Catalytic N?N bond cleavage of hydrazine by thiolate-bridged iron-ruthenium heteronuclear complexes

Article abstract of DOI:10.1016/j.inoche.2017.06.008

The novel thiolate-bridged iron-ruthenium heteronuclear complex [(PPh₃)(bdt)Ru(μ-η²:η⁴-bdt)FeCp*] (1, Cp*?=?η⁵-C₅Me₅, bdt?=?benzene-1,2-dithiolate) was prepared by one-electron reduction of

Full text of DOI:10.1016/j.inoche.2017.06.008

Inorganic Chemistry Communications 83 (2017) 66–69
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Inorganic Chemistry Communications
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Short communication
Catalytic N−N bond cleavage of hydrazine by thiolate-bridged
iron-ruthenium heteronuclear complexes
Yixin Zhang, Jinfeng Zhao, Dawei Yang ⁎, Yanpeng Zhang, Baomin Wang, Jingping Qu
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, PR China
a r t i c l e i n f o
a b s t r a c t
2
4
Article history:
The novel thiolate-bridged iron-ruthenium heteronuclear complex [(PPh )(bdt)Ru(μ-η :η -bdt)FeCp*]
3
Received 27 April 2017
Received in revised form 31 May 2017
Accepted 1 June 2017
5
(
[
1
1, Cp* = η -C
(PPh )(bdt)Ru(μ-η :η -bdt)FeCp*][FeCl
can also be one-electron oxidized by Fc·PF
5 5
Me , bdt = benzene-1,2-dithiolate) was prepared by one-electron reduction of complex
2
4
3
3
] (1[FeCl
3
]) using CoCp
2
as reducing agent. Meanwhile, complex
] or 1[BF ].
6
or HBF
4
to regenerate the ionic complex 1[PF
6
4
Available online 15 June 2017
Importantly, complex 1 shows good reactivity toward the catalytic N−N bond cleavage of hydrazine into
ammonia.
Keywords:
©
2017 Elsevier B.V. All rights reserved.
Iron-ruthenium complexes
Interconversion
Redox properties
N−N bond cleavage
Heterometallic complexes have received tremendous attention
owing to their unique reactivity, realizing transformations of substrates
that monometallic complexes cannot accomplish [1–6]. That is because
the cooperative interaction between different metals, the result of direct
metal-metal bond, can enhance catalytic properties [7–11]. In addition,
most biological enzymes featuring multi-metallic active sites also exert
the cooperative effect to accomplish catalytic cycles, for example, nitro-
genases [12–14]. Given that iron-sulfur clusters are widely distributed
in the active sites of these enzymes, synthetic chemistry of iron-sulfur
complexes was inspired to realize the biomimetic simulation for enzy-
matic function [15–18]. In the previous work of our group, thiolate-
bridged diiron complexes have been synthesized and investigated to-
ward their reactivity [19–25]. A series of nitrogenase model complexes,
mononuclear ruthenium complex RuCl
iron complex Cp*Fe(bdt) derived from [Cp*Fe(μ-η :η -bdt)FeCp*][BF
(bdt = benzene-1,2-dithiolate) [34]. After stirring the mixture of 1
equiv. of Cp*Fe(bdt) and 0.5 equiv. of RuCl (PPh in dichloromethane
2 3 3
(PPh ) [36] and mononuclear
2
4
4
]
2
3 3
)
at room temperature for 5 h, the resulting grey solution was dried under
vacuum and then the residue was washed with ethyl ether to afford a
2
4
grey powder [(PPh
51% yield. Resonances shown in the H NMR spectrum of complex
1[FeCl ] are difficult to be attributed due to the magnetic disturbance
of the anion FeCl
structure, complex 1[PF
exchange of complex 1[FeCl
of complex 1[PF ] in CD Cl , four doublets for bdt protons are shown
at δ = 8.35, 7.74, 7.65 and 7.45 ppm, indicative of the existence of two
bdt ligands. Three resonances for PPh protons at δ = 7.21, 7.10 and
6.84 ppm and one resonance for Cp* methyl protons at δ = 0.89 ppm
are also observed. The 31P NMR spectrum of complex 1[FeCl
] in
CD Cl exhibits one resonance assigned to PPh ligand at δ =
25.56 ppm. The electrospray ionization high-resolution mass spectrum
(ESI-HRMS) of complex 1[FeCl ] shows a molecular peak of 834.9971
(calcd 834.9987) to confirm the composition of the cation in 1[FeCl ].
Crystals suitable for X-ray diffraction were obtained by slow diffusion
of ethyl ether into a dichloromethane solution of complex 1[FeCl ].
The cationic structure of complex 1[FeCl ] is shown in Fig. 1. It is a
3 3 3
)(bdt)Ru(μ-η :η -bdt)FeCp*][FeCl ] (1[FeCl ]) in
1
3
−
3
[37]. In order to get a clear profile of the detailed
] [38] was obtained by the counteranion
6
1
3
6
] with NaPF . In the H NMR spectrum
6
2
2
1
1
1
2
1
2
[
Cp*Fe(μ-SR )
2
(μ-η :η -R N=NH)FeCp*] (R = Me, Et; R = Me, Ph;
), can catalytically cleave N−N bond of hydrazine and
5
Cp* = η -C
5
Me
5
3
its derivatives [20]. On the other hand, dinuclear ruthenium complexes
have excellent potentials on activating and transforming substrates
3
[26–30]. Based on the two above respects, constructing heterometallic
2
2
3
complexes incorporating iron-sulfur clusters and ruthenium could ex-
hibit good reactivity [31]. Generally, half-sandwich complexes contain-
ing Cp* ligand can play as good precursors for constituting
heteronuclear complexes [32–35]. Here, we report the synthesis and
characterization of thiolate-bridged iron-ruthenium heteronuclear
complexes derived from self-assembly, which show reactivity toward
the N−N bond cleavage of hydrazine.
3
3
3
3
dinuclear iron-ruthenium complex bridged by one bdt ligand, while
the iron center features one Cp* ligand and the ruthenium center fea-
As illustrated in Scheme 1, iron-ruthenium heteronuclear complex
1
[FeCl
3
]
was synthesized by self-assembly reaction between
3
tures another bdt ligand and one PPh ligand. The bridged bdt ligand
leans toward the iron center, which binds two thiolates and two adja-
cent carbons of aromatic ring in the bdt ligand. The shorter distances
of C23–C24 and C25–C26 than the others in the benzene ring indicate
⁎
Corresponding author.
E-mail address: yangdw@dlut.edu.cn (D. Yang).
http://dx.doi.org/10.1016/j.inoche.2017.06.008
387-7003/© 2017 Elsevier B.V. All rights reserved.
1

Y. Zhang et al. / Inorganic Chemistry Communications 83 (2017) 66–69
67
3
Scheme 1. Synthesis of complex 1[FeCl ].
that the bridged bdt ligand is a π-radical monoanionic ligand, which
transfers one electron to the iron center [39]. This leads to the inference
that the iron center is more electron-deficient than the ruthenium cen-
ter, even though the formal oxidation states of the two metal centers are
both +3. Interestingly, in the structure of a similar dinuclear iron-ruthe-
rich redox properties, which inspired us to further perform the chemical
reduction and oxidation of complex 1[FeCl ]. The dichloromethane
solution of complex 1[FeCl ] was added with 1 equiv. of CoCp at
3
3
2
−78 °C, and then the mixture was warmed slowly to room tempera-
ture. The suspension was filtered and dried under vacuum, and then
the residue was washed with n-hexane to give a grey-black powder
2
4
nium complex [Cp*Fe(μ-η :η -bdt)RuCp*][BF
our group, the bridged bdt ligand leans toward the ruthenium center
34]. This difference is presumably because of the steric effect of a sec-
ond bdt ligand and a PPh ligand instead of Cp* ligand binding to the ru-
thenium center of complex 1[FeCl ]. The Fe−Ru distance of complex
[FeCl ] is 2.6736(5) Å, implying a Fe−Ru single bond.
To get further insight into the heteronuclear complex 1[FeCl
redox behaviors of complex 1[FeCl ] were explored by the cyclic volt-
ammetry. The cyclic voltammogram of complex 1[FeCl ] in dichloro-
methane solution shows three reversible reductive waves at E1/2
4
] previously reported by
2
4
[(PPh
Moreover, complex 1 can be readily oxidized to 1[PF
as oxidant in 90% yield. In addition, treatment of complex 1 with 1
equiv. of HBF ·Et O in dichloromethane at room temperature also
afforded one-electron oxidized product 1[BF ] in 88% yield, accom-
3
)(bdt)Ru(μ-η :η -bdt)FeCp*] (1) in 72% yield (Scheme 2).
[
6
] with Fc·PF
6
3
3
4
2
1
3
4
3
], the
panied with the liberation of dihydrogen. Unfortunately, expected
oxidative addition of complex 1 didn't occur, but the one-electron
oxidation underwent, which should be due to the steric hindrance
effect [34].
3
3
red
=
+
/0
1
−
0.28, −0.52 and −1.30 V (versus Fc ), respectively (Fig. 2). The
Resonances shown in the H NMR spectrum of complex 1 are diffi-
above electrochemical data suggest that complex 1[FeCl ] possesses
3
cult to be exactly attributed, and one characteristic resonance assigned
to PPh ligand (δ = −4.57 ppm) is shown in the P NMR spectrum.
3
31
Crystals suitable for X-ray diffraction were obtained by slow diffusion
of n-hexane into a dichloromethane solution of complex 1 [40]. The
structure of complex 1 is similar to the cationic structure of complex
1
3
[FeCl ], yet with a longer Fe–Ru distance of 2.8627(4) Å. Complex 1
is a mixed-valence iron-ruthenium complex, in which two metal cen-
ters are in the formal oxidation states of +2 and +3. The bdt ligand
also leans toward the iron center, indicating the formal oxidation states
III
II
of Fe –Ru .
Fig. 1. ORTEP (ellipsoids at 50% probability) diagram of complex 1[FeCl
more populated position of the disordered Cp* ligand. All hydrogen atoms and the FeCl
anion are omitted for clarity. Selected bond distances (Å) and bond angles (deg): Fe1−Ru1
.6736(5), Fe1−S1 2.2303(10), Fe1−S2 2.2244(8), Fe1–C21 2.189(3), Fe1–C22 2.175(3),
Ru1–S1 2.3112(8), Ru1–S2 2.3073(8), Ru1–S3 2.2599(8), Ru1–S4 2.2646(8), Ru1–P1
.3026(8), S1–C21 1.753(3), S2–C22 1.753(3), C21–C22 1.420(4), C22–C23 1.416(4),
C23–C24 1.353(5), C24–C25 1.404(5), C25–C26 1.351(5), C26–C21 1.420(4), Fe1–S1–Ru1
2.11(3), Fe1–S2–Ru1 72.28(3), Fe1–Ru1–S3 110.18(3), Fe1–Ru1–S4 115.55(3),
Ru1–Fe1–C21 83.27(8), Ru1–Fe1–C22 83.46(8), S1–Fe1Ru1–S2 119.89(4).
3
] showing only the
−
3
2
2
7
n
3 4 6 2 2 2
Fig. 2. Cyclic voltammogram of 1[FeCl ] (1 mM in 0.1 M Bu NPF in CH Cl under N ).

68
Y. Zhang et al. / Inorganic Chemistry Communications 83 (2017) 66–69
Scheme 2. Interconversion of complexes [1]+ and 1. Reaction conditions: (i) 1 equiv. of CoCp
equiv. of HBF ·Et O, CH Cl , rt, 2 h, 88% for 1[BF ].
2 2 2 6 2 2 6
, CH Cl , −78 °C to rt, 24 h, 72%; (ii) 1 equiv. of Fc·PF , CH Cl , rt, 2 h, 90% for 1[PF ]; (iii) 1
4
2
2
2
4
Based on the studies of thiolate-bridged diiron complexes on the cat-
Acknowledgements
alytic cleavage of N−N bond in hydrazine [20], reactions of complex 1
and 1[FeCl
3
] with hydrazine were investigated. Stirring the THF solution
This work was supported by the National Natural Science Founda-
tion of China (Nos. 21231003, 21571026, 21690064), the Program for
Changjiang Scholars and Innovative Research Team in University (No.
IRT13008), and the “111” project of the Ministry of Education of China.
of complex 1 with 20 equiv. of hydrazine at room temperature afforded
ammonia in 74% yield (Eq. (1); Table 1, entry 1). The formation of am-
monia is the clear evidence for N−N bond cleavage of hydrazine by
complex 1, which requires no additional protons and electrons com-
pared to thiolate-bridged diiron complexes [20]. When the reaction of
Appendix A. Supplementary material
complex 1[FeCl
tions, ammonia was achieved in only 16% yield, accompanied with the
reduction of 1[FeCl ] to 1. By comparison, reactions of complexes
3
] and hydrazine was performed under similar condi-
CCDC1475867, CCDC1475868 and CCDC1475869 contain the sup-
plementary crystallographic data in CIF format for the structure report-
ed. This data can be obtained free of charge via http://www.ccdc.cam.ac.
uk/conts/retrieving.html, or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1E, UK; fax: (+44) 1223-336-
033; or e-mail: deposit@ccdc.cam.ac.uk. Supplementary data associated
with this article can be found in the online version, at http://dx.doi.org/
10.1016/j.inoche.2017.06.008.
3
2
4
2
4
[
Cp*Fe(μ-η :η -bdt)RuCp*][BF
4
] and [Cp*Fe(μ-η :η -bdt)RuCp*] [34]
with hydrazine were also performed, and the yields of ammonia were
3
7% and 13%, respectively.
Among these iron-ruthenium heteronuclear complexes, complex 1
exhibits the best reactivity toward the formation of ammonia from
hydrazine. In the reactions of complexes 1[FeCl ] and 1 with hydrazine,
3
complex 1 was considered to be responsible for ammonia formation. It
is assumed that the low-valent ruthenium(II) in complex 1 could play
a role of transferring electrons during the N−N bond cleavage of
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1
003–1004.
[40] Selected bond distances (Å) and bond angles (deg) of complex 1: Fe1−Ru1
2.8627(4), Fe1−S1 2.2449(8), Fe1−S2 2.662(8), Fe1−C21 2.126(3), Fe1−C22
2.122(3), Ru1−S1 2.3165(7), Ru1−S2 2.3110(7), Ru1−S3 2.3133(7), Ru1−S4
2.3027(8), Ru1−P1 2.2512(7), S1−C21 1.769(3), S2−C22 1.753(3), C21−C22
1.425(5), C22−C23 1.428(4), C23−C24 1.328(6), C24−C25 1.413(7), C25−C26
1.364(6), C26−C21 1.420(5), Fe1−S1−Ru1 77.73(2), Fe1−S2−Ru1 77.42(2),
Fe1−Ru1−S3 116.19(2), Fe1−Ru1−S4 113.21(2), Ru1−Fe1−C21 80.89(8),
Ru1−Fe1−C22 80.82(7), S1–Fe1Ru1–S2 123.37(4).
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29] K. Motoyama, M. Ikeda, Y. Miyake, Y. Nishibayashi, Ruthenium- and copper-cata-
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[41] 1H NMR data of complex [Cp*Fe(μ-η :η -bdt)(μ-η :η -HN=NH)RuCp*] (400 MHz,
CD Cl , ppm): δ 15.27 (d, J = 10.3 Hz, 1H, NH), 13.19 (d, J = 10.4 Hz, 1H, NH),
6.79 (m, 2H, bdt-H), 6.37 (br, 2H, bdt-H), 1.45 (s, 15H, Cp*-CH ), 1.30 (s, 15H,
2
2
1
1
[
30] H. Chai, Q. Wang, T. Liu, Z. Yu, Diruthenium(II)–NNN pincer complex catalysts for
transfer hydrogenation of ketones, Dalton Trans. 45 (2016) 17843–17849.
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nium complexes bearing a phosphine ligand and application to propargylic
2
2
[
3
Cp*-CH
3
). IR (Film; cm− ): 3231 (νNH).
1