Syntheses of Transition Metal Complexes of Pentafluorophenylhydrazine

Article abstract of DOI:10.1002/zaac.201800010

By reaction of pentafluorophenylhydrazine with metal chlorides the complexes M(NH₂NHC₆F₅)₄Cl₂ (M = Co, Ni), M(NH₂NHC₆F₅)₂Cl₂ (M = Mn, Fe, Pd, Zn,

Full text of DOI:10.1002/zaac.201800010

Title: Syntheses of Transition Metal Complexes of
Pentafluorophenylhydrazine
Authors: Wolfgang Beck
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of the final Version of Record (VoR). This work is currently citable by
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To be cited as: Z. anorg. allg. Chem. 10.1002/zaac.201800010
Link to VoR: http://dx.doi.org/10.1002/zaac.201800010

Zeitschrift für anorganische und allgemeine Chemie
10.1002/zaac.201800010
Syntheses of Transition Metal Complexes of Pentafluorophenylhydrazine
Wolfram Rieber and Wolfgang Beck*
th
Dedicated to Professor Hanns Peter Boehm on the Occasion of his 90 Birthday
Key Words : Pentafluorophenylhydrazine as Ligand, Transition Metal Chlorides
Abstract. By reaction of pentafluorophenylhydrazine with metal chlorides the complexes
M(NH
Hg(NH
Cr(CO)
2
NHC
NHC
(NH
6
F
5
)
4
Cl
Cl have been obtained. From Cr(CO)
NHC ) was synthesized.
2
(M = Co, Ni), M(NH
2
NHC
6
F
5
)
2
Cl
2
(M = Mn, Fe, Pd, Zn, Cd), Cu(NH
2
NHC
6
F
5
)Cl and
2
6
F
5
)
2
6
and pentafluorophenylhydrazine the complex
5
2
6 5
F
Introduction
Pentafluorophenylhydrazine reacts readily with aldehydes and ketones to give hydrazones and
therefore has been applied very often as derivatizing agent for the determination of these carbonyl
compounds in air, in water, biological fluids, on surfaces, or cosmetics, using chromatography and
mass spectrometry [1, 2].It has been applied in organic synthesis, e.g. for the synthesis of pyrazoles
[
1].
To our knowledge, pentafluorophenylhydrazine has been used only in a few cases in coordination
and organometallic chemistry:
5 5
The ferrocenylhydrazone (C H )Fe(C
5
H
4
CH=NNHC
6
F ) was reported [3]. The structures of cobalt(II)
5
complexes of Schiff bases from pentafluorophenylhydrazine and salicyl aldehyde or acetylpyridine
have been determined by X-ray diffraction [4]. Reactions of pentafluorohydrazine with
(
porphyrine)iron and hemoglobin [5] and with [(C
bonded phenyl complexes. RHgX compounds have been prepared by reactions of
polyfluoroarylhydrazines RHNNH with Hg, HgO or HgX and various oxidizing agents [7]. In a trimeric
carbonylosmium cluster Os (CO)10(NH NHC ) the hydrazine group of pentafluorophenylhydrazine
was found as bridge between two Os atoms [8].
5
H
5
)Fe(CO)
2
]- [6] have been carried out to give -
2
2
3
2
F
6 5
In the following we present reactions of pentafluorphenylhydrazine with metal halides and with
hexacarbonylchromium(0) [Cr(CO) ].Shortly after the discovery of hydrazine by Curtius in 1894, the
latter [9] and others [10] reported several metal halide complexes with hydrazine and
phenylhydrazine of type M(NH NHR) (R = H [9 - 13], Ph [14,15]., e.g. also K. A. Hofmann in Munich
NHPh) has been synthesized from the phenyl substituted hydrazine and
6
2
X
2 2
[
[
11]. Mo(CO)
5
(NH
2
–
Mo(CO)
5
Cl] [16]. Reviews on the many metal complexes containing monodentate and bridging
hydrazine, bidendate and substituted hydrazine ligands [17-19] have been published.
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Zeitschrift für anorganische und allgemeine Chemie
10.1002/zaac.201800010
Pentafluorophenylhydrazine is a weaker base than phenylhydrazine (K
= 1.4 .10-10 compared to 1.6.
b
-
9
1
=
*
0 ) [20] and should coordinate through the NH
=================================
Professor Dr. Dr. h.c. Wolfgang Beck
2
group for steric reasons.
Ludwig-Maximilians-Universität München
Department Chemie
Butenandtstr. 5-13
8
1377 München
E-mail: wbe@cup.uni-muenchen.de
Results and Discussion
The metal dichlorides MCl
2
(M = Co, Ni, Mn), which contain crystal water, and MCl
2
(M = Zn, Cd)
react with pentafluorophenylhydrazine in ethanol to give the complexes 1-5 in high yields.
2 6 5
[Co(NH NHC F )
4 2
Cl ] 1
2 6 5
[Mn(NH NHC F )
2
Cl
2
] 3
2 6 5
[Cd(NH NHC F )
2
Cl
2
] 5
2
[Ni(NH NHC
6 5
F )
4 2
Cl ] 2
2 6 5
[Zn(NH NHC F )
2
Cl
2
] 4
2 6 5
[Pd(NH NHC F )
2
Cl
2
] 6
These complexes are formed as nacreous, fine crystalline compounds, which mostly are not soluble
in the common organic solvents and are decomposed in water, as shown by the change of colour.
Reduction of Pd(II) to Pd(O) occurs on addition of pentafluorophenylhydrazine to PdCl
2
or Pd(NO
3
) in
2
ethanol. However, complex 6 was available by reaction of [AsPh
4 2 4
] [PdCl ] in aprotic solvents (e.g.
dichloromethane).
Long ago, it was already observed, that metal(III) chlorides and hydrazine yield metal(II) complexes
12, 17]. Reduction of Fe(III), Cu(II) and Hg(II) occurs also with pentafluorophenylhydrazine in
reactions with FeCl , CuCl and HgCl in ethanol and the complexes 7-9 could be isolated:
[
3
2
2
2 6
[Fe(NH NHC F
5
)
2
CL
2
] 7
2 6
[Cu(NH NHC F
5
)Cl] 8
[Hg(NH
2
NHC
6
F ) Cl] 9
5
2
Complexes 7 and 8 were also obtained from FeCl
2
and CuCl. No reaction was observed with Hg
Cl
2 2
and NH NHC . Hg(II) complexes were reported [11, 21] from HgCl
2
6
F
5
2
and N H .
2 4
Analogously to N
H
2 4
[17, 22], N
2
and pentafluorophenylaniline are formed by reaction of FeCl
3
with
pentafluorophenylhydrazine as reducing agent; C
spectrum and acetyl derivative.
6 5
F
NH could be identified by boiling point, IR-
2
In aqueous solution , CuCl
2
and pentafluorophenylhydrazine afforded a nitrogen free compound
under vigorous evolution of gas, which - presumably - is a fluorobenzene derivative [20].
-
1
In the IR spectra, besides the N-H absorptions at 3100-3300 cm (NH) and at 1580-1610
-
1
-1
cm (NH), the N-N absorption at 950 cm is characteristic (see experimental part) and may be
indicative for unidentate pentafluorophenylhydrazine as ligand , coordinated through the H N group
as for phenylhydrazine for which no hydrazine bridged complexes are known, probably for steric
2
-
1
reasons[17, 18].E.g. (For free pentafluorophenylhydrazine N-N = 940 cm ).
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Zeitschrift für anorganische und allgemeine Chemie
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The palladium(II) complex 6 is monomeric in acetone solution (osmometrically determined),
according to a planar tetracoordinated structure. For Zn-complexes with phenylhydrazine ligands a
tetrahedral structure was determined [23], which should be present also in 4, whereas for
2 4
[Zn(N H )
2 2
Cl ] a polymeric structure with infinite chains -Zn-NH
2
-NH -Zn- was found [24].
2
The complexes 1-7 exhibit the same composition as the corresponding phenylhydrazine (NH NHPh)
2
metal complexes [14].
The cobalt and nickel complexes 1 and 2 react with phenylisocyanate PhN=C=O and
phenylisothiocyanate PhN=C=S to give the complexes 10-13:
2
[M[NH -N(C
6 5 2 2
F )-C(NHPh)=O] Cl ]
2
[M[NH -N(C
6
F
5
)-C(=S)-N(HPh)]
4
Cl ]
2
1
0: M = Co
1: M = Ni
12: M = Co
13: M = Ni
1
For 10 and 11 a six coordinated bischelate structure has to be assumed as in various semicarbazide
complexes [25-27], whereas for 12 and 13 a chelate structure is not probable. In good accordance
-
1
with these proposals the C=O absorption of 10 and 11 is shifted from 1698 cm of the free
-
1
semicarbazide to 1640 cm in the complexes, whereas no comparable shift is observed for the C=S
absorption of the thiosemicarbazide compounds 12 and 13 (see e.g. [28]. In the reactions to 10-13
the amino group is protected by the metal atom against attack of an electrophile. By these reactions
1
,1-disubstituted hydrazines, which readily can be cleaved from the metal ion by water or weak
acids, are available in a directed way.
Finally, an organometallic complex has been synthesized by photochemical reaction [29] of
hexacarbonyl chromium with pentafluorophenylhydrazine and [Cr(CO)
5
(NH
isolated and characterized. The N-N absorption at 945 cm of 14 is again typical for the
unidendate hydrazine ligand. Pentacarbonyl complexes of Cr, Mo and W with N are interesting
) and dinitrogen
2
NHC
6
F )] (14) could be
5
-
1
H
2 4
2 2
H
and valuable starting compounds for the syntheses of Sellmann`s diazene (N
complexes [30].
Acknowledgement
Support by Department Chemie of Ludwig-Maximilians-Universität München (Professor Thomas
Carell) is gratefully acknowledged. We thank Dr. Markus Müller, MLU, for valuable advice and help in
preparing the manuscript, Günther Berger and Detlev Dräger for active experimental collaboration.
Experimental Part
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Zeitschrift für anorganische und allgemeine Chemie
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The solvents were saturated with nitrogen and distilled. The syntheses were performed under
nitrogen atmosphere. Pentafluorophenylhydrazine was purchased from PCR Peninsular
Chemresearch Inc., Gainesville, Florida, USA. It can be synthesized by reaction of hydrazine hydrate
with hexafluorobenzene [20].
The analyses have been in part performed by Mikroanlytisches Labor Dr. E. Pascher, Bonn, using
2
V O
5
as oxidant.
Co(NH NHC
2
6 5
F )
Cl
4 2
(1): To a concentrated solution of CoCl .
2
6 H O (0.48 g, 2 mmol) in ethanol a
2
solution of pentafluorophenylhydrazine (1.6 g, 8 mmol) in ethanol was dropped, whereby
immediately a rose coloured , acreous precipitate was obtained, which was washed with ethanol and
diethylether and dried in vacuo for 6 h. IR (nujol): 3330 sh, 3284 s, 3140 sh (NH), 1590 m (NH),
-
1
1
7
520 vs, 1480 s (C-C), 952 ss (N-N) cm . CoC24
2
H12Cl F
0
N (922.3): Calcd. C 31.20, H 1.30, N 12.15, Cl
8
.70, F 41.40, Co 6.40; found C 31.04, H 1.28, N 12.05. Cl 7.89, F 41.60, Co 6.20.
Ni(NH
2
NHC
6
F
5
)
4
Cl
2
(2); By dropping a solution of pentafluorophenylhydrazine (1.6 g, 8 mmol) in
.
ethanol to a solution of NiCl
2
6 H O (0.48 g, 2 mmol) in ethanol a bright blue, glittering precipitate
2
was obtained, which was washed with ethanol and diethylether and dried in vacuo for 6 h. IR
-
1
(
nujol):3320 sh, 3284 s, 3160 sh (NH), 1585 m (NH), 1520 vs, 1478 s (C-C), 948s (N-N) cm .
NiC24H
12Cl
2
F
20
N
8
(922.0): Calcd. C 31.20, H. 1.30, N 12.15; found C 31.43, H 1.44, N 11.84.
Cl
2 2
(3): To a solution of MnCl .
2
4 H O (0.4g, 2 mmol) in ethanol (10 ml) a solution of
2
2
Mn(NH NHC
6 5
F )
pentafluorophenylhydrazine (0.8 g, 4 mmol) in ethanol (5 ml) was added. The gradually formed fine
crystalline, flesh-coloured precipitate was filtered off, washed with ethanol and diethylether and
dried in vacuo for 6 h. IR (nujol): 3312 sh, 3299 s, 3280 vs, 3140 s (NH), 1608 (NH), 1536 vs, 1525
-
1
vs, 1481 vs (C-C) 947 (N-N) cm . MnC12
6
H Cl
2
F
10
N (521.9): Calcd. C 27.60, H 1.16, N 10.72; found C
4
2
9.03, H 1.41, N 11.14.- Mn(NH
2
NH)2.5Cl
2
(621.0): Calcd. C 29.01, H 1.22 N 11.28.
Zn(NH
2
NHC
6
5
F )
Cl
2 2
(4): To a solution of ZnCl (0.4 g, 2 mmol) in ethanol a solution of
2
pentafluorophenylhydrazine (1.2 g, 4 mmol) in ethanol was added. The gradually formed white
bright precipitate was washed with cold ethanol (few ml) and several times with petroleum ether.
The compound is moderately soluble in ethanol and diethylether. IR (nujol): 3330 s, 3190m (NH),
-
1
1
1
590 s (NH), 1526 vs (C-C), 149 s, 950 s (N-N) cm . ZnC12
0.55; found C 26.93, H 1.23, N 10.34.
H
6 2
Cl F
10
N (532.5): Calcd. 27.00 H 1.13 N
4
Cd(NH
2
NHC
6
5
F )
Cl
2 2
(5): To a solution of CdCl (0.36 g, 2 mmol) in ethanol (96 %, 30 ml) a solution of
2
pentafluorophenylhydrazine (0.8 g, 4 mmol) in ethanol (20 ml) was dropped. The white, fine
crystalline precipitate was filtered off, washed several times with ethanol and diethyether and dried
in vacuo for 6 h. IR (nujol): 3280 vs, 3141 s, 3100 sh (NH), 1610 s (NH), 1537 vs,1524 vs,1481vs (C-
-
1
C), 948 s (N-N) cm . CdC12
.58.
6 2
H Cl F
10
4
N (579.4): Calcd. C 24.85, H 1.05, N 9.68; found C 24.63, H 1.23, N
9
Pd(NH
2
NHC
6
F
5
)
2
Cl
2
(6): [AsPh
4
]
2
[PdCl
4
] was obtained by adding an aqueous solution of AsPh
and the formed precipitate was isolated and dried.
]( 1 g, 1.8 mmol, from AsPh Cl, Pd(NO , and NaCl) in dichloromethane
4
Cl to an
aqueous solution of NaCl (in excess) and Pd(NO
To a solution of [AsPh [PdCl
)
3 2
]
4 2
4
4
)
3 2
a solution of pentafluoprophenylhydrazine (1.1 g, 6 mmol) in dichloromethane was added. From the
dark brown solutions after 1 min a gold yellow, nacreous precipitate appeared, which was washed
with dichloromethane. The complex is moderately soluble in ethanol and diethylether. IR (nujol):
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Zeitschrift für anorganische und allgemeine Chemie
10.1002/zaac.201800010
-
1
3
280 s, 3218 s 3100sh (NH), 1582 s (NH), 1523 s, 1517 vs, 1468 s (C-C), 962 s (N-N) cm .
Cl (573,3): Calcd. C 25.10, H 1.05, N 9.79: found C 25.07, H 1.16 N 9.81, M 540
osmometrically in acetone).
PdC12
(
H
6
2 10
F N
4
(7): Under N
2
atmosphere to a solution of FeCl .
3
6 H O (0.4 g, 1.5 mmol) in ethanol
2
2 6
Fe(NH NHC F
5
)
2
Cl
2
a solution of pentafluorophenylhydrazine (1.55 g, 7.8 mmol) in ethanol (20 ml) was added. Under
slight evolution of gas a white precipitate appeared, which was filtered off after 1 h, washed with
ethanol and diethylether and dried in vacuo. The complex turned dark brown on air. From the fitrate
by addition of diluted NaOH and extraction with diethylether pentafluoroaniline could be isolated,
which was identified by its boiling point153-155 °C and its acetyl derivative (m.p. 129 °C) [31].
IR (nujol): 3330 vs, 3300 m, 3278 s, 3130 m (NH), 1604 m (NH), 1535 s, 1520 s, 1481 s (C-C), 943 s
-
1
(
N-N) cm . Fe12
6
H Cl
2
F
10
N (523.0): Calc. C 27.58 H 1.15, N 10.71, Cl 13.57; found C 28.35, H 1.64, N
4
1
0.50, Cl 13.71.
Under N
2
atmosphere to a solution of FeCl .
2
4 H O (0.2 g, 1 mmol) in ethanol (5 ml)
2
pentafluorophenylhydrazine (0.4 g, 2 mmol) was added and after 1 min a white precipitate
appeared, which showed an IR spectrum, identical with that of the complex from FeCl
3
.
Cu(NH
(
2
NHC
6
5
F )
2
Cl (8): Under N
2
atmosphere to a solution of CuCl .
10 ml) a solution of pentafluorphenylhydrazine (1.5 g, 7.5 mmol) in ethanol (20 ml) was added.
2
2 H O (0.4 g, 2.3 mmol) in ethanol
2
Immediately – with slight evolution of gas – the white, bright copper(I) complex precipitated, which
was washed with ethanol and diethylether. The complex turned brown on air and with NaOH
solution red Cu
518 vs, 1463 m(C-C), 953 s (N-N) cm . CuC
found C 27.02, H 1.33, N 9.50, Cl 12.0.C
2
O was formed on heating. IR (nujol): 3290 s, 3140 m (NH), 1583 (NH), 1527 sh,
-
1
1
6
H
3
ClF
5
N (302.1): Calc. 24.20, H 1.01, N 9.45, Cl 11,80;
2
Complex 8 was also obtained by addition of a solution of pentafluorophenylhydrazine (0.3 g, 1.5
mmol) in ethanol (4 ml) to a suspension of CuCl (0.1g, 1 mmol) in ethanol (2 ml). The suspension was
stirred for 1 d.
2
Hg(NH NHC
6 5
F )
Cl
2 2
[9]: To HgCl (0.54 g, 2 mmol) in ethanol (14 ml) a solution of
2
pentafluorophenylhydrazine ( 0.8 g, 4 mmol) in ethanol (10 ml) was added. The formed bright white
precipitate was filtered off and washed with diethylether. The complex is moderately soluble in
ethanol. IR (nujol): 3242 s, 3124 m, 3092 sh (NH), 1604 m (NH), 1537 vs.1524 vs, 1463 s (C-C), 953 s
-
1
(
N-N) cm . HgC12
H
6
ClF10N
4
(632.3): Calcd. C 22.80, H 0.86, N 8.86; found c 22.53, H. 1.12, N 9.46.
Co[NH2--N(C )-C(NHC
6
F
5
6
H
5
)=O] Cl (10) : Under N atmosphere to complex 1 (1 g, 1.1 mmol)
2
2
2
phenylisocyanate (3 ml) was added. After some min from the dark blue solution a light blue
precipitate was formed which - after 2 h - was filtered off and washed several times with petroleum
ether and with some ml of diethylether and dried in vacuo. The complex is soluble in diethylether,
ethanol and acetone. M.P. 130°C. Decomposition with water to give the free semicarbazone and Co
(
7
2
II). IR (nujol): 3290 vs (NH), 1640s (CO), 1598 s (NH), 1558 s, 1520 vs, 1448 m (C-C), 970 as (N-N),
-
1
52s, 690 m (CH) cm . CoC26
H
16Cl
2
F
10
N
6
O (764.3): Calcd. C 40.70, H 2.34, N 10.95; found C 41.44, H
2
.58, N 10.42.
Ni[NH
2
-N(C
6
5 6
F )-C(NHC H
5
)=O]
2
(11): Under N atmosphere to complex 2 ( 1 g, 1.1.mmol)
2
phenylisocyanate (3 ml) was added. From the dark green solution a light green precipitate was
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Zeitschrift für anorganische und allgemeine Chemie
10.1002/zaac.201800010
obtainded after some min, which –after 2 h-was filtered off and washed several times with
petroleum ether and diethylether and dried in vacuo. M. P. 176 °C, The complex is decomposed in
water to give the free semicarbazone and Ni(II). IR(nujol): 3265 vs (NH), 1640 s (CO), 1598 s (NH),
-
1
1
4
570 s,1520 ss, 1450 s, 968 s (N-N), 750s , 690 s( CH) cm : NiC26
0.80, H 2.34, N 10.95; found C 39.25, H 2.65, N 9.97.
H16Cl
2 10
F N
6
O (764.1): Calcd. C
2
2
Co[NH -N(C
6 5
F )-C(S)-NHC
6
H
5 4
]
Cl (12): To complex 1 (1 g, 1.1 mmol) phenythioisocyanate (3 ml) was
2
added and the mixture was stirred for 1 d and its color changed to violet. A light blue precipitate was
formed, which was washed several times with petroleum ether and then with some ml of
diethylether. The complex is well soluble in ethanol and acetone. IR (nujol): 3340 sh, 3305 sh, 3258
sh, (NH), 1595 m (NH), 1565 m, 1525 vs, 1455 m (C-C), 1276 (CS), 973 s (N-N),735 m, 692 S (CH)
-
1
cm . CoC52
2
H32Cl F
20 12
N S
4
(1463.0): Calcd. C 42.55, H 2.19, N 11.45; found C 42.58, H 2.27, N 10.87.
2
Ni[NH – N(C
6
F
5
)-C(S)-NHC Cl (13) : The mixture of complex 2 (1 g, 1.1 mmol) and
6
H
5
]
4
2
phenylthioisocyanate (3 ml) changed its color to green and after stirring for 1 d a light green
precipitate was obtained, which was washed several times with petroleum ether and some ml of
diethylether and dried in vacuo. . The complex is soluble in ethanol and acetone. IR (nujol): 3340 m,
3
260 sh, 3150 m (NH), 1595 sh (NH), 1515 vs, 1448 sh, 1276 m (CS), 960 s (N-N), 735 m, 690 s
-
1
(CH) cm . NiC52
H
32Cl
2 20
F N
12
4
S (1462.8): Calcd. C 42.55, H 2.19, n 11.45; found C 43.10, H 1.79, N
1
1.51.
Cr(CO)
5 2 6
(NH NHC F
5
) (14): A solution of Cr(CO) (0.22g, 1 mmol) and pentafluorophenylhydrazine (0.4
6
g, 2 mmol) In THF (20 ml) was irradiated for 100 min with a UV lamp (Quecksilberhochdruckbrenner
TQ 81, Fa. Hanau). 4 ml of CO gas were measured and the solution turned its color from yellow to
brown. The volume of the solution was reduced to about 7 ml in vacuo and ethanol and water were
added to give a dirty-yellow precipitate, which was dissolved in ethanol and then precipitated with
water. M.P. 80 °C (dec.). IR (nujol): 3350 m, 3270 sh (NH), 2075 s, 1925vs, 1855 s (CO), 1605 sh
-
1
(
NH), 1505 s,1495 s, 1460 s (C-C), 945 (N-N) cm . CrC11
H
F
3 5
N
2
O (390); Calcd. C 33.82, H 0.77, N
5
7
.18,; found C 34.00, H 1.30, N 7.30.
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2
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4
[
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