Synthesis and molecular structures of divalent bridged bis(guanidinate) europium complexes and their application in intermolecular hydrophosphination of alkenes and alkynes

Article abstract of DOI:10.1039/c6nj02508k

The reaction of anhydrous EuCl₃ with one equiv. of lithium salt of a three-carbon bridged bis(guanidinate) Li₂L¹ (L¹ = [ⁱPr(Me₃Si)NC(NⁱPr)N(CH₂)₃NC(NⁱPr)N(SiMe₃)ⁱPr]) in THF afforded chloride Eu^IIIL¹Cl(THF)₂ (1). The reduction reaction of complex 1 with Na/K alloy in a molar ratio of 1?:?1.2 in THF gave a novel Eu^II complex supported by an unexpected new bridged bis(guanidinate) ligand L³, [Eu^IIL³]₂ (L³ = [ⁱPr(Me₃Si)NC(NⁱPr)N(CH₂)₃N(SiMe₃)C(NⁱPr)₂]) (2), through the redistribution of one guanidinate in L¹ during the reduction. Complex 2 was structurally characterized to be a binuclear complex in which two Eu metals are connected together by two L³ ligands that adopted a μ-η¹:η²:η² coordination mode for one L³ ligand and a μ-η²:η²:η² mode for the other. Treatment of the in situ formed Eu^IIIL²Cl(THF)₂ (L² = 1,8-C₁₀H₆{NC(NⁱPr)(NHⁱPr)}₂) by the reaction of EuCl₃ with 0.5 equiv. of [Li₂L²₂Li₂] in THF with Na/K alloy yielded a novel Eu^II complex [Eu^IIL²(THF)]₂ (3) in good yield. Complex 3 was characterized by an X-ray crystal structure analysis. Complex 3 features an unusual μ-η¹:η²:η² coordination mode of the bridged bis(guanidinate) ligand onto Eu^II. Complexes 2 and 3 are efficient pre-catalysts for the intermolecular hydrophosphination of alkenes and alkynes to give exclusively anti-Markovnikov products and mainly anti-addition products for the alkyne reactions. For these transformations, the best performances were observed with complex 2.

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Synthesis and molecular structures of divalent bridged
bis(guanidinate) europium complexes and their application in
intermolecular hydrophosphination of alkenes and alkynes
Received 00th January 20xx,
Accepted 00th January 20xx
Qianqian Liu, Chuanyong Wang, Xingmin Zhang, Mingqiang Xue,* Yingming Yao, Yong Zhang
and Qi Shen*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Reaction of anhydrous EuCl3 with one equiv. of lithium salt of a threeꢀcarbon bridged bis(guanidinate) Li2L1 (L1 = [iPr(Me3
Si)NC(NiPr)N(CH2)3NC(NiPr)N(SiMe3)iPr]) in THF afforded the chloride EuIIIL1Cl(THF)2 (1). Reduction reaction of compl
ꢀex 1 with Na/K alloy in a molar ratio of 1:1.2 in THF gave a novel EuII complex supported by an unexpected new bridged b
ꢀis(guanidinate) ligand L3, [EuIIL3]2 (L3 = [iPr(Me3Si)NC(NiPr)N(CH2)3N(SiMe3)C(NiPr)2]) (2), through the redistribution of
one guanidinate in L1 during the reduction. Complex 2 was structurally characterized to be a binuclear complex in which tw
ꢀo Eu metals are connected together by two L3 ligands adopted a ꢁꢀη1:η2:η2 coordination mode for one L3 ligand and a ꢁꢀη2:
η2:η2 mode for the other. Treatment of the in situ formed EuIIIL2Cl(THF)2 (L2 = 1,8ꢀC10H6{NC(NiPr)(NHiPr)}2) by the reacti
ꢀon of EuCl3 with 0.5 equiv. of [Li2L22Li2] in THF with Na/K alloy yielded a novel EuII complex [EuIIL2(THF)]2 (3) in good
yield. Complex 3 was characterized by an Xꢀray crystal structure analysis. Complex 3 features an unusual ꢁꢀη1:η2:η2 coordin
ꢀation mode of the bridged bis(guanidinate) ligand onto EuII. Complexes 2 and 3 are efficient preꢀcatalysts for the intermolec
ꢀular hydrophosphination of alkenes and alkynes to give exclusively antiꢀMarkovnikov products and mainly antiꢀaddition pr
ꢀoducts for the alkyne reactions. For these transformations, the best performances were observed with complex 2.
progress has been made in the field of alkaline earth metal7 and
transition metal complexes.8 However, the application of LnII
complexes in this transformation has still attracted much less
Introduction
Divalent lanthanide (LnII) complexes, due to their pronounced
reductive properties1 and larger ion radii,2 have received
increasing interest as catalysts or preꢀcatalysts in various
transformations of unsaturated and saturated substrates such as
polymerization and organic reactions, and much progress has
been made.3ꢀ4 Hydrophosphination, the addition of the P–H
bond of a primary or secondary phosphine to an unsaturated C–
C bond, provides a potentially powerful and atomꢀeconomic
process to organic phosphine derivatives, which are an
important class of compound widely employed as synthetic
reagents in organic synthesis5 and as ligands for transitionꢀ
metal complexes in organometallic catalysis.6 Metalꢀcatalyzed
hydrophosphination was revealed to be an attractive method
that generally offers better control over regioꢀ and stereoꢀ
selectivity. Therefore, development of efficient metal catalysts
for hydrophosphination becomes one of the most interesting
themes in organometallic and organic chemistry. Much
attention till 1998,9 even the intramolecular hydrophosphination
by LnIII has been well documented.10 Very recently, the
intermolecular hydrophosphination has made success by use of
LnII amide complexes,11 such as YbII amide species supported
by tridentate iminoꢀamidinate,7a amide complexes of YbII and
EuII bearing an iminoanilide ligand,7b YbII amide complexes
stabilized by amidinate and 1,3,6,8ꢀtetraꢀtertꢀbutylcarbazolꢀ9ꢀyl
ligands11a,11b and heteroleptic amido YbII and SmII complexes
bearing aminoetherꢀphenolate ligands11c as well as YbII amide
complexes stabilized by Nꢀheterocyclic carbene ligands.11d All
these amide complexes were found to catalyze the
intermolecular hydrophosphination of alkenes and alkynes with
high activity and selectivity to afford antiꢀMarkovnikov regioꢀ
specific product under mild conditions.
EuII complexes, in comparison with the YbII and SmII
analogues, have received much less attention as active species
in homogeneous catalysis. Therefore, development of novel
EuII complexes as efficient catalysts in homogeneous catalysis
is required. Our recent work indicated that the EuII complexes
bearing two βꢀdiketiminate ligands are highly active preꢀ
catalysts (even more active than the YbII analogue) for catalytic
addition of amines to carbodiimides to substituted guanidines.
Moreover, they show different reaction mode from that with
SmII and YbII complexes, no oxidation step was included in the
a.The Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry,
Chemical Engineering and Materials Science, Dushu Lake Campus, Soochow
University, Suzhou 215123, People’s Republic of China.
b.E-mail: xuemingqiang@suda.edu.cn, qshen@suda.edu.cn; Fax: +86-512-
65880305; Tel: +86-512-65880329.
†
Electronic supplementary information (ESI) available: crystallographic data and
spectral data (1H NMR, 31P NMR and 13C NMR). CCDC reference numbers 1494633
(for ·THF), 1485799 (for ) and 1487480 (for ·2THF). For crystallographic data in
CIF or other electronic format see DOI: 10.1039/x0xx00000x
1
2
3
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catalytic cycle.12 The results stimulated us to further synthesize
novel EuII complexes and examine their performance in
catalytic intermolecular hydrophosphination of alkenes.
Bridged guanidinate ligands not only have the tunable
steric and electronic effects by variation of the substituents on
the nitrogen atoms, but also can provide the metal center with
rigid framework and more open coordination sphere, which are
useful in homogeneous catalysis. The YbII complex supported
by a naphthaleneꢀbridged bis(guanidinate) ligand was recently
reported by us to exhibit unique reactivity toward various
nitriles.13 Based on these results the two bridged
bis(guanidinate) ligands, a three carbonꢀ and a naphthaleneꢀ
Fig. 1 Molecular structure of complex
1
. Thermal ellipsoids are drawn at the 30%
probability level. Hydrogen atoms are omitted for clarity. Selected bond distances
(Å) and angles (deg): Eu(1)–N(1) 2.485(6), Eu(1)–N(2) 2.367(6), Eu(1)–N(3) 2.3
84(7), Eu(1)–N(4) 2.456(6), Eu(1)–O(1) 2.473(6), Eu(1)–O(2) 2.425(5), Eu(1)–C
(2) 2.876(8), Eu(1)–C(1) 2.875(8), Eu(1)–Cl(1) 2.709(2), N(1)–C(1) 1.309(11), N
(2)–C(1) 1.325(10), N(5)–C(1) 1.431(11), N(3)–C(2) 1.318(11), N(4)–C(2) 1.327
(10), N(6)–C(2) 1.424(10), N(1)–Eu(1)–N(2) 54.1(2), N(3)–Eu(1)–N(4) 54.3(2),
O(1)–Eu(1)–Cl(1) 86.97(15), O(1)–Eu(1)–O(2) 176.38(19), N(3)–Eu(1)–N(1) 127.
2(2), N(1)–C(1)–N(2) 114.2(7), N(3)–C(2)–N(4) 113.4(7).
briged
guanidinates
L1
and
L2
(L1
=
[iPr(Me3Si)NC(NiPr)N(CH2)3NC(NiPr)N(SiMe3)iPr]; L2 = 1,8ꢀ
C10H6{NC(NiPr)(NHiPr)}2) were chosen as the ancillary
ligands, and the syntheses of EuII complexes bearing these
ligands by the reduction of the corresponding EuIII chlorides
were tried. It was found that the reduction of EuIIIL1Cl(THF)2
by Na/K alloy afforded an unexpected bimetallic EuII complex
bearing a newly formed bridged bis(guanidinate) ligand L3,
crystal structure analysis. As shown in Fig. 1, the complex
adopts monomeric structure in the solid state. The center metal
EuIII ion is ligated by two guanidinate moieties of one ligand
L1, one chlorine atom, and two oxygen atoms in a distorted
trigonal bipyramid, if the guanidinate ligands are considered to
be point donors located at the central carbon atoms. The
[EuIIL3]2
(L3
=
[iPr(Me3Si)NC(NiPr)N(CH2)3N(SiMe3)C(NiPr)2]) (
2
), by the
molecular structure of complex
1
is quite similar to those of Nd,
Yb and Y analogues reported.14 The two C
N bond distances in
each Eu N unit are almost equal, indicating the electron
redistribution of one guanidinate group of the original ligand L1,
while the reduction of EuIIIL2Cl(THF)2 yielded a new binuclear
3
EuII complex [EuIIL2(THF)]2 ( ). The two EuII complexes were
–
–N–C–
delocalization within the NCN units. The bond parameters are
well comparable to those for the Nd, Yb and Y complexes14
(see the supporting materials).
found to act as highly active preꢀcatalysts in intermolecular
hydrophosphination of alkenes and alkynes to Ph2PH affording
selectively antiꢀMarkovnikov products. Here we report the
results.
Results and discussion
Syntheses and characterizations of EuIII chloride EuIIIL1Cl(THF)2 (1)
and EuII complex [EuIIL3]2 (2)
Reduction reaction of the corresponding EuIII chlorides with
Na/K alloy were conducted here for the syntheses of the title
EuII complexes. Therefore, the EuIII chloride supported by the
threeꢀcarbon bridged bis(guanidinate) ligand L1 was first
synthesized as it has not been reported yet. Reaction of
anhydrous EuCl3 with one equiv. of freshly prepared lithium
salt of the ligand Li2L1, which was formed by the published
procedure,14 in THF at room temperature for 24 h afforded the
Scheme 2 Synthesis of 2.
The reduction reaction of complex
1 by Na/K alloy was
then carried out at a molar ratio of 1:1.2 in THF at room
temperature. Evaporation of volatiles, filtration to remove the
LiCl from toluene solution and subsequent crystallization of the
residual solids from nꢀhexane at
53% yield.
The red crystals were further characterized by elemental
analysis, IR spectrum and Xꢀray crystal structure analysis, as
the strong paramagnetic shown by EuII, which prevents to get a
resolved nuclear magnetic spectrum. The IR spectrum of the
crystals shows a strong absorption at near 1630 cm−1 assigned
chloride EuIIIL1Cl(THF)2 (
crystallization from a mixture of THF/hexane (Scheme 1).
Elemental analysis of complex is consistent with its
formula. The IR spectra of complex showed the strong
absorption of C=N stretch at approximate 1620 cmꢀ1, indicative
of the delocalized double bond of N N linkage.
1) in 75% yield as red crystals upon
–5 °C afforded red crystals in
1
1
–C–
Complex
1
was further confirmed by an Xꢀray singleꢀcrysꢀ
THF
Me3Si
SiMe3
Me3Si
SiMe3
N
N
EuCl3
THF
N
N
N
N
Eu
N
N
Li Li
N
iPr
iPr
iPr
iPr
N
N
N
to the N
–C–C stretching mode of the guanidinate groups. The
Cl
THF
iPr
iPr
iPr
iPr
Xꢀray crystal structure analysis indicated the red crystals to be
1
the novel EuII complex [EuIIL3]2 (
2) with a newly formed ligand
Scheme 1 Synthesis of 1.
L3 not the original ligand L1 (Scheme 2). The elemental
analysis is consistent with its formula.
2 | New J. Chem., 2013, 00, 1-3
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ARTICLE
The molecular structure of complex
2 is shown in Fig. 2. N(2), N(3) and N(11) occupy equatorial positions. Interestingly,
Complex crystallizes in the triclinic space group
2
P
ī without fꢀ the distance of Eu(2) to C(10) is 3.0915 Å, indicating that there
is a weak interaction15 between Eu(2) and C(10). Moreover, an
agostic interaction between two hydrogen atoms (H(10A) and
H(10C)) on C(10) and Eu(2) was also observed as the distances
of Eu(2) to the two H atoms are 2.835 and 2.734 Å,
respectively.16 The distances of the two C
N unit are almost equal (Table 1), indicating
are delocalized in N N unit. The average Eu N bond distance
–N bonds in each Eu
–
N
–
C
–
π
electrons
–
C
–
–
is comparable with those for the YbII guanidinate complexes, if
the differences in ionic radii between the two metals were
considered.13
Complex
2 can also be synthesized by the reduction of the
in situ formed complex
1
by the reaction of EuCl3 with one
Fig. 2 Molecular structure of complex 2. Thermal ellipsoids are drawn at the 30%
probability level. Hydrogen atoms are omitted for clarity. Selected bond distances
and angles are listed in Table 1.
equiv. of Li2L1 in THF with Na/K alloy under the same
conditions in 62% yield (Scheme 2).
Table 1 Selected bond lengths (Å) and angles (o) for complex 2
Syntheses and characterizations of EuII complex (EuIIL2)2 (3)
The reduction reaction of the chloride EuIIIL2Cl(THF)2 formed
2
in situ by the reaction of anhydrous EuCl3 with [Li2L2 Li2]13
Bond lengths
Eu(1)–N(1)
Eu(1)–N(2)
Eu(1)–N(7)
Eu(1)–N(11)
Eu(1)–N(9)
Eu(1)–N(10)
N(1)–C(1)
N(2)–C(1)
N(5)–C(1)
N(4)–C(2)
N(3)–C(2)
Bond angles
2
2.564(8)
2.692(8)
2.659(8)
2.820(9)
2.521(8)
2.571(9)
1.291(13)
1.361(12)
1.450(13)
1.353(14)
1.331(13)
1.450(11)
1.308(13)
1.358(13)
1.306(14)
1.340(14)
N(9)–Eu(1)–N(1)
N(9)–Eu(1)–N(10)
N(1)–Eu(1)–N(10)
N(9)–Eu(1)–N(7)
N(1)–Eu(1)–N(7)
N(10)–Eu(1)–N(7)
N(9)–Eu(1)–N(2)
N(1)–Eu(1)–N(2)
N(1)–Eu(1)–N(11)
N(10)–Eu(1)–N(11)
N(2)–Eu(1)–N(11)
N(1)–C(1)–N(2)
N(10)–Eu(1)–N(2)
N(4)–Eu(2)–N(7)
113.0(3)
52.5(3)
134.3(3)
118.9(3)
125.3(3)
92.6(3)
125.3(3)
50.9(3)
94.3(3)
93.9(3)
87.5(2)
116.9(9)
174.4(3)
176.6(3)
with Na/K alloy at a molar ratio of 1:1.5 in THF at room
temperature afforded complex
3 as red crystals in 60% yield
upon crystallization from a mixture of THFꢀhexane (Scheme 3).
The crystals are very sensitive to air and moisture. It is soluble
in THF and toluene, but poorly soluble in hexane.
N(6)–C(2)
N(7)–C(24)
N(11)–C(24)
N(9)–C(25)
N(10)–C(25)
ree solvent molecule in its unit cell. It’s unexpected that
complex is a binuclear complex bearing a newly formed
2
Scheme 3 Synthesis of 3.
bridged bis(guanidinate) ligand L3 not the original ligand L1.
The formation of L3 should be resulted from the redistribution
of one guanidinate group of the original ligand L1 by the
change of the nitrogen atoms coordinated to Eu metal center
from the original N(5) and N(2) to the present N(2) and N(1)
for Eu(1) and N(8), N(11) to N(11) and N(7) for Eu(2) as
confirmed by the distances of these EuꢀN bonds, followed by
the shift of the ꢀSiMe3 group on the N(5) (N(11)) to the present
bridgehead N(2) (N(8)). The change of the original ligand
The elemental analysis of the crystals is consistent with
the formula. The IR spectrum shows a strong absorption at near
1630 cm−1 assigned to the N
–
C
–
C stretching mode of the
guanidinate groups. The identity of complex was
3
unequivocally established by an Xꢀray crystal structure
determination.
skeleton during the formation of complex
2 might be because of
the need of steric effect. The coordination environment of the
two metals is different. Eu(1) is sixꢀcoordinate bounded by four
nitrogen atoms of one bridged guanidinate group and two
nitrogen atoms of the other one. The coordination geometry
around Eu(1) can be described as a distorted octahedron. The
two nitrogen atoms (N(2) and N(10)) are located at axial
positions with an N(2)–Eu(1)–N(10) angle of 174.4(3)°, while
Fig. 3 Molecular structure of complex 3. Thermal ellipsoids are drawn at the 30%
four nitrogen atoms N(1), N(7), N(11) and N(9) occupy
equatorial positions. The center metal Eu(2) is fiveꢀcoordinate
around by five nitrogen atoms in a distorted trigonal bipyramid.
The two nitrogen atoms of N(4) and N(7) are located at axial
probability level. Hydrogen atoms (except those on the nitrogen atoms) and THF
molecule are omitted for clarity. Selected bond distances and angles are listed in
Table 2.
positions with an N(4)–Eu(2)–N(7) angle of 176.6(3)°, while
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Table 2 Selected bond lengths (Å) and angles (o) for complex 3
catalyst in this reaction to give the same antiꢀMarkovnikov
addition product 4a selectively. However, complex is somewꢀ
3
3
Table 3 Hydrophosphination of diphenylphosphane to styrene by complexes 2 and 3a
Bond lengths
Eu(1)–N(1)
Eu(1)–N(2)
Eu(1)–N(4)
Eu(1)–N(4A)
Eu(1)–N(5A)
Eu(1)–O(1)
N(1)–C(1)
N(2)–C(1)
N(3)–C(1)
N(4)–C(2)
N(5)–C(2)
N(6)–C(2)
Bond angles
2.534(5) N(1)–Eu(1)–N(2)
2.933(6) N(4A)–Eu(1)–N(5A)
2.491(5) N(4A)–Eu(1)–N(4)
2.711(5) Eu(1)–N(4)–Eu(1A)
2.675(5) N(1)–C(1)–N(2)
2.662(5) N(2)–C(1)–N(3)
1.341(8) N(3)–C(1)–N(1)
1.316(8) N(5)–C(2)–N(4)
1.369(7) N(5)–C(2)–N(6)
1.375(8) N(4)–C(2)–N(6)
1.302(8)
47.30(15)
48.76(15)
142.12(16)
109.23(11)
113.7(5)
123.6(6)
122.8(5)
116.4(6)
123.6(6)
119.9(6)
Entry Cat. (mol)
Solvent
Temp. (°C) Time (h) Yieldb (%)
1
2
2(1%)
2(0.8%)
3(1%)
2(1%)
2(1%)
2(1%)
2(1%)
2(1%)
2(1%)
2(1%)
2(1%)
2(1%)
ꢀ
60
60
60
60
60
60
60
60
60
60
40
r.t.
12
12
12
12
12
12
12
12
12
6
98
91
85
99
91
96
95
90
94
98
91
77
ꢀ
3
ꢀ
HMPA
CHCl3
PhCl
toluene
nꢀhexane
THF
ꢀ
1.406(9)
4
The molecular diagram of complex
3
is shown in Fig. 3
5
and the selected bond distances and angles are listed in Table 2.
Complex crystallizes in the monoclinic space group P21/c
with a crystallographic inversion center located at the center of
the Eu(1) N(4) Eu(1A) N(4A) plane. The two metals are
3
6
7
–
–
–
8
connected together by the two bridging guanidinate species
from the two ligands. Thus, both L2 ligands here adopt a ꢁꢀ
η1:η2:η2 coordination mode. Each Eu metal is sixꢀcoordinate
and bound to five nitrogen atoms of the three guanidinate
groups and an oxygen atom from a THF molecule. The
coordination geometry around each metal can be described as a
pseudoꢀtrigonal pyramid, if each guanidinate group in the
complex is considered to occupy a single coordination site at
9
10
11
12
ꢀ
12
12
ꢀ
a Conditions: neat substrates in a 1:1 ratio, 60 oC. b Yield determined by 1H NMR and 31P NMR
spectroscopy in CDCl3.
the central C atom of the N
structure of complex
is quite similar to that of its YbII
analogue.13 The bond parameters within Eu(1)
N(1) C(1) N(2)
unit match those of the related Eu(II) complexes supported by
nonꢀbridging guanidinate.17 The average Eu
Nꢁꢀguanidinate bond
distance (2.623(0) Å) is about 0.181 Å shorter than that for the
Eu Nguanidinate bonds (2.804(5) Å), which was likely that the
naphthalene bridge in complex shortens the bond distance
between the bridge head N and the center metal. The three CꢀN
bond distances of each guanidine group (N(1) C(1) = 1.341(8),
N(2) C(1) = 1.316(8) and N(3) C(1) = 1.369(7) Å) indicate that
the π electron of the C=N double bond is not delocalized within
the CN3 unit. The same bonding type is also found in the
complexes with the sterically bulky amidinate or guanidinate
ligands.18 The bond parameters are well compared to those of
the YbII complex reported, if the differences in the ion radius
between YbII and EuII were considered.13
–C–N fragment. The solid state
hat less active in comparison with complex
Several reaction conditions were then examined using complex
and the results are shown in Table 3. The reactions with a
2 (Table 3, entry 3).
3
–
–
–
2
o
loading of 1 mol% of complex
2 at 60 C could also take place
–
smoothly in HMPA (hexamethylphosphoramide), CHCl3 or in
the nonꢀpolar and polar solvents, such as toluene,
chlorobenzene, hexane and THF affording the product 4a in
excellent to good yields (Table 3, entries 4−9). Shortening the
reaction time to 6 h did not result in the decreasing of the yield
(Table 3, entry 10). The reaction temperature shows an effect
on the activity: decreasing the reaction temperature led to the
decreasing of the yield (Table 3, entries 11 and 12).
–
3
–
–
–
Thus complex
2 was chosen as the preꢀcatalyst, and the
hydrophosphination reactions with various alkene substrates
were evaluated using 1 mol% of catalyst loading at 60 oC.
Representative results are summarized in Table 4. It can be
seen that all the reactions with the halogen atom substituted
styrene afforded the corresponding products in excellent yields
(Table 4, entries 2−6). The substituted styrenes with electronꢀ
donating groups, such as OMe, Me or Ph, could also proceed
well to give the addition products in excellent yields, except for
the substrate with tBu group on the phenyl ring (Table 4, entries
7−10). Compared with those of alkaline earth metal,7aꢀ7d,7f
transition metal,8b,8c,8e,8g,8n,8q and LnII complexes7c,9,11a,11c, the
performance of this system is wellꢀmatched. Steric factor of the
substrate has a great influence on the reactivity. For example,
more hindered styrene derivatives are less active (Table 4, entry
11). The similar situation was also documented in the published
work.8b,8c,11c Interestingly, the reactions with 2ꢀvinylpyridine
and 4ꢀvinylpyridine also proceeded in the presence of CH3CN
affording the antiꢀMarkovnikov addition product in 84% and
Intermolecular hydrophosphination reaction of alkenes and
alkynes with Ph2PH catalyzed by complexes 2 and 3
With these novel complexes in hand the intermolecular
hydrophosphination reaction of styrene with Ph2PH was first
o
examined as a model reaction at 60 C under solvent free. We
were pleased to see that the reaction of styrene with Ph2PH
proceeded smoothly by use of 1 mol% of complex
antiꢀMarkovnikov addition product 4a exclusively in excellent
yield after 12 h (Table 3, entry 1). Complex is highly active in
this transformation. Even the loading of complex decreased to
0.8 mol%, the reaction still gave product 4a in a 91% yield after
2 to give the
2
2
12 h (Table 3, entry 2). Complex
3 is also an efficient preꢀ
4 | New J. Chem., 2013, 00, 1-3
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ARTICLE
68% yields, respectively (Table 4, entries 12 and 13), which can the catalyst loading decreased to 0.5 mol%, the addition could
be well compared with transition metal complexes8b,8g,8n,8q and still be realized smoothly to afford the conversion of 98% after
LnII complexes.11c However, these reactions under solvent free 2.5 h (Table 5, entry 7). The reaction with a loading of 1 mol%
afforded the product in much lower yields, because of the of complex
2 could also carry out smoothly in polar solvent
polymerization side reaction. The reaction with αꢀmethyl THF (Table 5, entry 3) with 83% translation, whereas, the
styrene did not afford the addition product, but the oligomer of usage of toluene and chlorobenzene as solvent led to obviously
αꢀmethyl styrene instead (Table 4, entry 14). The phenomenon decrease the conversion of phenylacetylene (Table 5, entries 4,
was also found in the catalytic systems reported.7b,8c,8e,11c The 5). In comparison with complex
2, complex 3 showed rather
application of hydrophosphination in the simple synthesis of low activity (Table 5, entry 9), which indicated that the
phosphinoester product is highlighted, as the phosphinoester framework of the ligand around the Eu metal had great effect
core is a dominant sector in the composition of diazo on the reactivity. The present hydrophosphination of
compounds applied in biochemistry. Thus, the reaction with diphenylphosphine to alkyne is stereoselective, which mainly lꢀ
methyl acrylate was examined and found that it could also
Table 5 Hydrophosphination of alkynes by complex 2 and 3a
proceed affording the product 4o in 70% yield (Table 4, entry
15).
Table 4 Intermolecular hydrophosphination of alkenes to Ph2PH by complex 2a
T
(°C)
Time
(h)
Conv.
(%)b
Entry
R
Solvent
Selectivityb
1
2
Ph
Ph
ꢀ
60
60
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
2
100
98
Z:E = 78:22
Z:E = 79:21
Z:E = 86:14
Z:E = 100:0
Z:E = 85:15
Z:E = 77:23
Z:E = 76:24
Z:E = 74:26
Z:E = 84:16
Z:E = 91:9
Z:E = 97:3
Z:E = 70:30
Z:E = 75:25
Entry
1
R1
Ph
R2
H
Product
4a
Conv.b (%)
Yieldc (%)
ꢀ
1.5
2.5
2.5
2.5
2.5
2.5
1.5
2.5
2.5
2.5
2.5
2.5
98
94
91
92
96
95
96
96
91
86
68
84
68
ꢀ
91
86
85
86
89
88
89
85
82
80
61
75
60
ꢀ
3
Ph
THF
83
2
3ꢀBrPh
4ꢀBrPh
2ꢀClPh
3ꢀClPh
4ꢀClPh
4ꢀOMePh
4ꢀMePh
4ꢀPhPh
4ꢀtBuPh
Ph
H
4b
4c
4
Ph
toluene
13
3
H
5
Ph
PhCl
34
4
H
4d
4e
6
7c
Ph
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
100
98
5
H
Ph
6
7d
8d
9e
10d
11f
12g
13h
14
15i
H
4f
8
Ph
91
H
4g
9d
10
11
12
13
Ph
22
H
4h
4i
4ꢀMePh
4ꢀOMePh
2ꢀpyridinyl
4ꢀClPh
80
H
96
H
4j
100
100
Ph
H
4k
4l
2ꢀPy
a Conditions: alkyne (1.0 mmol), Ph2PH (1.00 mmol, 1 eq), 2 (12.5 mg, 1 mol%). b
Based on 1H and 31P NMR spectroscopy in CDCl3. c 0.5 mol% of 2. d Complex 3.
4ꢀPy
H
4m
4n
4o
Ph
CH3
H
eads to antiꢀaddition products and Z isomers are preferable
(Table 5, entries 1−8). The stereoselectivity shown by complex
is different from that of the tridentate iminoꢀamidinate YbII
complex reported previously. With the latter one, a synꢀaddition
of diphenylphosphine to alkynes is favorable in most cases.7b
These
COOMe
70
63
a Conditions: alkene (1.00 mmol), Ph2PH (1.00 mmol, 1 eq.),
2
(12.5 mg, 1
2
mol%), neat, 60 oC, 6 h. Based on 1H and 31P NMR spectroscopy.
b
c
Isolated yield. d 24 h. e 24 h, when the loading of
2 up to 2 mol%, 76% conv.
f 24 h, PhCl as solvent (0.200 mL/1 mmol). g CH3CN as solvent (0.200 mL/1
mmol). h CH3CN as solvent (0.600 mL/1 mmol). i 12 h.
differences
in
stereoselectivity
for
the
hydrophosphination of alkynes has also been reported with
different calcium complexes19 along with iron8f and zirconium
The activity of complexes
2 and 3 for the catalytic
complexes.20
For
example,
regioselective
single
intermolecular hydrophosphination of alkyne to Ph2PH was
then examined taking the model reactions between
phenylacetylene and Ph2PH. The preliminary results are listed
hydrophosphination of terminal arylalkynes with secondary
phosphines was achieved with an iron complex,8f however,
more time and higher temperature were required in that
catalytic system compared with our system. The differences
shown by various metal complexes in stereoselectivity reveal
the impact of the ligand geometry on catalytic performance.
The reactions of the substrate with electronꢀdonating
groups of ꢀMe and ꢀOMe lowered the activity, but increase the
antiꢀaddition selectivity (Table 5, entries 10 and 11). For
example the ꢀOMe group substituted substrate could afford the
in Table 5. Complex
2 is a highly active preꢀcatalyst in this
transformation, and the activity is higher than that of alkene
reaction mentioned above.
The reaction could be conducted at room temperature
using 1 mol% of catalyst amount after 2.5 h to give the
products in a conversion as high as those obtained at 60°C
(Table 5, entries 1, 2 and 6). The reaction still gave the
conversion as high as 91% after 1.5 h (Table 5, entry 8). Even
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NJC
product with a much higher antiꢀaddition selectivity (Z : E = 97 : g, 2.90 mmol) in THF (15 mL). The mixture was stirred for 24
3) in 96% yield (Table 5, entry 11). The reaction with the h at room temperature. The solvent was evaporated under vacuu
electronꢀwithdrawing Cl group substituted substrate yielded the m to dryness and extracted with toluene to remove the LiCl. Th
product with the same high level as that for phenylacetylene in e black red toluene solution was evaporated under vacuum to dr
the antiꢀaddition selectivity in almost quantitative yield (Table yness. The solids was washed with hexane three times. Comple
5, entry 13). The reaction with 2ꢀenthylnylpyridine proceeded
x 1 was obtained as red crystals in the solution of THFꢀhexane
well under the present conditions to yield the product in a (1.90 g, 75%). Anal. Calcd for C31H68ClN6O2Si2Eu (800.49): C,
quantitative conversion. Steric factor of the substrate has a great 46.51; H, 8.56; N, 10.50, Eu, 18.98. Found: C, 46.92; H, 8.98;
influence
on
this
transformation.
More
hindered N, 10.94, Eu, 19.42. IR (KBr, cmꢀ1): 2973 (CH3, s), 2872 (m), 1
diphenylacetylene did not afford the addition product under the 628 (C=N, s), 1524 (m), 1470 (m), 1242(m), 1164 (m), 890 (w),
conditions used.
842 (m), 636 (w).
[EuIIL3]2
Method1. Into a solution of Na/K alloy (0.11 g, 4.08
mmol) in toluene (4 mL) was added solution of
(2)
Conclusions
a
EuIIIL1Cl(THF)2(2.97 g, 3.40 mmol) in THF (20 mL). The
reaction mixture was stirred for 48 h at room temperature. The
precipitate was removed by centrifugation. The volatiles was
evaporated under vacuum to dryness and extracted with toluene
to remove the NaCl. The clear solution was dried in vacuo, the
Two novel EuII complexes
2 and 3 supported by bridged
bis(guanidinate) ligands were synthesized and structurally
characterized. Complex is a bimetallic complex bearing two
2
newly formed three carbonꢀbriged guanidinates through the
change of the N atoms coordinated to Eu metal in a ꢁꢀη1:η2:η2
coordination mode for one ligand and a ꢁꢀη2:η2:η2 mode for the
residual solids crystallized under nꢀhexane at
–5 °C afforded
other interestingly. Complex
3
features an unusual ꢁꢀη1:η2:η2
complex as red crystals (1.12 g, 53%). Anal. Calcd for
2
C46H104N12Si4Eu2 (1241.69): C, 44.50; H, 8.44; N, 13.54; Eu,
24.48. Found: C, 44.88; H, 8.25; N, 13.79; Eu, 24.73.IR (KBr,
cmꢀ1): 2971 (s), 1628 (s), 1527 (m), 1456 (m), 1238(m), 1189
(m), 890 (w), 842 (m), 639 (w).
coordination mode of the naphthaleneꢀbridged guanidinates
onto EuII. Both complexes can serve as highly active preꢀ
catalysts
for
intermolecular
hydrophosphination
of
diphenylphosphine to styrene derivatives and alkynes affording
antiꢀMarkovnikov addition products exclusively and mainly
antiꢀaddition products in the reactions with alkynes. Further
development of new high active EuII complexes with high
selectivity and the investigation of the mechanism of the
intermolecular hydrophosphination by EuII complexes are
ongoing in our laboratory.
Method2. A newly formed Li2L1 (2.92 g, 5.26 mmol) was
added slowly to a white suspention solution of EuCl3 (1.36 g,
5.26 mmol) in THF (30 mL). The color of the solution turned
clearly red immediately. The mixture was stirred for 24 h at
room temperature. The solvent was evaporated under vacuum
to dryness and extracted twice with toluene followed by
centrifugation to remove the LiCl. Into a solution of Na/K alloy
(0.24 g, 9.47 mmol) in toluene (10 mL) was added the aboveꢀ
mentioned clear solution. The reaction mixture was stirred for
48 h at room temperature. The precipitate was removed by
centrifugation. The solvent was evaporated under vacuum to
dryness, washed with hexane three times and dried in vacuo
and extracted with toluene followed by centrifugation to
remove the NaCl. The volume of the extract was reduced to 5
Experimental
General procedures
All manipulations of airꢀsensitive materials were carried out
under an atmosphere of dry argon by using modified Schlenk
line and glovebox techniques. The solvents of THF, toluene,
and nꢀhexane were dried and freed of oxygen by distilling from
sodium benzophenone ketyl under argon before use.
Diphenylphosphine was purchased from Aldrich and used as
received. All the liquid alkenes and alkynes were dried over
CaH2, freshly distilled, and freeze−thaw degassed prior to use.
NMR spectra were recorded on a Bruker AVANCE III HDꢀ400
spectrometer (CDCl3 as solvent). Chemical shifts for 1H and
13C and 31P NMR spectra were referenced internally using the
residual solvent resonances and reported relative to TMS.
Lanthanide metal analysis was carried out by EDTA titration
with a xylenol orange indicator and a hexamine buffer.
Elemental analysis was performed by directly using a Carloꢀ
Erba EA1110 instrument. The IR spectra were recorded on a
MagnaꢀIR 550 spectrometer as KBr pellets. The uncorrected
melting points of crystalline samples in sealed capillaries
(under argon) are reported as ranges.
mL. Complex
2
was obtained as red crystals (2.02 g, 62%).
). A newly formed Li2L2 Li2 (2.49 g,
[EuIIL2(THF)]2
(
3
2
2.71 mmol) in THF (16 mL) was added slowly to a white
suspention solution of EuCl3 (1.40 g, 5.43 mmol) in THF (30
mL). The color of the solution turned clearly tan immediately,
The mixture was stirred for 24 h at room temperature. The
solvent was evaporated under vacuum to dryness and extracted
twice with toluene followed by centrifugation to remove the
LiCl. Into a solution of Na/K alloy (0.21 g, 8.14 mmol) in
toluene (10 mL) was added the aboveꢀmentioned clear solution.
The color of the solution changed from tan to claret, The
reaction mixture was stirred for 48 h at room temperature. The
undissolved portion was removed by centrifugation, the
volatiles were removed under reduced pressure and washed
with hexane three times and dried in vacuo, then extracted with
toluene followed by centrifugation to remove the NaCl and
EuIIIL1Cl(THF)2
(1
). A newly formed Li2L1 (1.61 g, 2.90
dried in vacuo. The extract was crystallized from a mixture of
o
mmol) was added slowly to an activated solution of EuCl3 (0.75
THFꢀhexane at 0 C for 2 days gave complex
3 as red crystals
6 | New J. Chem., 2013, 00, 1-3
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(2.30 g, 60%). Anal. Calcd for C56H88N12O2Eu2 (1265.30): C, We are grateful to the National Natural Science Foundation of
53.16; H, 7.01; N, 13.28; Eu, 24.02. Found: C, 53.58; H, 7.45; China (Grants No. 21132002 and 21372171), a project funded
N, 13.70; Eu, 24.45. IR (KBr, cmꢀ1): 3342 (m), 2971 (m), 2865 by the Priority Academic Program Development of Jiangsu
(w), 1616 (s), 1554 (s), 1546 (s), 1370 (w), 1368 (w), 1195 (s), Higher Education Institutions for financial support. The authors
1153 (s), 821 (w), 764 (m), 620 (m), 555 (m).
declare no competing financial interest.
NMR-scale catalytic reactions
Notes and references
The catalyst (0.01 mmol, 1 mol%) was loaded in a 10 mL
Sample bottle (with a stirring bar) in the nitrogen glovebox. To
the bottle were added the Ph2PH (5.747 M, 1.00 mmol) and the
alkene/alkyne (1.00 mmol). The reaction time started at 60 °C
or room temperature in a prepared apparatus. After the desired
reaction time, CDCl3 was added to the selected reaction mixture,
1
2
3
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The complex
2 (12.5 mg, 0.01 mmol) was loaded in a 10 mL
.
Sample bottle (with a stirring bar) in the nitrogen glovebox. To
the bottle were added the Ph2PH (0.175 mL, 5.747 M, 1.00
mmol) and the alkene (1.00 mmol). The reaction time started at
60 °C in a preheated apparatus. After the reaction was complete,
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acetate/petroleum ether). The identity of the product was
confirmed by NMR spectroscopy and TLC.
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in thinꢀwalled glass capillary filled with argon. Diffraction data
were collected on a Agilent Xcalibur CCD area detector in the
ω scan mode using Mo Kα radiation (λ = 0.71073 Å) for
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.
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5
6
7
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The hydrogen atoms in these complexes were all generated
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parameters, and allowed to ride on their parent carbon atoms.
All of the hydrogen atoms were held stationary and included in
the structure factor calculations in the final stage of fullꢀmatrix
leastꢀsquares refinement. The structures were solved and
refined using SHELXLꢀ2014/7 programs.
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New Journal of Chemistry
View Article Online
DOI: 10.1039/C6NJ02508K
Synthesis and molecular structures of
divalent bridged bis(guanidinate)
europium complexes and their
application
in
intermolecular
hydrophosphination of alkenes and
alkynes
Qianqian Liu, Chuanyong Wang,
Xingmin Zhang, Mingqiang Xue,* The bimetallic EuII complexes supported by bridged bis(guanidinate) ligands
Yingming Yao, Yong Zhang and Qi are efficient precatalysts for the intermolecular hydrophosphination of
Shen*
alkenes and alkynes.