Syntheses of hydrido selenophenolato iron(II) complexes and their catalytic application in hydrosilylation of aldehydes and ketones

Article abstract of DOI:10.1016/j.catcom.2018.06.015

Three novel selenophenolato hydrido iron(II) complexes [cis-(H)(SeAr)Fe(PMe₃)₄] (4–6) (Ar=C₆H₅ (4), p-MeOC₆H₄ (5) and o-MeC₆H₄ (6)) were prepared through the reaction of Fe(PMe₃)₄ with selenophenols ArSeH (1–3) via Se–H activation. The iron hydrido complexes 4, 5 and 6 could catalyze the hydrosilylation of aldehydes and ketones. Among them complex 5 is the best catalyst for this process. Furthermore, α,β-unsaturated alcohols could be obtained from the selective reduction reactions of the corresponding α,β-unsaturated carbonyls catalyzed by hydrido iron(II) complex 5. This catalytic system has good tolerance for some common groups but it is easy to reduce the nitro group to an amino group. The experiments indicate that the chemoselectivity for this catalytic system is –CHO>–NO₂>–C([dbnd]O)CH₃. The crystal structure of 6 was determined by X-ray diffraction.

Full text of DOI:10.1016/j.catcom.2018.06.015

Accepted Manuscript
Syntheses of hydrido selenophenolato iron(II) complexes and
their catalytic application in hydrosilylation of aldehydes and
ketones
Yangyang Wang, Shishuai Ren, Wenbo Zhang, Benjing Xue,
Xinghao Qi, Hongjian Sun, Xiaoyan Li, Olaf Fuhr, Dieter Fenske
PII:
DOI:
Reference:
S1566-7367(18)30226-7
doi:10.1016/j.catcom.2018.06.015
CATCOM 5430
To appear in:
Catalysis Communications
Received date:
Revised date:
Accepted date:
29 May 2018
14 June 2018
14 June 2018
Please cite this article as: Yangyang Wang, Shishuai Ren, Wenbo Zhang, Benjing Xue,
Xinghao Qi, Hongjian Sun, Xiaoyan Li, Olaf Fuhr, Dieter Fenske , Syntheses of hydrido
selenophenolato iron(II) complexes and their catalytic application in hydrosilylation of
aldehydes and ketones. Catcom (2018), doi:10.1016/j.catcom.2018.06.015
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ACCEPTED MANUSCRIPT
Syntheses of Hydrido Selenophenolato Iron(II) Complexes and their Catalytic Application in
Hydrosilylation of Aldehydes and Ketones
Yangyang Wang,a,b Shishuai Ren,a Wenbo Zhang,a Benjing Xue,a Xinghao Qi,a Hongjian Sun,a
Xiaoyan Li,a,* Olaf Fuhrc and Dieter Fenskec
a
School of Chemistry and Chemical Engineering, Key Laboratory of Special Functional
Aggregated Materials, Ministry of Education, Shandong University, Shanda Nanlu 27, 250199
Jinan, PR China
b College of Chemistry and Chemical Engineering, Northwest Normal University, 730070 Lanzhou,
PR China
c
Institut für Nanotechnologie (INT) und Karlsruher Nano-Micro-Facility (KNMF), Karlsruher
Institut für Technologie (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen,
Germany
E-mail: xli63@sdu.edu.cn; Fax: + 86 531 88564464.
________________________________________________________________________________

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Abstract
Three novel selenophenolato hydrido iron(II) complexes [cis-(H)(SeAr)Fe(PMe3)4] (4 - 6) (Ar =
C6H5 (4), p-MeOC6H4 (5) and o-MeC6H4 (6)) were prepared through the reaction of Fe(PMe3)4 with
selenophenols ArSeH (1 - 3) via Se-H activation. The iron hydrido complexes 4, 5 and 6 could
catalyze the hydrosilylation of aldehydes and ketones. Among them complex 5 is the best catalyst
for this process. Furthermore, α,β-unsaturated alcohols could be obtained from the selective
reduction reactions of the corresponding α,β-unsaturated carbonyls catalyzed by hydrido iron(II)
complex 5. This catalytic system has good tolerance for some common groups but it is easy to
reduce the nitro group to an amino group. The experiments indicate that the chemoselectivity for
this catalytic system is –CHO > -NO2 > -C(=O)CH3. The crystal structure of 6 was determined by
X-ray diffraction.
Keywords: hydrosilylation / selenophenol / iron hydride / α,β-unsaturated aldehyde.

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1. Introduction
Selenium and sulfur are in the same main family in the periodic table. Although the chemical
properties of selenium and sulfur are similar, the chemistry of selenium-containing ligands might
display significantly different characteristics from their sulfur-containing analogues. In comparison
with the publications on sulfur-coordinated metal complexes, there are fewer articles on
selenium-coordinated metal complexes. In recent years, it has been found that some transition metal
complexes coordinated by selenium atom(s) have good to excellent catalytic properties for some
organic reactions. Singh reported that the [SeNSe]-pincer Pd complexes had high catalytic activity
for the Heck reaction [1]. The [N, Se]-chelate half-sandwich ruthenium complex could catalyze
transfer hydrogenation of ketones [2]. The [Se, Se]-chelate palladium complex has excellent
catalytic activity for the Suzuki-Miyaura reactions [3]. The combination of N-heterocyclic carbene
with Se-coordination afforded the first [Ccarbene, Se]-chelate Pd complexes. These palladium
complexes are excellent catalysts for Suzuki-Miyaura reactions [4]. It was also found that double
Se-coordinated Rd(III) and Ir(III) complexes are efficient catalysts for both Oppenauer-type
oxidation of alcohols and transfer hydrogenation of ketones with 2-propanol [5].
Based on the high abundance, low-toxicity and price of iron, iron should be one of the most
utilized metals in homogeneous catalysis. Reduction reactions focusing on hydrosilylation and
hydrogenation of carbonyl compounds with iron catalysts have been actively devoleped [6-10].
Iron-catalyzed hydrosilylation is a popular reduction reaction and some transformations exhibit
good functional group tolerance and chemoselectivities [11-13]. Recently, Langer disclosed that a
new anthraquinoid-based iron(II) complex is active in hydrosilylation of carbonyls [14]. The
carbonyl iron complexes as catalysts were also used for aldehyde hydrosilylation [15]. A new series

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of piano stool iron(II) complexes with triazolylidene ligands was prepared for the hydrosilylation of
aldehydes and ketones [16]. Recently, we reported the synthesis of hydrido thiophenolato iron(II)
complexes by reaction of thiophenols with Fe(PMe3)4 and found that the hydrido thiophenolato
iron(II) complexes have dual catalytic activity for both hydrosilylation of carbonyl compounds [17]
and dehydration of amides [18]. As continuation to our study in this direction, in this paper we
report the synthesis of three novel hydrido selenophenolato iron(II) complexes through the reaction
of selenophenols with Fe(PMe3)4. The catalytic properties of these complexes for hydrosilylation of
carbonyls were explored.
2. Results and discussion
2.1 Synthesis of hydrido selenophenolato iron(II) complexes 4 - 6
The reactions of Fe(PMe3)4 with selenophenols 1 - 3 afforded hydrido iron complexes （4 - 6）
as Se-H bond activation products according to Eq. (1). In comparison with the analoge hydrido
-1
thiophenolato iron(II) complexes [17, 19], the Se-H bond (bond energy: 314 KJmol ) activation is
-1
easier than the S-H bond (bond energy: 339 KJmol ) activation. Therefore, the formation of
complexes 4 – 6 is faster than that of hydrido thiophenolato iron(II) complexes. Nevertheless,
complexes 4 – 6 are unstable and they decompose slowly in solution. By controlling the reaction
time, complexes 4 – 6 could be isolated only in the yields of 21 - 30%. In the solid state complexes
4 - 6 rapidly decompose when exposed to air. The decomposition temperatures of complexes 4 – 6
under the atmosphere of N2 are 94.4, 89.3 and 84.6 oC, respectively.
In the IR spectra of complexes 4 – 6, the typical signals for ν(Fe-H) vibrations were found at

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-1
1
1822 (4) 1843 (5) and 1826 (6) cm . In the H NMR spectra of 4 - 6, the signals of the hydrido
hydrogens appear at -10.58 (4), -10.64 (5) and -10.22 ppm (6) as dtd peaks with the same coupling
constants of 2JPH = 84.0, 55.0 and 27.0Hz, respectively. In the 31P NMR spectra of complexes 4 - 6,
three sets of signals (1 : 2 : 1) were observed at 10.5 (dt) / 14.1 (dd) / 28.8 (dt) (4), 10.2 (dt) / 14.4
(dd) / 29.1 (dt) (5) and 10.9 (dt) / 15.4 (dd) / 29.7 (dt) (6) ppm assigned to the four PMe3 ligands,
respectively. The similar results for the sulfur analogue iron complexes were also observed [17, 19].
Two trans-positioned PMe3 ligands have the same chemical environments. The spectroscopic data
are compatible with an octahedral configuration around the Fe atom consisting of a P-Fe-P axis and
an equatorial coordination of [P, P, Se, H] atoms. The expected molecular structure of complex 6
was confirmed by X-ray diffraction analysis (Figure 1). This molecule structure is completely
similar to that of the sulfur analogue [19]. However, the Fe1-H bond (1.34 Å) is significantly
shorter than the Fe-H bond (1.509 Å) in the sulfide. This difference may be caused by the stronger
electron-withdrawing ability of the sulfur atom.
Figure 1 Molecular structure of complex 6.
2.2 Catalytic application of iron hydrido complexes 4 - 6 in hydrosilylation of carbonyl compounds
As we know, some iron complexes could be used as efficient catalysts in the reduction of
unsaturated organic substrates [20 - 22]. Recently, our group reported the synthesis of several
hydrido iron complexes and their catalytic application in hydrosilylation of carbonyl compounds
[17, 19]. We found that the hydrido pincer iron complex [PSiP]Fe(H)(PMe3)2 [19, 23] and the
hydrido chelate iron complex [P,S]Fe(H)(PMe3)3 [24] as well as monodentate hydrido thiophenolato

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iron(II) complexes [cis–Fe(H)(SAr)(PMe3)4] [17] are effective catalysts for the reduction of
aldehydes and ketones. To extend the scope of the iron-based catalysts, the catalytic property of
hydrido selenophenolato iron(II) complexes 4 – 6 for the hydrosilylation of aldehydes was studied.
The hydrosilylation reaction (Eq. (2)) was carried out with benzaldehyde as model substrate and
hydrido iron complexes 4 - 6 as pre-catalysts using (EtO)3SiH as the reducing silylation agent
(Supporting Information, Table S1). Benzaldehyde has no conversion without catalyst (entry 1).
Improving the loading of catalyst 4 to 5%, the substrate has the highest conversion 99% in 2 hours
under 50°C (entries 2, 3 and 4). At lower temperature, the conversion is under 90% even in 4 hours
(entries 5 and 6). For complex 5, benzaldehyde could be converted to the silyl ether in the
conversion of 93% only with 1% catalyst loading (entry 7). The catalytic activity of complex 6 is
the lowest and the conversion of benzaldehyde is less than 40% with the catalyst loading from 1%
to 5% (entries 8 - 11). It could be confirmed that (EtO)3SiH is the best silane for this catalytic
system (entries 4, 12 - 14).
Catalyst,THF
20 50 C, 2 4h
PhCHO (EtO)3SiH
PhCH2OSi(OEt)3
(2)
Using complexes 4 (5 mol %) and 5 (1 mol %) as catalysts, we extended the scope of the
substrates. The silyl ether products were hydrolyzed with 10% of sodium hydroxide to afford the
corresponding alcohols (Eq. (3)). The isolated yields of the products were summarized in Table 1.
Cat.4or5,THF
50 C, 2h
10%NaOH
CH3OH,50 C
RCHO (EtO)3SiH
RCH2OSi(OEt)3
RCH2OH
(3)
Table 1 Catalytic Hydrosilylation of Aldehydes with 4 and 5

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Reaction conditions: RCHO (2.0 mmol), (EtO)3SiH (2.2 mmol) in 2.0 mL of THF at 50oC for 2h.
Isolated Yields: 4 as catalyst / 5 as catalyst.
From Table 1, it is concluded that the substrates could transform to the corresponding alcohols
in good yields after hydrolysis whether the phenyl rings of the aromatic aldehydes have
electron-donating groups or electron-withdrawing groups. These results indicate that the functional
groups, such as halides，heteroaromatic rings and cyano group, can be tolerated under catalytic
conditions except for nitro group. This suggests that the electronic effects on the reactivity of the
substrates are limited. Even if the aldehyde group has an ortho-substitution, the reaction yields are
still high. With 5 mol % of 4 as catalyst, the expected alcohols were obtained in good yields from
85% to 96% while the yield of the products were from 81% to 94% with 1 mol % of 5 as the
catalyst. As illustrated in Table 1, 5 displayed higher catalytic activity than 4. In comparison with 4,
the electron-donating methoxy group at the para-position of the phenyl group in 5 increases the
electron density of the iron center. In the catalytic cycle, the dissociation of PMe3 from the iron
center and the coordination of the carbonyl group to the iron center in 5 are easier. Therefore, the
catalytic reactivity of 5 is greater than that of 4. The lowest catalytic activity of 6 among them
might be caused by the steric effect of the ortho-methyl group at the phenyl ring in 6 since
ortho-MePh- group and the hydrido ligand are in the cis-position.
Cat.5,THF
60 C, 24h
10%NaOH
CH3OH,50 C
RCOR (EtO)3SiH
RR CHOH
(4)
Table 2 Catalytic Hydrosilylation of Ketones with 5
Catalytic reaction conditions: (1) RCOR’ (2.0 mmol), (EtO)3SiH (2.2 mmol) and 5 (0.1 mmol) in 3
ml THF, 60℃, 24h. (2) MeOH (2 mL) and 10% aqueous solution of NaOH (5 mL) with vigorous

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a
stirring at 60°C for 24h. When 1.1 eq of (EtO)3SiH was added, only the nitro group of
p-nitroacetophenone was selectively reduced. When the amount of (EtO)3SiH was increased to 3
eq, both the nitro and the carbonyl group of p-nitroacetophenone were reduced.
With acetonphenone as a model substrate we found that the conversion almost kept unchanged
with the increase of reaction temperature (Supporting Information: Table S2, entries 1 - 3). At the
same reaction temperature, the conversion increased by only 3% when the reaction time was
extended from 24h to 48h (Table S2, entries 4 - 6). However, when the catalyst loading was
increased from 2 mol% to 5 mol%, the conversion was increased from 67% to 94% (Table S2,
entries 1 and 7). Therefore, we expanded the scope of the ketone substrates with the catalyst loading
of 5 mol% (Eq. (4), Table 2) and found that the yields are from moderate to excellent with the 12
ketones. The aromatic ketones with reducible groups could also be reduced to the related alcohols.
The properties of the substituent groups at the phenyl rings do not have significant influence on the
yields. It is interesting that the nitro group of p-nitroacetophenone could be selectively reduced to
p-aminoacetophenone under certain conditions (Table 2, c). This is a rare examples [25 - 29].
Table 3 Selective reduction of α,β-unsaturated carbonyls catalyzed by 5.a,b
a
Catalytic reaction conditions: (1) cinnamaldehyde (2.0 mmol), (EtO)3SiH (2.2 mmol) and 5 (0.02
mmol) in 2 ml THF, 50℃, 4h. (2) MeOH (2 mL) and 10% aqueous solution of NaOH (5 mL) with
b
c
vigorous stirring at 60°C for about 24h. Isolated Yields. Catalyst 2%, 24h and 60°C. dGC Yield.
The selective reduction of the C=C and C=O bond of α,β-uns aturated aldehyde is regarded as
a challenge in organic synthesis. Some heterogeneous catalysts containing precious metals were

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found for the selective hydrogenation of ,-unsaturated aldehydes [30, 31]. Beller reported the
homogeneous iron catalysts for the selective hydrogenation of ,-unsaturated aldehydes [32, 33].
In comparison with heterogeneous catalysts for the selective hydrogenation of ,-unsaturated
aldehydes and ketones, less reports on homogeneous catalysts were reported for the reduction
transformations. Using complex 5 as catalyst, the selective reduction reactions of α,β-unsaturated
aldehydes were also studied (Eq. (5), Table 3). In the presence of 1 mol% of 5, the corresponding
cinnamyl alcohols could be obtained in the yields of 60% - 89% after 4 h at 50 °C. It’s worth noting
that the corresponding cinnamyl alcohol was formed in the lowest yield (60 %) if the phenyl ring of
cinnamaldehyde was substituted by chlorine atom. The corresponding cinnamyl alcohol was
produced in the highest yield (89 %) in the case of cinnamaldehyde with methyl group at the
α-position. For α-bromocinnamaldehyde, 3-phenyl-2-propyn-1-ol was isolated in a yield of 71% as
a result of elimination of HBr from the corresponding cinnamyl alcohol. ,-Unsaturated ketones
are also applicable to this catalytic system by increasing the catalyst loading to 2%, extending the
reaction time to 24h and raising the temperature to 60°C.
Scheme 1
It is worth noting that p-nitroacetophenone was reduced to 1-(4-aminophenyl)-ethanone with
1.1 eq of (EtO)3SiH, while the carbonyl group is retained. However, when the amount of (EtO)3SiH
is 3 eq, both the nitro and carbonyl group are simultaneously reduced (Scheme 1). While
benzaldehyde, acetophenone, and p-nitroacetophenone were present in the reaction system, only
benzaldehyde was reduced to benzyl alcohol with 1.1 eq of (EtO)3SiH. For the competition of
chalcone and acetophenone, the carbonyl group of chalcone was first reduced. These results
indicate that the order of the chemoselectivity for this catalytic system is –CHO > -NO2 >

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-C(=O)CH3 and the carbonyl group of chalcone is more active than that of acetophenone for the
reduction reaction.
It must be pointed out that the catalytic activity of hydrido selenophenolato iron(II) complex 4
is not so good as that of its S analogue complex [15] under similar catalytic reaction condations.
This difference might be caused by the decreasing of the polarity of the Fe-H bond in complex 4 in
comparison with that in the hydrido thiophenolato iron(II) complex. S and Se are located in the
same main group, and S has stronger electron-withdrawing ability than Se. Therefore, the polarity
of the Fe-H bond in the Se complex is reduced compared to that in the related S-type complex.
Great polarity of the Fe-H bond is favorable for the coordination and insertion of the C=O double
bond. Therefore, S-type complexes should have higher catalytic activity than Se-type complexes.
3. Conclusions
In this paper, three selenophenolato hydrido iron(II) complexes [cis-(H)(SeAr)Fe(PMe3)4] (4 - 6)
(Ar = C6H5 (4), p-MeOC6H4 (5) and o-MeC6H4 (6)) were prepared and characterized. Complexes 4
- 6 were used as catalysts for hydrosilylation of aldehydes and ketones. Among them complex 5 is
the best catalyst. Furthermore, α,β-unsaturated alcohols could be obtained from the selective
reduction reactions of the corresponding α,β-unsaturated carbonyls catalyzed by hydrido iron(II)
complex 5. This catalytic system has good tolerance for some common groups but it is easy to
reduce the nitro group to an amino group. The experiments indicate that the chemoselectivity for
this catalytic system is –CHO > -NO2 > -C(=O)CH3. It must be pointed out that the S-type
complexes should have higher catalytic activity than Se-type complexes.
Acknowledgements
We gratefully acknowledge the support by NSF China No. 21372143.

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Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.........
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Highlights
 Hydrido selenophenolato iron(II) complexes were prepared via Se-H activation / Iron
hydrido complexes could catalyze hydrosilylation of aldehydes and ketones / This catalytic
system has tolerance to halide, heteroaromatic ring and cyano group / α,β-unsaturated
carbonyls were selectively reduced to α,β-unsaturated alcohol / S-type complexes have
higher catalytic activity than Se-type complexes

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Pictogram
Graphical abstract