,7-dienyldiethylamine.
bSelectivity toward octa-2,7-dienyldiethylamine.

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cCatalyst turnover frequency(number) with respect to 1,3-butadiene
dReaction conditions: 1,3-butadiene:Pd = 20000, Et2NH:Pd = 10000, 1.3·10-5 mol Pd (0.005
mol% with respect to 1,3-butadiene), 70ºC, 9 h.
Telomerization of isoprene with diethylamine. The telomerization reaction of isoprene and
diethylamine catalyzed by complexes 1-6 gives four isomers as major reaction products (Scheme
3). The telomerization reaction of isoprene and diethylamine catalyzed by a 2:1 mixture of PPh3
and PdCl2 has been reported to give isomer IV as the largest component (28%) of the product
mixture (Scheme 3) [66]. In our case, when the complexes 1-6 used as catalyst isomer I becomes
the major component of the product mixture (Table 5, entry 1-6). Detailed studies of the reaction
(influence of the ligand, palladium precursor, reaction conditions, solvent, L/Pd ratio) using other
types of palladium precursors was described by Finn et al. [67] and Keim et al. [53a,b]. The
same selectivities to tail-to-head isomer were reported using PdCl2- [67] and [(cod)Pd(η3-
allyl)]BF4- based [53a,b, 67] systems with similar ligands, e.g. PPh3, P(p-Tol)3 and dppp
(phosphine:Pd ratio of 1:1) [67]. Selectivity profile for complex 5 in MeCN (Table 5, entry 10)
are comparable with the literature data [53b]. MeOH proved to be a better solvent than other
organic solvents, especially with respect to selectivity towards telomers. Using MeCN, CH2Cl2,
or CH3NO2 as solvents substantially decrease selectivity towards telomers (Table 5, entry 9-12).
The reaction profile also changed dramatically with addition of Lewis acid, 20BF3·OEt2, as co-
catalyst. In this case, more products of amination (Table 6, entry 13-14) were obtained or,
furthermore, polymeric products (Table 5, entry 15-16) were observed in the reaction mixture.
The highest selectivity for tail-to-head coupling (giving a 59.4%) was observed with the dppm
ligand, although the reaction was very slow. Complex 8 showed no activity in these conditions.
Activity increase is observed on going to 1 equiv. of phosphine (entry 7), and the rate falls when

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2 equiv is used (entry 8). These data are consistent with results by Finn et al. where a similar
trend was observed. Authors speculated that “as more PPh3 is added, Pd(PPh3)2 complexes are
generated, which are relatively inactive compared with the monophosphine species, causing a
drop in observed rate” [67].
Scheme 3

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Table 6. Telomerization of isoprene with diethylamine
Selectivity
Amt of telomers
Catalyst
system
Entry
Solvent
Conversion
Products of
Telomers
I
II
III
IV
aminations
1
2
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeCN
CH2Cl2
CH3NO2
MeOH
MeCN
8,00%
44,00%
83,00%
96,00%
75,00%
100,00%
94,00%
82,40%
78,00%
79,00%
84,00%
71,00%
67,00%
93,00%
100%
100%
99%
99%
95%
96%
99%
99%
94%
86%
83%
49%
69%
44%
0%
59,4%
51,0%
51,2%
51,3%
48,3%
47,8%
52,6%
48,1%
49,4%
44,9%
41,3%
38,0%
58,0%
38,2%
28,6%
23,0%
24,0%
21,2%
23,7%
26,0%
18,0%
21,9%
26,4%
32,5%
36,5%
48,4%
31,5%
53,4%
7,0%
15,9%
15,0%
16,5%
14,3%
14,4%
16,8%
16,3%
12,8%
10,4%
9,8%
5,0%
10,0%
9,8%
1
0%
2
3
1%
3
4
1%
10,9%
13,6%
11,8%
12,7%
13,7%
11,3%
12,2%
12,3%
7,1%
4
5
5%
5
6
4%
6
7
8/1PPh3
1%
8
8/2PPh3
1%
9
6%
5
10
11
12
13
14
14%
17%
51%
31%
56%
5
5
6,5%
5
5/20BF3·OEt2
5/20BF3·OEt2
6,6%
3,9%
4,1%
4,3%
polymeric
product
15
16
CH2Cl2
5/20BF3·OEt2
5/20BF3·OEt2
–
–
–
–
–
–
–
–
–
–
–
–
polymeric
product
CH3NO2
Reaction conditions: isoprene/Pd=200, 2.5·10-5 mol Pd (0.5 mol%), 0.5 mL of isoprene, 0.5 mL of NHEt2, 0.5 mL
of solvent, 25°C, 20 h.
CONCLUSION
New cationic palladium complexes containing diphosphines were prepared in good yields. The
tests of the [Pd(acac-O,O′)(P^P)]BF4 and [Pd(acac-O,O′)(PR3)2]BF4 complexes revealed the high
potential of 2, 3, 5-7 for butadiene telomerization of diethylamine.

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EXPERIMENTAL SECTION
General Information. All air- and/or moisture-sensitive compounds were manipulated by
using standard high-vacuum line, Schlenk, or cannula techniques under an argon atmosphere.
Diethyl ether and benzene were distilled from sodium−benzophenone. CH2Cl2, CH3NO2,
CH3CN, diethylamine and isoprene were distilled from CaH2. Solvents were stored over
molecular sieves. All glassware were dried for at least 3 h in a 180°C oven and cooled under an
argon atmosphere. All NMR spectra were recorded at room temperature on a Varian 500S
1
spectrometer. Chemical shifts refer to signals of tetramethylsilane in the case of H and 13C
31
11
spectra, H3PO4 in the case of P, and BF3·OEt2 in the case of B. Compound 8 was prepared
according to literature procedures [47]. All other reagents were obtained commercially and used
as received.
Preparation of [Pd(acac)(dppm)]BF4 (1). To the mixture of dppm (0,577 g, 1.5 mmol) and 1
(0,562 g, 1.50 mmol) was added Et2O (50 mL). Then, the reaction mixture was stirred for 2 h at
ambient temperature. The resulting reaction mixture was filtered, and residue was dried under
vacuum to yield an orange solid (0.926 g, 91%). The product was insoluble in acetone.
chloroform, DMSO, methylene chloride, and nitromethane. IR, cm–1: ν(C=O and C=C), 1553, 1518;
δ(C–H from CH3 in acac), 1437, 1366; ν(C–CH3 in acac), 1270; δ(C–H from CH in acac), 1190, 777; δ(CH in Ph and CH2)
,
762, 738, 716, 687; ν(B–F in BF4), 1150-980. Anal. Calcd for C30H29BF4O2P2Pd: C, 53.24; H,
4.32%. Found: C, 53.10; H, 4.24%. Since there were no evidences for η2-coordination of dppm,
one can suppose that complex 3a is oligomeric material with the following formula [Pd(acac)n(ꢀ-
dppm)]n[BF4]n.
Preparation of [Pd(acac)(dppp)]BF4(2). dppp (0,619 g, 1.50 mmol) was dissolved in
dichloromethane (40 mL) and 1 (0,562 g, 1.50 mmol) was slowly added. Then, the reaction

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mixture was stirred for 1 h at ambient temperature. The resulting yellow solution was filtered,
and the solvent of the filtrate was removed under reduced pressure. The residue was washed with
1
Et2O (3 × 5 mL) and dried under vacuum to yield a yellow solid (0.850 g, 85%). H NMR
(CDCl3): δ 7.7-7.2 (m, 20H, CH, Ph), 5.3 (s, 1H, CH), 2.9-2.7 (m, 6H, CH2), 1.6 (6H, CH3).13C
NMR (CDCl3): δ 187.4 (s, C=O), 139.0 (d, o-CH, Ph), 132.6 (d, p-CH, Ph), 129.5 (d, m-CH, Ph),
128.5 (s, C, Ph), 100.1 (d, CH), 26.0 (q, CH3), 26.0 (t, CH2), 23.7 (t, CH2). 31P NMR (CDCl3): δ
37.5. 11B ((CD3)2CO): δ -0.54 (quintet, BF4). Anal. Calcd for C32H33BF4O2P2Pd: C, 54.53; H,
4.72%. Found: C, 54.60; H, 4.79%.
Preparation of [Pd(acac)(dppb)]BF4 (3). dppb (0,639 g, 1.50 mmol) was dissolved in Et2O
(20 mL), 1 (0,562 g, 1.50 mmol) was slowly added, and 20 mL of Et2O were added. Then, the
reaction mixture was stirred for 1 h at ambient temperature. The resulting reaction mixture was
1
filtered, and residue was dried under vacuum to yield a lemon-yellow solid (1.029 g, 96%). H
NMR (CDCl3): δ 7.8-7.2 (m, 20H, CH, Ph), 5.4 (1H, CH), 3.5(2H, CH2), 2.8(2H, CH2), 2.1(2H,
13
CH2), 1.7 (6H, CH3), 1.3 (2H, CH2). C NMR (CDCl3): δ 187.7 (s, C=O), 134.0 (d, o-CH, Ph),
132.5 (d, p-CH, Ph), 129.5 (d, m-CH, Ph), 126.5 (s, C, Ph), 100.3 (d, CH), 26.0 (q, CH3), 23.3 (t,
31
11
CH2), 18.9 (t, CH2). P NMR (CDCl3): δ 40.3. B ((CD3)2CO): δ -0.55 (quintet, BF4). Anal.
Calcd for C33H35BF4O2P2Pd: C, 55.14; H, 4.91%. Found: C, 54.82; H, 5.01%.
Preparation of [Pd(acac)(dppf)]BF4 (4). To the mixture of dppf (0,187 g, 0.337 mmol) and 1
(0.127 g, 0.337 mmol) was added Et2O (20 mL). Then, the reaction mixture was stirred for 2 h at
ambient temperature. The resulting reaction mixture was filtered, and residue was dried under
1
vacuum to yield a red solid (0.262 g, 92%). H NMR (CDCl3): δ 8.0-7.2 (m, 20H, CH, Ph), 5.4
13
(1H, CH), 4.8 (4H, CH, Cp*), 4.5 (4H, CH, Cp*), 1.6 (6H, CH3). C NMR (CDCl3): δ 186.5 (s,
C=O), 134.4 (d, o-CH, Ph), 132.6 (d, p-CH, Ph), 129.2 (s, C, Ph), 129.1 (d, m-CH, Ph), 101.7 (d,

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CH), 78.2 (d, CH, Cp*), 76.5 (d, CH, Cp*), 25.7 (q, CH3). 31P NMR (CDCl3): δ 43.5. Anal. Calcd
for C40H38BF4FeO2P2Pd: C, 55.75; H, 4.44%. Found: C, 55.49; H, 4.17%.
Preparation of [Pd(acac)(PPh3)2]BF4 (5). PPh3 (0,750 g, 2.78 mmol) was dissolved in
dichloromethane (10 mL) and 1 (0,520 g, 1.39 mmol) was slowly added. Then, the reaction
mixture was stirred for 0.5 h at ambient temperature. The resulting yellow solution was filtered,
and the solvent of the filtrate was removed under reduced pressure. The residue was washed with
Et2O (3 × 5 mL) and dried under vacuum to yield an yellow solid (1.056 g, 93%). 1H NMR
(CDCl3): δ 7.2–7.8 (m, 30H, Ph), 5.6 (s, 1H, CH), 1.5 (s, 6H, CH3).13C NMR ((CD3)2CO): δ
188.4 (s, C=O), 128-136 (m, Ph), 102.3 (d, CH), 27.5 (q, CH3). Spectroscopic data were found
to match literature data [45,48].
Preparation of [Pd(acac)(P(p-Tol)3)2]BF4 (6). P(p-Tol)3 (0,913 g, 3.00 mmol) was dissolved
in dichloromethane (20 mL) and 1 (0,562 g, 1.50 mmol) was slowly added. Then, the reaction
mixture was stirred for 1 h at ambient temperature. The resulting yellow solution was filtered,
and the solvent of the filtrate was removed under reduced pressure yielding an yellow solid
(1.283 g, 95%). 1H NMR (CDCl3): δ 7.2–7.6 (m, 24H, Ar), 5.5 (s, 1H, CH), 2.4 (s, 18H, Ar), 1.5
(s, 6H, CH3).13C NMR ((CD3)2CO): δ 186.2 (s, C=O), 141.5 (d, p-CH, Ar), 134.0 (d, o-CH, Ar),
129.3 (d, m-CH, Ar), 100.4 (d, CH), 26.0 (q, CH3), 21.3 (q, CH3, Ar). Spectroscopic data were
found to match literature data [45,48].
Preparation of [Pd(acac)(P(i-Pr)3)2]BF4 (7). P(i-Pr)3 (0,490 g, 3.06 mmol) was dissolved in
dichloromethane (20 mL) and 1 (0,573 g, 1.53 mmol) was slowly added. Then, the reaction
mixture was stirred for 1 h at ambient temperature. The resulting yellow solution was filtered,
and the solvent of the filtrate was removed under reduced pressure. The residue was washed with
cold (~-15°C) Et2O (3 × 5 mL) and dried under vacuum to yield a bright-yellow solid (0.871 g,

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93%). 1H NMR (CDCl3): δ 5.5 (1H, CH), 2.5 (6H, CH3), 2.0 (6H, CH), 1.4 (36H, CH3).13C NMR
(CDCl3): δ 185.7 (s, C=O), 100.7 (d, CH), 26.0 (q, CH3), 24.3(d, CH), 19.9 (q, CH3).
Spectroscopic data were found to match literature data [68].
Calculations. All density functional theory (DFT) calculations were performed with the
ORCA program [69]. All geometry optimizations were run with tight convergence criteria, using
the BP86 functional [70,71], making use of the resolution of the identity (RI) technique [72]. The
applicability of gradient-corrected functionals as BP86 for the structural prediction of transition
metal compounds is well documented [73–76]. The basis sets that were used were the
Weigend−Ahlrichs basis sets [77,78]. Triple-ξ-quality basis sets with one set of polarization
functions (def2-TZVP) were used for the palladium, iron and the phosphorus atoms. The
remaining atoms were described by slightly smaller def2-SVP basis sets. A scalar relativistic
correction was applied using the zeroth-order regular approximation (ZORA) method [79–82].
Figure 1, and figures in Supporting Information were generated with Gabedit 2.3.0 [83].
X-ray Diffraction Studies
Crystallographic data and refinement details are given in Table 6. The diffraction data were
collected on a Bruker X8Apex CCD diffractometer with MoKα radiation (λ = 0.71073 Å) by
doing φ and ω scans of narrow (0.5°) frames at 296 K. Structure of 3b was solved by direct
method and refined by full-matrix least-squares treatment against F2 in anisotropic
approximation with SHELXTL programs set [84].Absorption corrections were applied
empirically with SADABS program [85]. All non-hydrogen atoms of [Pd(acac)(dppp)]+ were
refined anisotropically. The hydrogen atoms were refined in their geometrically calculated
-
positions; a riding model was used for this purpose. BF4 anion was found to be disordered over
three close positions with 0.4/0.3/0.3 occupancy ratio. Since anion is highly disordered with

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small occupancies, their atoms were refined in isotropic approximation. Further details may be
obtained from the Cambridge Crystallographic Data Center on quoting the depository numbers
CCDC 896672. This information may be obtained free of charge from
http://www.ccdc.cam.ac.uk.
Table 7. Experimental details
Chemical formula C32H33BF4O2P2Pd
Mr
704.73
Crystal
space group
system,
Monoclinic, C2/c
Temperature (K)
a, b, c (Å)
β (°)
296
28.8084(6), 14.2418(3), 15.7720(3)
94.919 (1)
6447.2 (2)
8
V (Å3)
Z
F(000)
2864
Radiation type
µ (mm-1)
Mo Kα
0.73
Crystal size (mm) 0.30 × 0.22 × 0.15
Bruker
Diffractometer
Nonius
X8Apex
CCD
diffractometer
Absorption
correction
Multi-scan SADABS (Bruker-AXS, 2004)
Tmin, Tmax
0.812, 0.899
No. of measured,
independent
observed
2σ(I)] reflections
and
>
42878, 4973, 4022
0.069
[I
Rint

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Range of h, k, l
R[F2 2σ(F2)],
-32≤ h ≤32, -16≤ k ≤16, l = -17≤ l ≤17
>
0.041, 0.136, 1.13
wR(F2), S
No. of reflections,
parameters,
4973, 386, 0
restraints
2
w
=
1/[σ2(Fo )
+
(0.0866P)2
+
2.9504P]
Weighting scheme
2
2
where P = (Fo + 2Fc )/3
∆ρmax, ∆ρmin (e Å-3)
0.78, -0.94
Computer programs: APEX2 (Bruker-AXS, 2004), SAINT (Bruker-AXS, 2004), SHELXS97
(Sheldrick, 1998), SHELXL97 (Sheldrick, 1998), SHELXTL (Bruker-AXS, 2004), CIFTAB-97
(Sheldrick, 1998).
General procedure for catalytic telomerizations of 1,3-butadiene. Palladium complex
(0.013 mmol) was added in a dried and sealed vessel under argon. The stainless steel autoclave
was cooled with liquid nitrogen and 4.2 g (78 mmol) of 1,3-butadiene was condensed (volume
and mass control). Afterwards cold (-15°C) diethylamine (5.4 mL, 42.5 mmol) was added via
syringe into the cooled (-10°C) autoclave and the vessel was heated to the desired reaction
temperature. After 3 h the autoclave was cooled to room temperature and 1 mL of benzene as
internal standard was added. In general, the yield of telomers was determined by GC. The main
product was isolated from the reaction mixture via distillation and analyzed by GC-MS and
1H,13C NMR.
General procedure for catalytic telomerizations of isoprene. Palladium complex (0.025
mmol), MeOH (0.5 mL), isoprene (0.5 mL, 5 mmol), and diethylamine (0.5 mL) were stirred for
20 h at 25°C. The yield of telomers was determined by GC/GS-MS.
ASSOCIATED CONTENT
Supporting Information.

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Optimized geometries, energies, Cartesian coordinates for all the calculated species, and
crystallographic data for 3b (in CIF format).
AUTHOR INFORMATION
Corresponding Author
*E-mail: suslov.dmitry@gmail.com, suslov@chem.isu.ru
ACKNOWLEDGMENT
We thank G.V. Ratovsky, Irkutsk State Universisty, and M.N. Sokolov, Nikolaev Institute of
Inorganic Chemistry, for helpful discussions. This research was supported by the Ministry of
Education and Science of the Russian Federation, contract N14.132.21.1461.
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A series of novel [Pd(acac-O,O′)(P^P)]BF4 complexes [Pd(acac-O,O′)(PR3)2]BF4
(P^P = dppm (1), dppp (2), dppb (3), dppf (4)) were prepared
Models of the structure and IR wavenumbers assignments of the cations of 1-4 were
obtained by DFT calculations.
Synthesized complexes were tested as catalysts in the telomerization of isoprene and
butadiene with diethylamine. In the case of telomerization of butadiene with
diethylamine high catalyst activity was obtained.