CaII, YbII and SmII Bis(Amido) Complexes Coordinated by NHC Ligands: Efficient Catalysts for Highly Regio- and Chemoselective Consecutive Hydrophosphinations with PH3

Article abstract of DOI:10.1002/chem.201804549

The first example of intermolecular hydrophosphination of styrene, 2-vinylpyridine and phenylacetylene with PH₃ catalyzed by bis-(amido) complexes [(Me₃Si)₂N]₂M(NHC)₂ (M=Ca, Yb, Sm) coordinated by NHC

Full text of DOI:10.1002/chem.201804549

A Journal of
Accepted Article
Title: Ca(II), Yb(II) and Sm(II) bis(Amido) Complexes Coordinated
by NHC Ligands – Efficient Catalysts for Highly Regio- and
Chemoselective Consecutive Hydrophosphinations with PH3
Authors: Alexander Trifonov, Ivan Lapshin, Ivan Basalov, Konstantin
Lyssenko, and Anton Cherkasov
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To be cited as: Chem. Eur. J. 10.1002/chem.201804549
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Ca(II), Yb(II) and Sm(II) bis(Amido) Complexes Coordinated by
NHC Ligands – Efficient Catalysts for Highly Regio- and
Chemoselective Consecutive Hydrophosphinations with PH3
Ivan V. Lapshin,[a] Ivan V. Basalov,[a] Konstantin A. Lyssenko,[b] Anton V. Cherkasov,[a] Alexander A.
Trifonov*[a,b]
Abstract: The first example of intermolecular hydrophosphination of
styrene, 2-vinylpyridine and phenylacetylene with PH3 catalyzed by
bis-(amido) complexes [(Me3Si)2N]2M(NHC)2 (M = Ca, Yb, Sm)
coordinated by NHC ligands is described. The reactions of styrene
with PH3 proceed under mild conditions in quantitative yields to
afford only anti-Markovnikov product and allow for the
chemoselective synthesis of primary, secondary and tertiary
phosphines. Addition of phenylacetylene to PH3 regardless the initial
molar substrates ratio results in the exclusive formation of a tertiary
tris-(Z-styryl)-phosphine. Crucial effect of the Lewis base
coordinated to the metal ion in precatalyst on catalytic activity in
styrene hydrophosphination with PH3 was demonstrated. Free NHCs
were also found to be able to promote addition of PH3 to styrene,
however they provide much lower reaction rates compared to the
metal complexes.
acrylate[12], formaldehyde[13]) with PH3 was published by Pringle
and co-workers. No examples of PH3 addition to non-activated
olefins, vinyl arenes and alkynes catalyzed by rare- and alkaline-
earth metals complexes have been published so far. Moreover,
the examples of hydrophosphination reactions catalyzed by free
carbenes also still remain unknown despite the immense
progress in organocatalysis achieved through their use [14]
.
We found that homo- and heteroleptic Yb(II), Sm(II) and Ca(II)
amido complexes[4a], [4c], [5b] performing high catalytic activity in
styrene hydrophosphination with Ph2PH and PhPH2 proved to be
completely
inert
in
the
case
of
PH3.
Complex
{LONO4}YbN(SiMe3)2 (1)[4a] was the only exception which enabled
transformation of PH3 into phenethylphosphines with high
conversions, reaction rates and perfect anti-Markovnikov
regioselectivity at 60°C, albeit with moderate chemoselectivity at
molar ratios [styrene]0:[PH3]0 < 3 (Table 1, entries 1,2). Whereas
at [styrene]0:[PH3]0 = 3 (PhCH2CH2)3P was obtained in 99% yield.
In the case of 2-vinylpyridine 1 demonstrated noticeably lower
catalytic activity and did not enable insertion of olefin molecule
towards third P-H bond even at [2-vinylpyridine]0:[PH3]0 = 3
(Table 1, entry 4). No reaction of PH3 with tolane and
phenylacetylene was detected in the presence of 1.
The formation of C−P bonds via single step intermolecular
hydrophosphination reactions of unsaturated substrates is a
promising, atom-efficient route to a variety of phosphorus-
containing compounds. To date, a number of examples of this
transformation realized due to acid[1], base[2], d-transition[3],
5]
alkaline-earth[4], and rare-earth[4a, metals catalysis or radical
initiation[2a, c, 6] was reported and is covered in several reviews[2c,
5e,
7]. Despite the progress achieved in this area a substrate
Table 1. Hydrophosphination of styrene and 2-vinylpyridine with PH3,
catalyzed by complex 1.
scope of this reaction remains limited and mainly involves
activated olefins and ubiquitous phenyl- and diphenylphosphine.
Meanwhile, PH3 addition to alkenes and alkynes which is a
progressive and convenient synthetic route to a variety of
primary, secondary and tertiary phosphines still remains poorly
explored. Ease of synthesis of PH3, its low cost (vs PhPH2) and
availability make it commercially attractive starting compound for
the synthesis of phosphines. Hydrophosphination of multiple C-
C bonds with PH3 becomes feasible under free radical initiation[8],
acid[1] and superbasic[9] conditions, or UV-irradiation[10], however,
suffers from a lack of selectivity. The only example of application
№
[Alkene]0:[PH3]0
Time, h
Conv., %[e]
prim-P / sec-P / tert-P[f]
70:25:5
1[a]
2[b]
3[c]
4[d]
1:1
2:1
3:1
3:1
2
3
99
99
99
40
of
late
transition
metal
complexes
for
catalytic
10:74:16
hydrophosphination of activated substrates (acrylonitrile[11], ethyl
10
24
0:1:99
[a]
[b]
Mr. Ivan V. Lapshin, Dr. Ivan V. Basalov, Mr. Anton V. Cherkasov
G. A. Razuvaev Institute of Organometallic Chemistry of Russian
Academy of Sciences,
603950, 49 Tropinina str., Nizhny Novgorod, GSP-445, Russia
Prof. Dr. Konstantin A. Lyssenko, Prof. Dr. Alexander A. Trifonov*
A. N. Nesmeyanov Institute of Organoelement Compounds of
Russian Academy of Sciences,
80:20:0
[a] [PH3]0:[styrene]0:[cat]0 = 50:50:1, [cat]0 = 21.0 mM, T[°C] = 60, C6D6. [b]
[PH3]0:[styrene]0:[cat]0 = 50:100:1, [cat]0 = 21.0 mM, T[°C] = 60, C6D6. [c]
[PH3]0:[styrene]0: [cat]0 = 50:150:1, [cat]0 = 21.0 mM, T[°C] = 60, C6D6. [d]
[PH3]0:[2-vinylpyridine]0:[cat]0 = 50:150:1, [cat]0 = 21.0 mM, T[°C] = 60, C6D6.
[e] Conversion determined by 1H NMR spectroscopy. [f] Chemoselectivity was
determined by 31P NMR spectroscopy.
119991, 28 Vavilova str., Moscow, GSP-1, Russia
E-mail: trif@iomc.ras.ru.
Supporting information for this article is given via a link at the end of
the document.
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10.1002/chem.201804549
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Despite high activity complex
Figure 1. Molecular structures of complexes 4 (M = Ca (4Ca), Yb (4Yb), Sm
(4Sm)) and 5 (M = Ca (5Ca), Yb (5Yb), Sm (5Sm)). Hydrogen atoms and
methyl substituents of iPr groups are omitted for clarity; thermal ellipsoids
drawn at the 30% probability level.
1
features a considerable
drawback: low stability. According to 1H NMR spectroscopy
monitoring 1 decomposes completely in C6D6 solution in vacuum
in 4 days with liberation of ethylene most likely due to cleavage
of aza-crown moiety. We focused on elaboration of simple in
preparation, accessible catalysts efficient in intermolecular
hydrophosphination of multiple C-C bonds with PH3. The
analysis of the state of the art suggests that electron-donating
properties, denticity of the Lewis base coordinated to a metal in
pre-catalyst as well as its ability to provide stabilization of the
catalytic centre and solubility of a real catalytic species are
among the factors that strongly affect catalytic activity of
complexes in intermolecular olefin hydrophosphination.[4a], [5b], [5e]
Bis(amido) complexes [(Me3Si)2N]2M(NHC)2 (M = Ca, Yb, Sm)
coordinated by NHC–ligands were obtained in high yields by the
reactions of [(Me3Si)2N]2M(THF)2 with two equivalents of 2 and 3
in toluene (Scheme 1). The synthesis of 5Yb was previously
reported by Cui and co-workers.[15]
Complexes 4,5M proved to be highly efficient catalysts for
styrene hydrophosphination with PH3 in neat substrates at 70°C.
They enable addition of one equivalent of styrene to PH3 with
excellent anti-Markovnikov regioselectivity and chemo-selectivity
over 95% of formation of the target primary phenethylphosphine
(prim-P) (Table 2). The reaction proceeds with high rates even
at low catalyst loading (0.4 molar %). The overall turnover
number TON = 247 and apparent turnover frequency TOF = 15
h−1 were reached in 16 h. Interestingly despite the difference in
ion size and M(II) redox properties in the PH3 monalkylation
step, all compounds exhibit similar activity. No noticeable
influence of the nature of NHC-ligand on catalytic activity was
also observed.
Table 2. Hydrophosphination of styrene with PH3 ([PH3]0:[styrene]0 = 1:1),
catalyzed by complexes 4-5.
№
Cat.
4Ca
5Ca
4Yb
5Yb
4Sm
5Sm
Loading,
mol. %
Time, h
Conv., %[b]
99
prim-P / sec-P /
tert-P[c]
Scheme 1. Synthesis of complexes 4-5.
1
2[a]
3
2
0.4
2
2
16
2
2:95:3
0:1:99
3:95:2
0:2:98
5:92:3
0:15:85
6:92:2
0:18:82
0:94:6
0:1:99
2:93:5
0:1:99
97(95[d]
99
)
)
)
)
)
)
Complexes 4-5M (M = Ca, Yb, Sm) were isolated in 83-87%
yields. All complexes are stable in both solid state and in hexane
or toluene solutions under conditions excluding contact with
oxygen and moisture. Crystal structures of 4-5M were
established by X-ray analysis and are depicted in Figure 1. The
crystal and structural refinement data are listed in the Tables S1-
3 (ESI). The isostructural complexes 4Ca, 4Yb, 4Sm crystallize
as solvates 4M·½C7H8, while 5Ca, 5Yb, 5Sm form solvates with
one toluene molecule 5M·C7H8. The substitution of THF
molecules with the NHC ligands in the coordination sphere of
the metal ion in bis(amido) complexes results in some (0.04-0.07
Å) increase in the M-N bond lengths compared to the parent
amide [(Me3Si)2N]2M(THF)2 most likely due to greater steric
demand of NHC-ligands (See Table S4 in ESI). No significant
difference in M-C bonds lengths in the couples 4,5Ca, 4,5Yb
and 4,5Sm was observed. The N-M-N bond angles in
complexes 4,5M and the parent [(Me3Si)2N]2M(THF)2 are almost
indistinguishable. The C-M-C bond angles in complexes 4,5M
(81.3(5)-85.4(2)°) have values close to the O-M-O bond angles
in [(Me3Si)2N]2M(THF)2 complexes (81.4(1)-85.4(4)°).[16]
4[a]
5
0.4
2
16
3
95(93[d]
99
6[a]
7
0.4
2
24
3
97(95[d]
99
8[a]
9
0.4
2
24
2
98(96[d]
99
10[a]
11
12[a]
0.4
2
16
2
96(94[d]
99
0.4
16
98(96[d]
Reaction in neat substrates [PH3]0:[styrene]0:[cat]0 = 50:50:1, [cat]0 = 140.0
mM, T[°C] = 70. [a] [PH3]0:[styrene]0:[cat]0 = 250:250:1, [cat]0 = 28.0 mM, T[°C]
= 70. [b] Conversion determined by 1H and 31P NMR spectroscopy. [c]
Chemoselectivity determined by 31P NMR spectroscopy. [d] Yield of isolated
product.
Moreover complexes 4,5M allow for the addition of two and
three equivalents of styrene to PH3 leading to the selective
formation of secondary and tertiary phosphines. At 70°C and 2
mol.% of catalyst loading complexes 4,5M enable the formation
of secondary or tertiary phosphines with quantitative conversion,
chemoselectivity over 95% and absolute anti-Markovnikov
regioselectivity (Table 3). Surprisingly unlike the monoalkylation
step in the double and triple olefin addition to PH3 complexes
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4,5Yb proved to be noticeably less catalytically active and
chemoselective compared to the Ca and Sm congeners. Thus,
for the complexes of Ca and Sm quantitative conversions in the
formation of secondary and tertiary phosphines were reached in
16 and 48 h respectively, for the Yb analogues the completion of
the same reactions required 24 and 60 h.
Table 3. Hydrophosphination of styrene with PH3 at different [PH3]0:[Styrene]0
ratios, catalyzed by complexes 4-5M and free carbenes 2-3.
Figure 2. Plot of the reagents conversion vs reaction time for the
hydrophosphination of styrene with PH3 catalyzed by 4Sm in benzene-d6 at
25 °C. Reaction conditions: [PH3]0:[styrene]0:[4Sm]0 = 20:160:1; total volume
0.67 mL; [4Sm]0 = 30.0 mM.
№
1[a]
Cat.
[styrene]0:[PH3]0
Time, h
16
prim-P / sec-P / tert-P[c]
2:95:3
2:1
3:1
2:1
3:1
2:1
3:1
2:1
3:1
2:1
3:1
2:1
3:1
2:1
3:1
2:1
3:1
4Ca
2[b]
48
0:1:99
The kinetic profile reflects chemospecific formation of primary,
secondary and tertiary phosphines. First, PH3 is selectively
converted into PhCH2CH2PH2 and the latter started to react only
when PH3 was consumed completely. The formation of
secondary phosphine (PhCH2CH2)2PH was detected only in ~4 h
after the start of the reaction. Similarly, tertiary phosphine
(PhCH2CH2)3P began to appear only after full consumption of
PhCH2CH2PH2 nearly in 28 h after the reaction start. The plots of
the concentration of PH3, PhCH2CH2PH2 and (PhCH2CH2)2PH
vs time in the presence of the excess of styrene obtained in the
kinetic experiment are linear and are indicative of the zeroth
order of the reaction in phosphines. Remarkably, the observed
3[a]
16
3:95:2
5Ca
4Yb
5Yb
4Sm
5Sm
4[b]
48
0:2:98
5[a]
24
5:92:3
6[b]
60
0:15:85
6:92:2
7[a]
24
8[b]
60
0:18:82
0:94:6
9[a]
16
rate constants of the subsequent stages of the reaction kobs1
=
10[b]
11[a]
12[b]
13[a]
14[b]
15[a]
16[b]
48
0:1:99
3.50(1)∙10-2 h-1, kobs2 = 8.32(1)∙10-3 h-1, kobs3 = 1.65(1)∙10-3 h-1
differ noticeably. The similar tendency was observed for the
rates of consumption of PH3, PhCH2CH2PH2 and
16
2:93:5
(PhCH2CH2)2PH k1
=
1.6812(1)∙10-1 mol L-1 h-1, k2
=
48
0:1:99
3.4980(1)∙10-2 mol L-1 h-1, k3 = 5,9400(1)∙10-3 mol L-1 h-1 thus
giving a plausible explanation of the observed chemospecificity.
On the other hand the difference of the reaction rates of the σ-
bond metathesis of the reaction intermediate with PH3, primary
and secondary phosphines can also contribute into the
chemoselectivity control.[4a] This suggestion is consistent with
the difference of pKa values of PH3, primary, secondary
phosphines.[17] We assume that the catalytic cycle of olefin
hydrophosphination with PH3 is similar to that previously
established for the reactions involving Ph2PH and PhPH2.[4a,15]
Complexes 4,5M proved to be inactive in catalysis of PH3
addition towards double C=C bonds of 1-nonene, 2,3-
dimethylbutadiene, cyclohexene and norbornene.
2
2
3
3
48
4:93:3
72
0:31:69
4:94:2
48
72
0:23:73
[a] Reaction in neat substrates [PH3]0:[styrene]0:[precat]0 = 50:100:1, [cat]0
=
75.0 mM, T[°C] = 70. [b] Reaction in neat substrates [PH3]0:[styrene]0:[precat]0
= 50:150:1, [cat]0 = 50.0 mM, T[°C] = 70. [c] Chemoselectivity, determined by
1H, 31P NMR spectroscopy, at styrene conversion > 95%.
In order to evaluate the effect of the nature of the Lewis base
coordinated to the metal ion on activity in catalysis of PH3
addition to styrene, the catalytic tests with [(Me3Si)2N]2M(L)2 (M
= Ca, Yb, Sm; L = THF, Et2O) were performed under analogous
conditions. It is noteworthy that unlike 4,5M the bis(amides)
coordinated by THF or Et2O turned out absolutely catalytically
inactive in this transformation thus giving an evidence for a
decisive role of the Lewis base coordinated to the metal in the
stabilization of the real catalytic species. As evidenced by the
stoichiometric reactions of PH3 with [(Me3Si)2N]2M(L)2 (2:1 molar
ratio, benzene-d6) affording the black precipitates regardless of
the presence or absence of styrene in the reaction mixture
insolubility of the resulting species in hydrocarbon solvents is
the most likely reason of their catalytic inertness. Moreover,
ability of free carbenes 2 and 3 to promote addition of PH3 to
To follow the formation of primary, secondary and tertiary
phosphines in the course of stepwise PH3 hydrophosphination
and to evaluate chemospecificity of the reaction stages kinetic
monitoring of the reaction of styrene with PH3 catalyzed by 4Sm
(25 °C, benzene-d6, [styrene]0:[PH3]0 = 8) was carried out. The
kinetic profile for the concentrations (Figure 2) in the various
phosphines is not typical of consecutive reactions.
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styrene was verified. Surprisingly 2 and 3 were found to enable
this reaction under the same conditions as 4,5M affording
selectively primary, secondary and tertiary phoshines (Table 2,
entries 13-14; Table 3, entries 13-16). However at the stage of
addition of third equivalent of styrene to PH3 the reaction
catalyzed by 2 and 3 is somewhat less selective compared to
the results obtained with 4,5M. The kinetic monitoring of the
reaction of PH3 with styrene (Figure 3) revealed that in the
presence of 2, 3 the reaction proceeds selectively and follows
the same kinetic law as in the case of 4,5M. However, free
NHCs 2, 3 provide much lower reaction rates compared to metal
complexes 4,5M (kobs1(4Sm)/kobs1(3) = 4.67) (Figure 3).
№
Cat.
[2-vinylpyridine]0:[PH3]0
Time,
h
prim-P / sec-P / tert-P [a][b]
1
2
3
4
5
6
4Ca
5Ca
4Yb
5Yb
4Sm
5Sm
6:1
6:1
6:1
6:1
6:1
6:1
10
10
10
10
10
10
0:50:50
0:10:90
40:60:0
50:50:0
0:25:75
0:20:80
Reaction in neat substrates [PH3]0:[2-vinylpyridine]0:[precat]0
= 50:300:1,
[precat]0 = 30.0 mM, T[°C] = 70°C. [a] Conversion determined by NMR
spectroscopy. [b] Chemoselectivity was determined by 31P NMR spectroscopy.
Surprisingly unlike olefin hydrophosphination the addition of
PH3 towards terminal CC triple bond of phenylacetylene
regardless the initial molar ratio of substrates affords exclusively
tertiary tris-(Z-styryl)-phosphine (Table 5). The kinetic monitoring
of the reaction by 31P NMR spectroscopy did not give any
evidence for the formation of primary and secondary
styrylphosphines even at low consumption of PH3, only tris-(Z-
styryl)-phosphine was detected in the reaction mixture (Figure
4).
Figure 3. Comparative plot of the reagents conversion vs reaction time for the
hydrophosphination of styrene with PH3 catalyzed by 4Sm and 3 (free NHC) in
benzene-d6 at 25 °C. Reaction conditions: [PH3]0:[styrene]0:[Cat]0 = 20:160:1;
total volume 0.67 mL; [Cat]0 = 30.0 mM.
To the best of our knowledge this is the first example of
intermolecular hydrophosphination catalyzed by NHCs reported
so far. NHCs being rather strong bases[18] are known to be able
Table
5.
Hydrophosphination
of
phenylacetylene
with
PH3
([PH3]0:[phenylacetylene]0 = 1:4), catalyzed by complexes 4-5.
[19]
[20]
to activate small molecules like H2, NH3 and PH3 via their
addition towards сarbene atom. We assume that the
С
formation of organophosphines in the reactions catalyzed by
free carbenes proceeds via transient carbene-PH3 adduct.[19]
Currently, detailed mechanistic and kinetic studies of styrene
hydrophosphination with PH3, catalyzed by both free carbenes
and their Ln(II) complexes, are underway.
№
1
Cat.
4Ca
5Ca
4Yb
5Yb
4Sm
5Sm
2
Time, h
16
Conv., %[a]
99
99
99
98
99
99
91
93
When 2-vinylpiridine was used as an olefinic substrate
hydrophosphination with PH3 proved to be less chemoselective
and the reaction course was complicated by the simultaneous
sluggish substrate polymerization. Nevertheless complexes 5Ca
and 4,5Sm enable formation of tertiary tris(2-(pyridin-2-
yl)ethyl)phosphine with high conversion and chemoselectivity up
to 90%. Surprisingly Yb complexes were less active in the case
of 2-vinylpiridine; the reactions with PH3 afforded only mono-
and double addition products. No formation of tertiary phosphine
was detected. Hydrophosphination of 2-vinylpiridine with PH3
can be applied as a convenient one-pot synthetic approach to
2
16
3
24
4
24
5
16
6
16
7
48
8
3
48
tris(2-(pyridin-2-yl)ethyl)phosphine,
coordination chemistry.[21]
a
useful
ligand for
Reaction in neat substrates [PH3]0:[phenylacetylene]0:[precat]0 = 50:200:1,
[precat]0 = 50.0 mM, RT. [a] Conversion determined by NMR spectroscopy.
Table 4. Hydrophosphination of 2-vinylpyridine with PH3, catalyzed by
complexes 4-5.
It should be noted that the same reaction can be also
promoted by free NHC, however this reaction was found to be
much slower than those catalyzed by their M(II) complexes.
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Figure 4. Plot of reagent concentration vs reaction time for the
hydrophosphination of phenylacetylene with PH3 catalyzed by 4Sm in
benzene-d6 at 25 °C. Reaction conditions: [PH3]0/[phenylacetylene]0/[4Sm]0
20/200/1; total volume 0.67 mL; [4Sm]0 = 30.0 mM.
=
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In conclusion, we demonstrated that M(II) (M = Ca, Yb, Sm)
bis(amides) coordinated by NHC ligands enable addition of PH3
to double and triple C-C bonds under mild conditions and with
high reaction rates. In styrene hydrophosphination complexes
4,5M perform exceptional regio- and chemoselectivities, thus
allowing for a selective synthesis of the whole range of primary,
secondary and tertiary phosphines in excellent yields. The
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We also demonstrated the first example of catalytic activity of
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free
NHCs
in
intermolecular
hydrophosphination.
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to
a
tetradentate
tris(2-(pyridin-2-yl)ethyl)phosphine.
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Acknowledgements
The authors thank Russian Science Foundation (Grant № 17-
73-20262). The X-ray study was carried out using the equipment
of The Analytical Centre of IOMC RAS and INEOS RAS.
Keywords: homogeneous catalysis • phosphanes • lanthanides
• carbene ligands • calcium
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This article is protected by copyright. All rights reserved.

10.1002/chem.201804549
Chemistry - A European Journal
COMMUNICATION
COMMUNICATION
The first example of intermolecular
hydrophosphination of styrene, 2-
vinylpyridine and phenylacetylene with
PH3 catalyzed by Ca(II), Yb(II) and
Sm(II) bis-(amido) complexes
Ivan V. Lapshin, Ivan V. Basalov,
Konstantin A. Lyssenko, Anton V.
Cherkasov, Alexander A. Trifonov*
Page No. – Page No.
coordinated by NHC ligands is
described. The reactions of styrene
with PH3 proceed under mild
conditions in quantitative yields to
afford only anti-Markovnikov product
and allow for the chemoselective
synthesis of primary, secondary and
tertiary phosphines.
Highly Regio- and Chemoselective
PH3 Addition to Double and Triple C-
C Bonds Catalyzed by Ca(II), Yb(II)
and Sm(II) bis(Amido) Complexes
Coordinated by NHC Ligands
This article is protected by copyright. All rights reserved.