Vanadium(V) hydrazido(2-) thiolate imine alkoxide complexes

Article abstract of DOI:10.1039/b718968k

The reaction of (Me₃Si)₂TIP with V(NNMe ₂)(OAr)₃ results in the production of V(NNMe ₂)(TIP)(OAr), where TIP is 2-((2-thiolatophenylimino)methylene) phenolate. The aryloxide is readily displaced by ISiMe₃ to form an insoluble iodide complex formulated as V(NNMe₂)(TIP)(I). The iodide was used to prepare three different complexes: [V(NNMe₂)(TIP)(dmpe)] I, [V(NNMe₂)(TIP)(Bu^tbpy)][OTf], and [V(NNMe ₂)(TIP)(Bu^tbpy)][SbF₆]. The phosphine derivative, [V(NNMe₂)(TIP)(dmpe)]I, was characterized by X-ray diffraction and shows a quite short N-N distance of 1.293(3) A indicative of a dominant isodiazene resonance form. The Royal Society of Chemistry.

Full text of DOI:10.1039/b718968k

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Vanadium(V) hydrazido(2−) thiolate imine alkoxide complexes†
Sanjukta Banerjee and Aaron L. Odom*
Received 10th December 2007, Accepted 28th January 2008
First published as an Advance Article on the web 28th February 2008
DOI: 10.1039/b718968k
The reaction of (Me3Si)2TIP with V(NNMe2)(OAr)3 results in the production of V(NNMe2)(TIP)(OAr),
where TIP is 2-((2-thiolatophenylimino)methylene)phenolate. The aryloxide is readily displaced by
ISiMe3 to form an insoluble iodide complex formulated as V(NNMe2)(TIP)(I). The iodide was used to
prepare three different complexes: [V(NNMe2)(TIP)(dmpe)]I, [V(NNMe2)(TIP)(Butbpy)][OTf], and
[V(NNMe2)(TIP)(Butbpy)][SbF6]. The phosphine derivative, [V(NNMe2)(TIP)(dmpe)]I, was
˚
characterized by X-ray diffraction and shows a quite short N–N distance of 1.293(3) A indicative of a
dominant isodiazene resonance form.
Pri2C6H3, has been reported.21 However, to the best of our
Introduction
knowledge, no examples of vanadium hydrazido(2−) complexes
are known where all of the elemental connections found in the
enzyme, S, N, and O, are in the same coordination sphere.
As part of our ongoing interest in the study of transition
metal hydrazido(2−) complexes,22 we report the syntheses of
vanadium(V) hydrazido(2−) complexes with a chelating ligand
containing a thiolate, alkoxide, and donor imine (eqn (1)), 2-((2-
thiol-phenylimino)methylene)phenol (H2TIP).23
Metal hydrazido(2−) complexes are well known intermediates in
dinitrogen activation to produce NH3.1 Hydrazido(2−) complexes
have been synthesized for a large variety of metal centers including
Mo, W,2 Ti, Zr,3 Re,4 Os,5 Pt,6 Au,7 Li,8 U,9 and Tc.10 Among these,
Mo-based hydrazido complexes have been studied extensively
due to their presence in nitrogenase.11 Similarly, there has been
considerable interest in vanadium hydrazido(2−) complexes since
the discovery of vanadium in the active sites of similar enzymes.12,13
The reduction of dinitrogen by these nitrogenase enzymes is
believed to involve metal-bound (Fe, Mo, V) hydrazine and
hydrazido intermediates.14 The FeMoco enzyme has been studied
extensively and shown by X-ray crystallography to contain a
cluster with the Mo atom ligated by one nitrogen, three sulfurs, and
two oxygen atoms.11 It is thought that vanadium in nitrogenase15
enzymes occupies a similar site. As it is believed that the Mo or V
may be the coordinating site for N2, it is important to understand
the hydrazido(2−) chemistry of vanadium with ligands containing
S, N, O atoms. In particular, reduction of N2 to NH3 by these
enzymes might involve intermediate species N2Hm and NHn (m =
0–4, n = 0–3) bound at a vanadium site.14
(1)
Results and discussion
In order to synthesize vanadium(V) hydrazido(2−) complexes with
the TIP ancillary, we initially attempted direct reaction of H2TIP
with V(NNMe2)(OAr)3.21 However, these reagents did not result in
the elimination of 2 HOAr and synthesis of V(NNMe2)(OAr)(TIP)
(1) as expected. However, (Me3Si)2TIP was synthesized readily
and treatment with V(NNMe2)(OAr)3 produced 1 in good yield
(Scheme 1).
In terms of mode of action for vanadium-containing nitroge-
nase, it has been demonstrated that S3-ligated vanadium in cluster
anions such as [Fe3S4X3V(DMF)3]− (X = Cl, Br, or I) binds
hydrazines16 and imides,17 and catalyzes their reduction.
In order to explore the chemistry of the V(NNMe2)(TIP)
framework further, we exchanged the aryloxide ligand in 1
with iodide. Treatment of 1 with ISiMe3 in toluene eliminated
Me3SiOAr and produced V(NNMe2)(TIP)(I) (2) in 95% crude
yield (eqn (2)). The iodide complex was quite insoluble in most
solvents but was effective as a starting material without further
purification.
Vanadium(V) hydrazido(2−) complexes with different ligands
(L = S, N, or O) are known in the literature.18–21 The first
example of a vanadium(V) hydrazido(2−) complex with sulfur
donor ligands appeared in 1997,18 V(NNMe2)(NS3) where NS3 =
(SCH2CH2)3N. This was followed by the synthesis of a series of
similar complexes with NS3 and OS2 ligand backbones on
vanadium(V).19 More recent examples have involved the synthesis
of V(NS3)(NNC5H10) using 1-aminopiperidine to introduce the
hydrazido(2−) moiety.20 In addition, a hydrazido(2−) complex
with alkoxide ligands, Me2NNV(OAr)3, where Ar = O-2,6-
3−
2−
(2)
Michigan State University, Department of Chemistry, East Lansing, MI,
48824, USA. E-mail: odom@chemistry.msu.edu
† CCDC reference number 670307. For crystallographic data in CIF or
other electronic format see DOI: 10.1039/b718968k. Electronic supple-
mentary information (ESI) available: Additional experimental data. See
DOI: 10.1039/b718968k
A brown suspension of iodide 2 in CH2Cl2 reacted with
dmpe, 1,2-(dimethylphosphino)ethane, to generate a dark red
solution (Scheme 2). The new complex, [V(NNMe2)(TIP)(dmpe)]I
(3), was isolated in 62% purified yield. Similarly, treatment
of 2 with 4,4ꢀ-tert-butyl-2,2ꢀ-bipyridine (Butbpy) and triflate or
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Fig. 1 ORTEP representation of the cation in 3 from X-ray diffraction.
Hydrogens and iodide anion are not shown. Ellipsoids are drawn ◦at
˚
the 50% probability level. Selected bond lengths (A) and angles ( ):
V(1)–N(1) 1.698(2), N(1)–N(2) 1.293(3), V(1)–O(1) 1.908(2), V(1)–N(3)
2.162(2), V(1)–S(1) 2.3383(8), V(1)–P(1) 2.5078(8), V(1)–P(2) 2.5079(8),
N(2)–N(1)–V(1) 168.5(2), O(1)–V(1)–S(1) 119.53(6).
Scheme 1 Synthesis of V(NNMe2)(OAr)(TIP) (1).
hexafluoroantimonate silver(I) salts resulted in cationic, hexaco-
ordinate complexes isolable in good yield (Scheme 2).
Fig. 2 Hydrazido(2−) versus isodiazene resonance forms.
˚
bond, 1.698(2) A, suggests a significant contribution from the
hydrazido(2−) resonance form as well.
Concluding remarks
Using readily prepared V(NNMe2)(OAr)3 as
a
starting
material, an example of
a
hydrazido(2−) TIP complex,
V(NNMe2)(OAr)(TIP) (1), can be prepared. Replacement of
the OAr ligand with iodide proceeds smoothly with ISiMe3.
While this iodide was not fully characterizable due to very low
solubility in common solvents, it served as starting material for
cationic hydrazido complexes. An X-ray diffraction study on one
of the cationic vanadium complexes, [V(NNMe2)(TIP)(dmpe)]I
(3), revealed a quite short N–N bond. This short N–N bond is
indicative of the V(III) cation having poor backbonding into the
=
N N p* orbital of an isodiazene.
Experimental
General considerations
All manipulations of air sensitive compounds were carried out
in an MBraun drybox under a purified nitrogen atmosphere.
Pentane (Spectrum Chemical Mfg. Corp.), toluene (Spectrum
Chemical Mfg. Corp.), ether (Columbus Chemical Industries
Inc.), dichloromethane (EM Science), acetonitrile (Spectrum
Chemical), and tetrahydrofuran (JADE Scientific) were sparged
with nitrogen to remove oxygen then dried by passing through
activated alumina. VCl3(THF)3 was purchased from Strem Chem-
ical Co. and used as received. 1,1-dimethylhydrazine was pur-
chased from Aldrich Chemical Co. and distilled from KOH prior
to use. 4,4ꢀ-di-tert-butyl-2,2ꢀ-bipyridine (Butbpy) was purchased
from Aldrich Chemical Co. and used as received. H2TIP23 and
Scheme 2 Synthesis of cationic hydrazido(2−) complexes.
The dmpe complex 3 was characterized by X-ray diffraction,
and an ORTEP representation is shown in Fig. 1. Unlike the Ti22
dimethylhydrazido(2−) complexes reported, this hexacoordinate
complex has a planar Me–N–Me moiety, which is common
for hydrazido(2−) complexes of most metals.24 This cationic
˚
complex has a short N–N bond of 1.293(3) A. The shortest
hydrazido N–N distances, for example in an iron porphyrin
complex,25 are ∼1.23 A. The hydrazido ligand is similar in metric
˚
parameters to a related cationic vanadium complex reported by
Dilworth and coworkers.26 The short N–N bond is indicative of
a double bond, and the NNMe2 ligand in this case may be better
described as an isodiazene (Fig. 2). While quite different from
21
V(NNMe2)(OAr)3 were synthesized according to the literature
procedures. Deuterated solvents were dried over purple sodium
benzophenone ketyl (C6D6) or phosphoric anhydride (CDCl3)
=
hydrazido(2−) ligands of Ti in many respects, the short V N
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and distilled under nitrogen. 1H and 13C NMR spectra were
V(NNMe2)(TIP)(I) (0.18 g, 0.39 mmol), and the powder was
suspended in CH2Cl2 (1.9 mL). To the stirred suspension was
added dmpe (0.058 g, 0.39 mmol). The mixture was stirred
overnight. The brown suspension gradually turned into a bright
red solution. The volatiles were removed in vacuo. The product
was crystallized from 1:1 CH2Cl2:THF in 62% yield (0.15 g,
0.24 mmol). 1H NMR (500 MHz, CDCl3): d = 9.47 (s, 1 H, imine-
CH), 8.19 (s, 1 H, aryl-CH), 7.93 (d, 1 H, JHH = 7.6, aryl-CH),
7.70 (t, 1 H, JHH = 4.5, aryl-CH), 7.65 (t, 1 H, JHH = 7.6, aryl-CH),
7.34 (q, 2 H, J = 2.4 and 3.0, aryl-CH), 7.28 (d, 1 H, J = 8.34,
aryl-CH), 7.18 (t, 1 H, J = 6.8, aryl-CH), 3.69 (s, 6 H, NCH3),
2.11–2.03 (br s, 2 H, CH2), 1.78–1.75 (dd, 6 H, J = 1.7 and 10.3,
PCH3), 1.78–1.66 (br s, 2 H, CH2), 0.54–0.37 (dd, 6 H, J = 9.9
1
recorded on Inova 300 or VXR-500 spectrometers. H and 13C
NMR spectral assignments were confirmed, when necessary, with
the use of 2-D 1H–1H and 13C–1H correlation NMR experiments.
Routine coupling constants in 13C NMR spectra are not reported.
All spectra were referenced internally to residual protiosolvent
(1H) or solvent (13C) resonances. Chemical shifts are quoted in
ppm and coupling constants in Hz.
Synthesis of (Me3Si)2TIP. All the manipulations were carried
out inside an inert atmosphere glove box. An Erlenmeyer flask
(100 mL) was loaded with H2TIP (1.00 g, 4.36 mmol) and toluene
(1.5 mL). The solution was cooled in a liquid nitrogen cooled
cold well inside the box. Triethylamine (1.78 g, 17.6 mmol) in
toluene (0.5 mL) was added to the solution. Trimethylsilyl iodide
(3.52 g, 17.6 mmol) in toluene (0.5 mL) then was added. After
the additions, the reaction was then allowed to warm to room
temperature and stir overnight. The reaction mixture became pale
yellow with a white precipitate. The precipitate was filtered with
a fritted funnel, and the volatiles were removed in vacuo. The
product was collected as a viscous, pale yellow oil in 87% yield
1
and 10.3, PCH3). 13C{ H} NMR (125 MHz, CDCl3): 165.6, 164.7,
149.8, 144.1, 144.1, 134.9, 134.7, 129.2, 127.3, 126.1, 121.7, 121.2,
119.2, 44.2, 29.3 (dd, JCP = 12.5 and 27.5 Hz, CH2), 25.2 (dd,
JCP = 9.6 and 26.8, CH2), 18.9 (dd, JCP = 3.0 and 27.8, PCH3),
1
14.6 (dd, JCP = 17.2 and 22.2, PCH3). 31P{ H} NMR (200 MHz):
39.2 (br s). 51V NMR (131.6 MHz, CDCl3):–21.7 (m1/2 = 1382 Hz).
Elemental analysis: Exp. (Calc.), C: 41.11 (41.12); H: 5.15 (5.09);
N: 6.77 (6.85). M.p.: 179–181 ◦C.
1
(1.43 g, 3.9 mmol). H NMR (300 MHz, C6D6): d = 7.56 (d,
J = 7.48, 1 H, imine-CH), 7.01–6.61 (m, 8 H, aryl), 0.23 (s, 9 H,
Synthesis of [V(NNMe2)(TIP)(Butbpy)][SbF6] (4). Under an
atmosphere of dry nitrogen, a filter flask (125 mL) was loaded
with 2 (0.30 g, 0.65 mmol) and CH2Cl2 (30 mL). The filter flask
was cooled inside a liquid nitrogen cooled cold well. Two separate
vials (20 mL) were loaded with Butbpy (0.17 g, 0.65 mmol) and
AgSbF6 (0.21 g, 0.61 mmol). To each reagent vial was added
CH2Cl2 (0.5 mL). Both the vials were cooled inside the cold well.
The cold solution of Butbpy was added to the filter flask. The
mixture was allowed to stir for 10 min followed by addition of
the AgSbF6 suspension. The reaction mixture then was allowed
to warm up to room temperature, sealed, and stirred overnight.
The dark brown suspension gradually turned into a reddish-purple
solution. The volatiles were removed in vacuo. Then solid products
were stirred with THF (25 mL), and AgI separated as a grey solid.
The solid was filtered using a fritted funnel. The volatiles were
removed in vacuo from the filtrate resulting in a reddish-purple
solid containing the crude product. The product was crystallized
1
SiCH3), 0.15 (s, 9 H, SiCH3). 13C{ H} NMR (125 MHz, C6D6):
d = 150.7, 147.9, 136.1, 128.3, 128.0, 126.2, 124.8, 122.5, 121.4,
120.0, 118.0, 110.7, 64.9, 0.69, 0.23.
Synthesis of V(NNMe2)(TIP)(OAr) (1). Under an atmosphere
of dry nitrogen, a threaded pressure tube was loaded with
V(NNMe2)(OAr)3 (1.50 g, 2.30 mmol) and (SiMe3)2TIP (0.87 g,
2.30 mmol) in toluene (9 mL). The pressure tube was taken outside
the box and heated at 120 ◦C for 2 d. After cooling the tube
to room temperature, the reaction mixture was filtered using a
fritted funnel. Volatiles were removed from the brown filtrate in
vacuo. This resulted in a dark brown solid. The brown solid was
washed with cold pentane, and the residue was dried in vacuo.
Finally, the product was crystallized as a dark brown solid from
1
1:1 ether:pentane in 74% yield (0.87 g, 1.70 mmol). H NMR
(500 MHz, C6D6): d = 9.21 (s, 1 H, imine-CH), 7.82–6.76 (m,
11 H, aryl-CH), 3.08 (s, 6 H, NCH3), 2.80 (m, 2 H, CHMe2), 0.84
1
from 1:1 CH2Cl2:pentane in 80% yield (0.34 g, 0.48 mmol). H
1
(d, 6 H, J = 6.9, CHCH3), 0.81 (d, 6 H, J = 6.9, CHCH3). 13C{ H}
NMR (300 MHz, CDCl3): d = 8.82 (d, 1 H, J = 6, bpy-CH),
8.77 (d, 1 H, J = 6, bpy-CH), 8.73 (s, 1 H, imine CH), 7.84–
6.83 (m, 12 H, aryl-CH and bpy-CH), 3.76 (s, 6 H, NCH3), 1.22
NMR (75 MHz, CDCl3): 167.2, 159.5, 147.8, 145.4, 134.8, 134.3,
134.0, 128.0, 127.2, 124.3, 122.3, 121.6, 120.7, 119.5, 119.4, 116.7,
43.8, 26.2, 22.9, 22.5. 51V NMR (131.6 MHz, CDCl3): 215.2 (m1/2
=
1
(s, 9 H, CCH3), 1.20 (s, 9 H, CCH3). 13C{ H} NMR (75 MHz,
1813 Hz). Elemental analysis: Exp. (Calc.), C: 63.47 (63.17); H:
CDCl3): 166.2, 165.9, 164.7, 163.0, 155.8, 153.2, 152.3, 150.4,
149.1, 147.6, 134.7, 134.1, 127.08, 127.06, 125.7, 122.7, 122.3,
121.7, 121.5, 119.5, 119.1, 118.2, 117.7, 43.6, 35.5, 29.99, 29.92.
51V NMR (131.6 MHz, CDCl3): 423.8 (m1/2 = 2832 Hz). Elemental
analysis: Exp. (Calc.), C: 47.74 (47.16); H: 4.82 (4.68); N: 8.01
(8.33). M.p.: 186–188 ◦C.
6.44 (6.24); N: 8.00 (8.19). M.p.: 152–154 ◦C.
Synthesis of [V(NNMe2)(TIP)(I) (2). Under an atmosphere of
dry nitrogen, a threaded pressure tube (20 mL) was loaded with
V(NNMe2)(TIP)(OAr) (0.76 g, 1.50 mmol) and ISiMe3 (0.33 g,
1.70 mmol) in toluene (6 mL). The solution was then heated at
45 ◦C overnight. A brown precipitate appeared from the reaction
mixture. The precipitate was filtered using a fritted funnel. The
solid was dried in vacuo. The product was isolated as brown
powder in 95% crude yield (0.66 g, 1.40 mmol). Several attempts to
purify this compound were unsuccessful as it was highly insoluble,
and the compound was used without further purification. M.p.:
216–218 ◦C.
Synthesis of [V(NNMe2)(TIP)(Butbpy)][OSO2CF3] (5). Under
an atmosphere of dry nitrogen, a filter flask (125 mL) was loaded
with 3 (0.30 g, 0.65 mmol) and CH2Cl2 (30 mL). The filter
flask was cooled inside a liquid nitrogen cooled cold well. To
the suspension was added a cold solution of Butbpy (0.17 g,
0.66 mmol) in CH2Cl2 (10 mL) followed by a cold suspension
of AgOTf (0.17 g, 0.65 mmol) in CH2Cl2 (5 mL). The reaction
mixture was allowed to warm up to room temperature and stir
overnight. The brown suspension gradually turned into a dark
Synthesis of [V(NNMe2)(TIP)(dmpe)]I (3). Under an at-
mosphere of dry nitrogen, a vial (20 mL) was loaded with
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purple solution. The volatiles were removed in vacuo resulting in
a dark purple solid. The solid was stirred in THF (25 mL) for
5 h. AgI separated as a grey solid, which was filtered away using a
fritted funnel. The volatiles were removed in vacuo from the filtrate.
The product was crystallized from 1:1 THF:pentane in 81% yield
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1
(0.31 g, 0.49 mmol). H NMR (300 MHz, CDCl3): d = 8.87 (d,
1 H, J = 8, bpy-CH), 8.80 (d, 1 H, J = 8, bpy-CH), 8.79 (s,
1 H, imine-CH), 7.96–6.84 (m, 12 H, bpy-CH and Ph-CH), 3.75
1
(s, 6 H, H3CN), 1.27 (s, 9 H, CCH3), 1.23 (s, 9 H, CCH3). 13C{ H}
NMR (75 MHz, CDCl3): 166.3, 166.0, 164.8, 163.2, 155.9, 153.1,
152.3, 150.6, 149.1, 147.6, 134.6, 134.3, 127.2, 125.6, 122.7, 122.3,
121.5, 119.9, 119.4, 118.4, 117.7, 43.6, 35.6, 30.1, 30.0. 19F NMR
(282.4 MHz, CDCl3): d = −79.4. 51V NMR (131.6 MHz, CDCl3):
423.6 (m1/2 = 2046 Hz). Elemental analysis: Exp. (Calc.), C: 54.43
(54.18); H: 5.07 (5.22); N: 9.18 (9.29). M.p.: 178–180 ◦C.
Crystal structure determination of [V(NNMe2)(TIP)(dmpe)]I (3).
A red needle crystal with dimensions 0.28 × 0.12 × 0.10 mm
was mounted on a Nylon loop using paratone oil. Data were
collected using a Bruker CCD diffractometer equipped with
an Oxford Cryostream low-temperature apparatus operating at
173 K. Data were measured using x and ␾ scans of 0.5◦/frame
for 10 s. The total number of images was based on results from
the program COSMO27 where redundancy was expected to be
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˚
4.0 and completeness of 100% out to 0.83 A. Cell parameters
were retrieved using APEX II software and refined using SAINT
on all observed reflections. Data reduction was performed using
the SAINT software. Scaling and absorption corrections were
applied using SADABS multi-scan technique supplied by George
Sheldrick. The structure was solved by the direct method using
the SHELXS-97 program and refined by the least squares method
on F2, SHELXL-97, incorporated in SHELXTL-PC V 6.10. The
structure was solved in the space group Pbca. All non-hydrogen
atoms are refined anisotropically. Hydrogens were calculated by
geometrical methods and refined as a riding model. Crystal data:
˚
C21H31IN3OP2SV, M = 613.33, orthorhombic, a = 10.8685(2) A,
3
˚
˚
˚
b = 18.3385(3) A, c = 26.2108(5) A, U = 5224.13(16) A , space
group Pbca, Z = 8, 67170 reflections were collected, 6199 were
unique (Rint = 0.0556) which were all used in calculations. The
final R1 = 0.0566 and wR(F2) = 0.0701 for all data. The final R1 =
0.0325 and wR(F2) = 0.0627 for all data I > 2r(I).
Acknowledgements
24 S. Kahlal, J.-S. Saillard, J.-R. Hamon, C. Manzur and D. Carrillo,
J. Chem. Soc., Dalton Trans., 1998, 1229.
25 J.-P. Mathy, P. Battioni, D. Mansuy, J. Fisher, R. Weiss, J. Mispelter,
I. Morgenstern-Badarau and P. Gans, J. Am. Chem. Soc., 1984, 106,
1699.
The authors thank the National Science Foundation of the United
States and the Petroleum Research Fund administered by the
American Chemical Society for funding. The authors also thank
Michigan State University for recent upgrades to the X-ray
diffraction facility.
26 J. Bultitude, L. F. Larkworthy, D. C. Povey, G. W. Smith, J. R. Dilworth
and G. J. Leigh, J. Chem. Soc., Chem. Commun., 1986, 1748.
27 (a) COSMO V1.56, Software for the CCD Detector Systems for
Determining Data Collection Parameters, Bruker Analytical X-ray
Systems, Madison, WI, 2006; (b) APEX2 V 1.2–0 Software for the
CCD Detector System; Bruker Analytical X-ray Systems, Madison,
WI, 2006; (c) SAINT V 7.34 Software for the Integration of CCD
Detector System Bruker Analytical X-ray Systems, Madison, WI,
2001; (d) SADABS V2.10 Program for absorption corrections using
Bruker-AXS CCD based on the method of Robert Blessing; R. H.
Blessing, Acta Crystallogr., Sect. A, 1995, 51, 33–38; (e) SHELXTL 6.14
(PC-Version), Program library for Structure Solution and Molecular
Graphics, Bruker Analytical X-ray Systems, Madison, WI, 2000.
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2008 | Dalton Trans., 2008, 2005–2008
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