Synthesis of nitrido(phthalocyaninato)metal(V) complexes RnPcMN (M = Re, Mo, W) and new compounds with nitrido-bridges between rhenium and elements of the third main group

Article abstract of DOI:10.1002/zaac.200390149

New tetra- and octasubstituted nitrido(phthalocyanina to)metal(V) complexes R_nPcMN (M = Re, Mo, W) were synthesized to obtain soluble nitrido-bridged phthalocyanines. Phthalocyanines with nitrido bridges between rhenium and boron, aluminium, ga

Full text of DOI:10.1002/zaac.200390149

Synthesis of Nitrido(phthalocyaninato)metal(V) Complexes RnPcMN (M ؍ Re,
Mo, W) and New Compounds with Nitrido-Bridges between Rhenium and
Elements of the Third Main Group
Sanjiv Verma and Michael Hanack*
Tübingen, Institut für Organische Chemie der Universität
Received December 4th, 2002.
Abstract. New tetra- and octasubstituted nitrido(phthalocyanina-
to)metal(V) complexes RnPcMN (M ϭ Re, Mo, W) were synthe-
sized to obtain soluble nitrido-bridged phthalocyanines. Phthalocy-
anines with nitrido bridges between rhenium and boron, alumi-
nium, gallium and indium, respectively, were synthesized from
substituents at the boron atom. Additionally, the possibility to in-
crease the nucleophilicity of (C5H11)8PcWN by reducing this com-
plex with C8K was studied. The reaction of the reduced complex
with electrophiles, e.g. with tBuMeSiCl, Ph3SiCl and Me3GeCl in-
dicates the formation of nitrogen-bridged complexes.
nitrido(tetra-tert.-butylphthalocyaninato)rhenium(V)
complex,
tBu4PcReN and suitable electrophilic reagents like BCl3, B(C6F5)3,
BPh3, BEt3, AlCl3, GaCl3, GaBr3, InCl3, etc. The nitrido-bridged
compounds prepared show different stabilities depending on the
Keywords: Phthalocyanines; Nitrido bridges; Nitrides; Rhenium;
Tungsten; Molybdenum
Synthese von Nitrido(phthalocyaninato)metall(V)-Komplexen RnPcMN (M ؍ Re, Mo,
W) und neuen Verbindungen mit Nitridobrücken zwischen Rhenium und Elementen der
3. Hauptgruppe
Inhaltsübersicht. Für die Darstellung von löslichen Phthalocyanin-
Nitridobrücken-Verbindungen wurden neue tetra- und oktasubsti-
tuierte Nitrido(phthalocyaninato)metall(V)-Komplexe RnPcMN
(M ϭ Re, Mo, W) synthetisiert.
Durch Umsetzung des Nitrido(tetra-tert.-butylphthalocyaninato)-
rhenium(V)-Komplexes tBu4PcReN mit geeigneten „elektrophilen“
Reagenzien wie BCl3, B(C6F5)3, BPh3, BEt3, AlCl3, GaCl3, GaBr3,
InCl3, etc. erhält man Phthalocyanin-Verbindungen mit Nitrido-
brücken zwischen Rhenium und Bor, Aluminium, Gallium bzw. In-
dium. Abhängig von den Substituenten am Bor-Atom weisen die
entsprechenden Nitridobrücken-Verbindungen unterschiedliche
Stabilität auf.
Zusätzlich wurde untersucht, ob sich die Nukleophilie von
(C5H11)8PcWN durch Reduktion mit C8K erhöhen lässt. Die an-
schliessende Umsetzung des reduzierten Komplexes mit Elektro-
philen z.B. mit tBuMeSiCl, Ph3SiCl und Me3GeCl deutet ebenfalls
auf die Bildung stickstoffverbrückter Komplexe hin.
I Introduction
time several groups have studied similar reactions and syn-
thesized different nitrido-bridged compounds with
ReϪNϪB- and ReϪNϪGa-bonds [7].
Various nitrido complexes of transition metals of groups 4
to 8 are known [1]. In 1968 Chat and Heaton reported for
the first time on the synthesis of the complex, [Re(NBX3)-
Cl2(Et2PhP)3] (X ϭ F, Cl, Br) with a nitrido bridge between
rhenium and boron [2]. Other similar complexes were syn-
thesized by Chat [3], Strähle [4] and Dehnicke [5]. Reaction
of [ReNCl2(Me2PhP)3] with BCl3 led to [Re(NBCl3)-
Cl2(Me2PhP)3], which was characterized by X-ray structural
analysis [4]. The nitrogen atom in the complex is sp hybrid-
ized and the MϵNϪBCl3 group is linear [6]. In the mean-
The aim of our work is to prepare phthalocyanine com-
plexes with nitrido bridges between a transition metal and a
main group element. For this purpose we synthesized highly
soluble peripherallysubstituted nitrido(phthalocyaninato)-
metal(V) complexes. Fig. 1 shows the structures of the re-
quired tetra- (R, R’ ϭ H, tBu) and octasubstituted ( R ϭ
R’ ϭ CH3, C3H7, C4H9, C5H11, C6H13, C7H15) nitrido-
(phthalocyaninato)metal(V) complexes.
Nitrido(phthalocyaninato)metal(V) complexes of chro-
mium, PcCrN [8], manganese, PcMnN [9], technetium,
PcTcN [10], and rhenium, PcReN (1) [11,12,13], have been
described. (PcFe)2N [14] and (PcRu)2N [15] are also well-
known. Recently we synthesized peripherally substituted ni-
trido(phthalocyaninato)rhenium(V) complexes such as
tBu4PcReN (2) [11, 16], (C4H9)8PcReN (3), (C5H11)8PcReN
(4) [17,18], (C6H13)8PcReN (5), (C7H15)8PcReN (6) [17, 18]
and different nitrido(phthalocyaninato)tungsten(V) com-
* Prof. Dr. Dr. h. c. M. Hanack
Institut für Organische Chemie, Lehrstuhl II,
Universität Tübingen,
Auf der Morgenstelle 18, D-72076 Tübingen
Fax: (internat.) ϩ49-7071/295-244
e-mail: hanack@uni-tuebingen.de
http://www.uni-tuebingen.de/hanack/index.html
880
 2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 0044Ϫ2313/03/629/880Ϫ892 $ 20.00ϩ.50/0 Z. Anorg. Allg. Chem. 2003, 629, 880Ϫ892

Synthesis of Nitrido(phthalocyaninato)metal(V) Complexes RnPcMN (M ϭ Re, Mo, W)
Table 1 Spectroscopic Data of R8PcReN Complexes
IR/cmϪ1
(ReϵN)
UV/VIS/nm
(Q-Band max.)
(CH3)8PcReN (36)
(C3H7)8PcReN (37)
988
964
DMSO: 694.0
Toluene: 703.0
(C3H7)8PcReN (37) were prepared from 4,5-dimethylph-
thalonitrile (30) and 4,5-di-n-propylphthalonitrile (31) with
ammonium perrhenate, respectively. In the IR spectrum of
octasubstituted nitrido(phthalocyaninato)rhenium(V) com-
plexes 3Ϫ6, the ReϵN stretching frequency appears with
weak intensity at ν˜ ϭ 950Ϫ1000 cmϪ1 [11Ϫ13, 16Ϫ18]. The
ReϵN stretching frequency in 36 and 37 is observed at the
expected region (Table 1).
The corresponding ReϵN stretching frequency for
OEPReN compounds lies at ν˜ ϭ 1075 cmϪ1 [22]. The lower
value of the stretching vibration in PcReN can be explained
by the occupation of the trans-position of PcReN (1) by the
nucleophilic nitrogen atom of a neighbouring PcReN (1). A
continuation of this principle leads to a polymeric structure,
thereby the bond order between rhenium and nitrogen is
reduced [11, 20].
Fig. 1 Structure of Nitrido(phthalocyaninato)metal(V) Complexes
plexes, for example PcWN (7), tBu4PcWN (8),
(C5H11)8PcWN (9) and several nitrido(phthalocyaninato)-
molybdenum(V) complexes PcMoN (10), (C3H7)8PcMoN
(11), (C4H9)8PcMoN (12) and (C5H11)8PcMoN (13) [19].
The terminal nitrogen ligand in nitrido(phthalocyaninato)-
metal(V) complexes are sufficiently nucleophilic to react
with Lewis acids with formation of nitrido-bridged com-
pounds. For example, we showed [17,20] that the reaction
of BBr3 with tBu4PcReN (2) or (C5H11)8PcReN (4) leads to
the unstable compounds tBu4PcReNBBr3 (14) and
(C5H11)8PcReNBBr3 (15). Thus, a nitrido bridge between
rhenium and boron could be produced in this system for
the first time. The reaction of acetone with the nitrido-
(phthalocyaninato)rhenium(V) complex is also reported
[17].
The Q-band maxima in the UV/VIS spectra of 36 and 37
in DMSO appear in the expected region [11Ϫ13, 16Ϫ18]
(Table 1) and they possess two satellite peaks. A splitting of
the B bands is observed in the UV/VIS spectra of 36 and
37 and other analogous tetra- and octasubstituted nitri-
We describe here the preparation of peripherally substi-
tuted rhenium, tungsten and molybdenum nitrido(phthalo-
cyaninato)metal complexes and the reaction of tBu4PcReN
(2) and (C5H11)8PcWNϪ Kϩ (16) with different elec-
trophilic reagents.
do(phthalocyaninato)rhenium(V)
complexes
[11Ϫ13,
16Ϫ18].
The aromatic and aliphatic protons in the 1H NMR
solid-state spectrum of 36 occur as singlets at δ ϭ 7.7 (H-
b) and 3.9 (H-1), respectively. In the 13C CP/MAS solid-
state NMR spectrum of 36, 13C signals of the aromatic car-
bon atoms are observed at δ ϭ 121.6 (C-b) and the aliphatic
ones at δ ϭ 22.2 (C-1).
II Results and Discussion
1 Nitrido(phthalocyaninato)metal Complexes
Scheme 1 illustrates the synthetic routes to nitrido com-
plexes. The transition metals rhenium, tungsten and molyb-
denum are used as the central atom in the phthalocyanines.
Soluble nitrido(phthalocyaninato)metal(V) complexes are
preferred as reactants to obtain the corresponding nitrido-
bridged complexes.
1.2 Nitrido(okta-n-alkylphthalocyaninato)-
tungsten(V) complexes [methyl (38), n-propyl (39), n-
butyl (40), n-hexyl (41), n-heptyl (42)]
Tungsten has an oxidation state of ϩV in PcWCl3 [23] and
(ClPc)W(O)OH [24]. The octasubstituted RnPcWN com-
plexes 38Ϫ42 are prepared in yields between 7 and 45% by
melting the corresponding substituted phthalonitriles
30Ϫ32, 34, 35 with WNCl3 [25Ϫ28] under argon (Scheme
1). The WϵN valence stretching bands in the IR spectra
of PcWN (7), tBu4PcWN (8) and (C5H11)8PcWN (9), are
observed in the range of ν˜ ϭ 950Ϫ1000 cmϪ1 [19] and they
lie also in the expected region as found for 38؊41 (Table 2).
An intensive and broad signal in the ESR spectra is ob-
served for 38 (solid state) and 39Ϫ42 (in toluene) each at
g ϭ 1.89 without hyperfine structure [19, 20].
1.1 Nitrido(octa-n-alkylphthalocyaninato)-
rhenium(V) complexes [methyl (36), n-propyl (37)]
The synthesis of PcReSO4·2H2O [21] from phthalonitrile
and ammonium perrhenate purified with sulfuric acid, was
reported in 1970 [21]. Later this compound was identified
as PcReN (1) [12]. PcReN (1) can be synthesized by melting
ammonium perrhenate with phthalonitrile at 280Ϫ290°C
for 50 min. Synthesis of PcReN (1) [13] from ReOCl3-
(PPh3)2, phthalonitrile and ammonium chloride is also pos-
sible [12]. According to Scheme 1, (CH3)8PcReN (36) and
It is possible to realize nitrido bridges in phthalocyanine
complexes in one reaction step. Attempts were made to pre-
Z. Anorg. Allg. Chem. 2003, 629, 880Ϫ892
881

S. Verma, M. Hanack
Scheme 1 Synthesis of Nitrido(phthalocyaninato)metal(V) Complexes 36Ϫ43
pare (C5H11)8PcW[N(Tos)]2 from W(TosN)2Cl2 [29] and
4,5-dipentyl-1,2-dicyanobenzene (33), however, (C5H11)8-
PcWN (9) [20] was obtained. By an analogous synthetic
step, the already known tBu4PcWN (8) could be synthe-
sized. Similarly, the synthesis from Mo(TosN)2Cl2 and 4,5-
dimethyl-1,2-dicyanobenzene (30) leads to (CH3)8PcMoN
(43).
1.3 Nitrido(octamethylphthalocyaninato)-
molybdenum(V) (43)
Up to now only few phthalocyaninatomolybdenum com-
pounds, PcMoO, PcMo(O)OH and (PcMo)2 have
been reported [30Ϫ35]. On the contrary, molybdenumpor-
phyrins [36] have been better investigated, and the derivat-
882
Z. Anorg. Allg. Chem. 2003, 629, 880Ϫ892

Synthesis of Nitrido(phthalocyaninato)metal(V) Complexes RnPcMN (M ϭ Re, Mo, W)
Table 2 Spectroscopic Data of R8PcWN Complexes
also obtained by the reaction of 2 with tBuMe2SiCl
(Scheme 2).
IR/cmϪ1
(WϵN)
UV/VIS/nm
(Q-Band max.)
The electrophile can be removed easily from the nitrogen-
bridged phthalocyninatorhenium compounds, especially in
solution with the formation of tBu4PcReN (2). The stability
of the nitrido-bridged compounds 44Ϫ54 is judged with the
help of UV/VIS spectra in solution.
(CH3)8PcWN (38)
(C3H7)8PcWN (39)
(C4H9)8PcWN (40)
(C6H13)8PcWN (41)
(C7H15)8PcWN (42)
982
957
953
955
DMSO: 764.5
Toluene: 759.5
Toluene: 763.0
Toluene: 762.0
Toluene: 763.0
2.1.1 Reaction of tBu4PcReN (2) with Boron
Electrophiles
ives TMPMoN, TTPMoN and TPPMoN [37] possess some
structural similarities with substituted and unsubstituted
PcMoN complexes. Similar to the preparation of PcMoN
[38] (CH3)8PcMoN (43) can be prepared from a melt of 4,5-
dimethyl-1,2-dicyanobenzene (30) with Mo(TosN)2Cl2 [29] at
220°C (Scheme 1). The MoϵN stretching frequency of sev-
eral substituted nitrido(phthalocyaninato)molybdenum(V)
complexes R8PcMoN 11Ϫ13 [19] lies in the same region
between ν˜ ϭ 950Ϫ1000 cmϪ1 as that of R8PcWN and
R8PcReN [11a,16a,17,19,20]. The peak at ν˜ ϭ 991 cmϪ1 in
the IR spectrum of (CH3)8PcMoN (43) has been assigned
to MoϵN stretching frequency.
In the UV/VIS spectrum of (CH3)8PcMoN (43) in DMF
or toluene, the Q-band maximum appears at 710 nm.
This value is in agreement with those found for R8PcMoN
complexes 11Ϫ13, which is in the range of 709Ϫ716 nm
[19]. The B-band of 43 in UV/VIS spectrum is found at
344 nm.
tBu4PcReN (2) is dissolved in dichloromethane at Ϫ5°C to
give a blue solution. On addition of appropriate elec-
trophiles [BF3·OEt2, BCl3, BCl2Ph, B(C6F5)3, BPh3, BEt3],
the colour turns from blue to green and the solution is
stirred for several hours at Ϫ5°C till no more change of
colour occurs. Reaction of BF3·OEt3 with 2 replaces the
coordinated diethyl ether by the nitridophthalocyanine li-
gand of 2 with the formation of tBu4PcReNBF3 (44). Sim-
ilarly, BCl3 reacts with the nucleophilic nitrido ligand of
[ReN(Me2PhP)(Et2dtc)2] to form [Re(NBCl3)(Me2PhP)-
(Et2dtc)2] [7g]. BCl2Ph reacts with the terminal nitrido li-
gands of [ReNCl2(Me2PhP)3], [ReN(Cl)(MePhP)2(Et2dtc)],
[ReN(Me2PhP)(Et2dtc)2] and [ReNCl2(Ph3P)2] to the cor-
responding “ReϪNϪB” complexes [7j]. Recently, com-
pounds with nitrido bridges between Rhenium and
B(C6F5)3 [7i,k,l,m] and BPh3 [7n] are also reported. The
fragmentation pattern of nitrido-bridged compounds
44Ϫ53 in the FAB mass spectra is similar to the fragmenta-
tion pattern of cis, mer-[Re(NBCl3)Cl2(Me2PhP)3] [4],
[Re(NBCl3)Cl2(Me2PhP)3] [7p] and [Re(NBCl3)(Me2PhP)-
(Et2dtc)2] [7g] and other ReϪNϪB compounds [7hϪr]. The
structures of the prepared nitrido-bridged complexes are
corroborated by elemental analyses.
The solid-state ESR spectrum of 43 shows a broad signal
with a g factor of 1.97 [19].
2 Nitrido-Bridged Compounds
An important evidence for the formation of a nitrido
bridge in these systems is the shift of the ReϵN stretching
vibration to higher wavelengths. AsPh4[ReNBr4] [5], not
possessing a phthalocyanine moiety, shows the ReϵN
stretching vibration at 1099 cmϪ1. The vibration is shifted
to 1170 cmϪ1 for the product [5]. After reaction of boron
electrophiles with the nitrido group of a rhenium complex
(nitrido complex without phthalocyanine), the ReϵN
stretching frequency tends to shift from 1050 to 1160 cmϪ1
[3,5,7fϪq]. This shift of ReϵN stretching frequency
can also be observed after the reaction of nitrido
The nucleophilic character of the nitrido ligand of
tBu4PcReN (2) and (C5H11)8PcWN (9) towards various
electrophiles in solution was studied. tBu4PcReN (2) is a
d2 complex and (C5H11)8PcWN (9) is a d1 complex. The
nucleophilicity of 9 can be increased by reducing the d1
complex to a d2 complex to ease the formation of a nitrido
bridge by treatment of the nitrido complex with an elec-
trophile.
2.1 Reaction of tBu4PcReN (2) with Electrophiles
complexes
[ReNCl2(Me2PhP)3],
[ReN(Cl)(Me2PhP)2-
tBu4PcReN (2) is soluble in organic solvents and is suitable
for the synthesis of soluble phthalocyaninatometal nitrido-
bridged compounds. The reaction of 2 with BEt3, BPh3,
B(C6F5)3, BF3·OEt3, BCl3, AlCl3, GaCl3, GaBr3 and InCl3
leads to non-ionic, green nitrido-bridged compounds
44Ϫ53 (Scheme 2). The choice of the electrophile that has
to be attached to the nitrido ligand of 2 depends on the
electron-donating or -attracting ability of the substituents
on the boron atom. The substituents at the boron atom in-
fluences the stability of the nitrido bridge in this system.
The green ionic complex tBu4PcReNSitBuMe2ϩClϪ (54) is
(Et2dtc)], [ReN(Me2PhP)(Et2dtc)2] and [ReNCl2(Ph3P)2]
with boron electrophiles [7j]. The structural studies of these
compounds show that the rheniumϪnitrogen triple bond
has only become slightly longer on account of formation of
the ReϪNϪB bridge [7j]. The short wave length shift of
ReϵN stretching frequency is explained due to the coupling
of ReϵN vibration with the NϪB valence vibration [7, 26].
According to this the ReϵN valence vibration band is
shifted hypsochromically from ν˜ ϭ 978 to ca. 1090 cmϪ1
after the reaction of boron electrophiles with 2. The ReϵN
valence vibration band in these systems are of weak intens-
Z. Anorg. Allg. Chem. 2003, 629, 880Ϫ892
883

S. Verma, M. Hanack
Scheme 2 Reaction of 2 with Electrophiles and tBuMe2SiCl
ity and is overlapped by phthalocyanine vibration
signals. The ReϵN valence vibration band of 2 at ν˜ ϭ
978 cmϪ1 has disappeared in the IR spectra of nitrido-
bridged compounds 44Ϫ49. The IR spectrum of
tBu4PcReNB(C6F5)3 (47) shows a characteristic band at
ν˜ ϭ 980 cmϪ1, which is not due to the ReϵN valence vibra-
tion of the starting material 2. The intensity of the peak at
ν˜ ϭ 978 cmϪ1 in the IR spectrum of 2 is much weaker than
that of 47. The vibration band at ν˜ ϭ 980 cmϪ1 is also
observed as highly intensive peak in other MϪNϪB(C6F5)3
complexes and is caused by the pentafluorophenyl groups
[71].
The UV/VIS spectra of the nitrido-bridged compounds
44Ϫ49 in dichloromethane display a clear reduction of the
absorption of the Q-bands after the reaction of boron elec-
trophiles with 2. This leads to a change in the relation of
absorption of Q-bands:B-bands from 3:1 to 1:1 (Fig. 2).
When the Q-band:B-band absorption ratio does
not correspond to 1:1 and changes on account of an in-
crease of Q-band absorption, the retro-reaction to
884
Z. Anorg. Allg. Chem. 2003, 629, 880Ϫ892

Synthesis of Nitrido(phthalocyaninato)metal(V) Complexes RnPcMN (M ϭ Re, Mo, W)
Fig. 3 UV/VIS Spectra of tBu4PcReNBCl3 (45) in Toluene
Fig. 2 UV/VIS Spectra of
a) 47 in CH2Cl2
b) 48 in CH2Cl2 between glass plates
c) 49 in CH2Cl2 between glass plates
d) 2 in CH2Cl2
solution than 44 and 45. Analogous to 14 (725 nm),
the electron-attracting BX3ϪnRn groups (X ϭ Cl, Br, C6F5,
n ϭ 0; X ϭ Cl, R ϭ Ph, n ϭ 1) are responsible for the shift
of Q-bands in UV/VIS spectra of 45Ϫ47. The inductive and
mesomeric effects of the halogen substituent at the boron
atom are probably decisive.
Table 3 UV/VIS-Data of 44؊49 in Dichloromethane
Q-Band max./nm
tBu4PcReNBPh3 (48) and tBu4PcReNBEt3 (49) decom-
pose immediately in dilute solutions to the starting material
(cf. Fig. 2) by changing the colour of the solution from
bluish-green to blue. Concentrated solutions (dichlorome-
thane) of 48 (Fig. 2b) and 49 (Fig. 2c) were measured be-
tween glass plates taking care that no change of colour
takes place during the measurement (Fig. 2c). The UV/VIS
spectrum of tBu4PcReNBPh3 (48) is almost identical to that
of tBu4PcReNBEt3 (49) (Fig. 2c) with the Q-band maxima
lying in the region of tBu4PcReN (2). It is possible that a
scission of BPh3 or BEt3 has already taken place during the
measurement of the concentrated solution between glass
plates, pointing out that the Q-band maximum of 48 and
49 is indeed that of the already formed tBu4PcReN (2). In
this connection a comparison of 47Ϫ49 is especially inter-
esting, because a similar band pattern can be observed in
the UV/VIS spectra (Fig. 2). The electron-attracting
B(C6F5)3 group causes only a bathochromic shift of the Q-
and B-bands in the UV/VIS spectrum of 47 in comparison
to tBu4PcReNBPh3 (48) and tBu4PcReNBEt3 (49). At the
same time 47 is stabilized through the electron-attracting
B(C6F5)3 group. There is no band at 697 nm in the UV/VIS
spectrum of 47 (Fig. 2a) indicating that B(C6F5)3 is not
split off from 47 and hence the starting material tBu4PcReN
(2) is not formed. The relation of Q-band:B-band is ca. 1:1
for 47Ϫ49 and the analogous compounds 14, 15, 44Ϫ46.
This indicates that the complex 48 and 49 have not split off
BPh3 or BEt3 in concentrated solution (Fig. 2) and hence 2
is not formed.
tBu4PcReNBF3 (44)
tBu4PcReNBCl3 (45)
tBu4PcReNBCl2Ph (46)
tBu4PcReNB(C6F5)3 (47)
tBu4PcReNBPh3 (48)
tBu4PcReNBEt3 (49)
676.0
721.0
733.5
715.5
695.5
696.0
tBu4PcReN (2) will take place. The maximum of the Q-
band of 2 in dichloromethane lies at 697 nm and
contains a satellite vibration at 627.5 nm (Fig. 2d). The
absorption ratio of Q-band:B-band in the UV/VIS spec-
trum of 2 is 3:1. Table 3 shows the UV/VIS data of 44Ϫ49.
After four hours, the Q-band at 676 nm in the
UV/VIS spectrum of 44 splits into two with maxima at
663 and 669 nm, which is due to the slow splitting off of
boron trifluoride in 44. After three days the Q-band max-
imum in the UV/VIS spectra of 44 appears at 695 nm,
i.e. BF3 has been completely split off from 44 with the
formation of tBu4PcReN (2).
The Q-band at 721 nm in the UV/VIS spectrum of
tBu4PcReNBCl3 (45) disappears completely and instead
of this a Q-band of 2 at 696 nm is clearly observed.
An immediate decomposition of 45 to 2 takes place by dis-
solving 45 in toluene instead of dichloromethane (Fig. 2d).
One can notice a shoulder on the Q-band if a UV/VIS spec-
trum of 45 is measured during the dissolution of 45 in tolu-
ene. This shoulder is due to the decomposing product 45.
Within two minutes 45 is completely converted to
tBu4PcReN (2) and BCl3 (cf. Fig. 3).
11B signals of four-coordinated boron atoms are already
reported [39]. Fig. 4 shows the known 11B NMR spectra
(CDCl3) of BBr3 (Fig. 4a), 14 in test tube (Fig. 4b) and 14
after substracting the 11B NMR spectrum (CDCl3) of the
Even after 15 hours, the Q-band maximum can be still
clearly seen in the UV/VIS spectrum of 47 in dichlorome-
thane (Fig. 2a), which shows that 47 is more stable in the
Z. Anorg. Allg. Chem. 2003, 629, 880Ϫ892
885

S. Verma, M. Hanack
Q-Band max./nm
Table 4 UV/VIS-Data for 50Ϫ53
tBu4PcReNAlCl3 (50)
tBu4PcReNGaCl3 (51)
tBu4PcReNGaBr3 (52)
tBu4PcReNInCl3 (53)
696.0
720.5
721.5
694.5
Fig. 4 11B NMR Spectrum (CDCl3) of
a) BBr3
b) tBu4PcReNBBr3 (14) with Test Tube
c) Difference Spectrum of 14 b) and Test Tube
test tube spectrum (Fig. 4c). The 11B signal of 14 appears
at δ ϭ Ϫ12.90 [17, 20].
Fig. 5 UV/VIS Spectrum of
a) 50 in CH2Cl2
b) 53 in CH2Cl2
The 11B NMR spectra of 44, 45, 47 and 49 in CD2Cl2
show the 11B signal in the expected region [39] using
BF3·OEt2 as standard. The boron nucleus is electron-rich
due to the formation of the nitrido bridge. At the same
time, the boron nucleus is influenced by the aromatic π-
system of the phthalocyanine complex. The 11B signals of
44, 45, 47 and 49 are shifted to high field in comparison to
the 11B signal of the boron electrophiles used. For example,
the 11B signals of BCl3, BPh3 in CD2Cl2 are at δ ϭ 46.5
and 68.0, respectively. The 11B signal at δ ϭ 45.7 in the 11B
NMR spectrum of 48 is assigned to the degraded product
tBu4PcReNBPh2. In comparison, 11B NMR spectrum of
R2BNMe2 (R ϭ alkyl) give a 11B NMR signal at δ ϭ 45
[40]. The 11B signal of BEt3 is located at δ ϭ 86 [41].
ReϵN vibration band in the IR spectra of 50Ϫ53 are over-
lapped with the phthalocyanine bands and the ReϵN vi-
bration bands of 2 at ν˜ ϭ 978 cmϪ1 has disappeared.
The UV/VIS data of tBu4PcReNAlCl3 (50), tBu4PcReN-
GaCl3 (51), tBu4PcReNGaBr3 (52) and tBu4PcReNInCl3
(53) are shown in Table 4 and confirm that the reaction of
AlCl3 and InCl3 with tBu4PcReN (2) result in tBu4PcReN-
AlCl3 (50) and tBu4PcReNInCl3 (53) (Scheme 2).
The decrease of Q-band absorption as compared to B-
band in the UV/VIS spectrum of 50Ϫ53 corresponds to the
already made observations, when a nitrido-bridged com-
pound is prepared from tBu4PcReN (2) and a boron elec-
trophile. The starting material 2 is formed immediately from
a dilute dichloromethane solution of tBu4PcReNAlCl3 (50)
(cf. Fig. 2d). The recording of the UV/VIS spectra of 50
(Fig. 5a) and 53 (Fig. 5b) is possible only in concentrated
dichloromethane solution between glass plates.
While recording the UV/VIS spectrum of tBu4PcReN-
GaCl3 (51) in dichloromethane, 51 is destroyed within five
minutes and a Q-band maximum at 685 nm is formed.
The UV/VIS spectrum of tBu4PcReNGaBr3 (52) shows
an already split Q-band. The same splitting of the Q-band
is also observed during the decomposition of 51 indicating
that 51 is more stable than 52.
After one day, only a maximum of Q-band at 684 nm
is observable in the UV/VIS spectrum of 52 (similar to the
UV/VIS spectrum of 51). While the absorption ratio of Q-
band:B-band, after decomposition of 51 and 52 is ca. 1:1,
a substitution of halide ion at gallium might have taken
place. Thereby the nitrido bridge between rhenium and gal-
2.1.2 Reaction of tBu4PcReN (2) with AlCl3, GaCl3,
GaBr3, and InCl3
Up to now practically no information is known about
nitrogen-bridged ReϪAl and ReϪIn compounds. A solu-
tion of 2 in dichloromethane changes the colour from blue
to green on addition of AlCl3, GaCl3, GaBr3, and
InCl3 (Scheme 2). [Re(NGaCl3)(Cl)(Me2PhP)3(CH3CN)]ϩ
[GaCl4]Ϫ and [Re(NGaCl3)Cl2(Me2PhP)3] are known nitro-
gen-bridged ReϪNϪGa compounds [7g,i,o,p]. The FAB
mass spectrum of nitrido-bridged complexes 50Ϫ53 show a
[tBu4PcReN]ϩ signal of nitrido complexes. The elemental
analyses confirms the structure of 51. tBu4PcReNAlCl3 (50)
and tBu4PcReNInCl3 (53) are very labile in solution.
The ReϵN valence vibration is shifted to shorter wave
length by ca. 60 cmϪ1 in the reaction of GaX3 with the
nitride of the corresponding nitrido complex [7g,i,o,p]. The
886
Z. Anorg. Allg. Chem. 2003, 629, 880Ϫ892

Synthesis of Nitrido(phthalocyaninato)metal(V) Complexes RnPcMN (M ϭ Re, Mo, W)
2.2 Reduction of (C5H11)8PcWN (9) and its
Reaction with Electrophiles
A d2 complex with a high nucleophilic character is pro-
duced by reduction of a d1 complex thereby making the
reaction of electrophiles with the complex easy. Another ad-
vantage of the d2 complex is the possibility of immediate
NMR analyses of these compounds.
After reduction of (C5H11)8PcWN (9) with C8K in
THF to [(C5H11)8PcWN]ϪKϩ (16), the latter can form
an
adduct
with
BCl3
to
give
the
ionic
[(C5H11)8PcWNBCl3]ϪKϩ or it can react with Me3SiCl. In
the latter case, the chloride ion in Me3SiCl gets substituted
by the reduced nitrido complex 16. We have recently de-
scribed this reaction [20] which gives a non-ionic compound
(C5H11)8PcWNSiMe3. Preliminary experiments show that
16 gives mainly a brown solution with BEt3, B(C6F5)3,
BCl3, BBr3, GaCl3, and InBr3. Under these reaction condi-
tions (room temperatures, 1 atmosphere) this does not lead
to the expected ionic phthalocyanine complexes. Non-ionic
nitrido-bridged compounds are formed in the reaction
of 16 with Me3SnCl, tBuMe2SiCl, (C4H9)8PcGeCl2,
tBu4PcSnCl2, Ph3SiCl, Me3GeCl, (C5H11)8PcSi(OH)2,
tBu4PcSnI2 and tBu4PcInCl by nucleophilic substitution on
the „electrophiles„. The UV/VIS spectra of the compounds
obtained after the reaction of 16 with tBuMe2SiCl, Ph3SiCl,
Me3GeCl, (C4H9)8PcGeCl2 and tBu4PcSnCl2 show Q- and
B-bands which are distinctly different than the Q- and B-
bands in the UV/VIS spectrum of (C5H11)8PcWN (9). Thus,
nitrido complexes are also formed here, which decompose
in solution.
Fig.
Toluene
6
Decomposition of [tBu4PcReNSitBuMe2]ϩClϪ (54) in
lium remains intact and the absorption relation Q-band:B-
band of 1:1 is unaltered.
2.1.3. [tBu4PcReNSitBuMe2]ϩClϪ (54)
The ionic complex [tBu4PcReNSitBuMe2]ϩClϪ (54) is pre-
pared by reacting tBu4PcReN (2) with tBuMe2SiCl (Scheme
2). The colour of the solution changes from blue to green
on addition of BuMe2SiCl while the chloride anion of tBu-
t
Me2SiCl is replaced by 2. The UV/VIS spectrum of 54
shows an absorption ratio of Q-band:B-band of ca. 1:1. A
weak Mϩ signal of [tBu4PcReNSitBuMe2]ϩ and a clear
peak for [tBu4PcReN]ϩ can be seen in the FAB mass spec-
trum, showing that a substitution has taken place here. The
ionic nitrogen-bridged [tBu4PcReNSitBuMe2]ϩClϪ (54) is a
very labile compound and decomposes immediately in di-
lute solution (toluene) as compared to the non-ionic ni-
trido-bridged compounds 44Ϫ53.
Analogous to the already described non-ionic nitrido-
bridged compounds, the ReϵN vibration band at ν˜ ϭ 978
cmϪ1 has disappeared in the IR spectrum of 54.
The UV/VIS spectrum of 54 is measured as a concen-
trated solution in toluene between glass plates and shows
several Q-band maxima at 725.5, 696 and 666 nm. The
maximum at 696 nm indicates a decomposition of 54
with formation of 2 (cf. Fig. 2d), which takes place within
three minutes (Fig. 6).
In the UV/VIS spectrum of 54 recorded in a dilute solu-
tion of toluene, the Q-band at 695.5 nm is already larger
compared to the B-band. [tBu4PcReNSitBuMe2]ϩClϪ has
split off [SitBuMe2]ϩ during the dissolution process. The
nitrido bridge is completely destroyed after 90 minutes and
the UV/VIS spectrum of 54 corresponds to the spectrum of
2. The maximum of the Q-band at 725.5 nm is assigned
to the nitrido bridge of 54. The UV/VIS spectrum of
45 in toluene (Fig. 3) shows similarities with the electronic
spectrum of 54 (Fig. 6).
Scheme 3 shows the synthetic route to (C5H11)8PcWNSi-
tBuMe2 (55) and (C5H11)8PcWNGeMe3 (56). (C5H11)8-
PcWN (9) does not react with tBuMe2SiCl without re-
duction. The products show the Mϩ signal for
[(C5H11)8PcWN]ϩ in the FD mass spectra.
The WϵN vibration of 9 at ν˜ ϭ 957 cmϪ1 is missing in
the IR spectra of (C5H11)8PcWNSitBuMe2 (55) and
(C5H11)8PcWNGeMe3 (56), but can be seen at ν˜ ϭ 1140
cmϪ1 in the IR spectra of other WϪNϪSi complexes [42].
Little is known on the nitrido-bridges in phthalocyanine
between tungsten and silicon/germanium, and hence the as-
signment of WϵN in 55 and 56 is difficult.
The UV/VIS data of 55 and 56 are assembled in Table 5.
The UV/VIS spectrum of (C5H11)8PcWN (9) in toluene has
a Q-band at 770.5 nm and a B-band at 376 nm. Contrary
to the rheniumϪnitrido bridge in phthalocyanines, the in-
tensity of absorption of Q-band in the UV/VIS spectrum of
55 does not decrease but mainly shifts to shorter waves. An
analogous blue shift is noted in the product obtained from
the reduction of (C5H11)8PcWN (9) with C8K followed by
reaction with ClSiPh3 indicating that (C5H11)8PcWNSiPh3
is formed.
1
The H NMR signals for the eight pentyl groups in the
periphery of 55 (in THF-d8) appear at δ ϭ 1.02 (H-8), 1.37
(H-7), 1.61 (H-6), 2.37 (H-5) and 2.72 (H-4). The eight aro-
matic protons of 55 give a multiplet at δ ϭ 7.29Ϫ7.68. The
singlets at δ ϭ 1.29 (H-1) and 0.91 (H-2) are assigned to
Z. Anorg. Allg. Chem. 2003, 629, 880Ϫ892
887

S. Verma, M. Hanack
Scheme 3 Reduction of 9 and Reaction with Me3GeCl and tBuMe2SiCl
Table 5 UV/VIS-Data of compounds 55 and 56
spectrum of 56 (THF-d8) shows the eight peripheral pentyl
groups at δ ϭ 13.3 (C-6), 22.4 (C-5), 30.6 (C-4), 31.7 (C-3)
and 32.8 (C-2). The aromatic carbon atoms appear at δ ϭ
123.2 (C-b), 127.1 (C-c), 129.2 (C-a) and 147.5 (C-d). The
three methyl groups of 56 at germanium occur at δ ϭ 20.4
(C-1).
t
Q-Band max./nm
(C5H11)8PcWNSitBuMe2 (55)
(C5H11)8PcWNSitBuMe2 (55)
(C5H11)8PcWNGeMe3 (56)
(C5H11)8PcWNSiPh3
725.5 (Toluene)
723.0 (THF)
731.5 (Toluene)
725.0 (THF)
III Summary
the axial SitBuMe2 group. The nitrogen atom in 55 between
We have prepared and characterized several nitrido(phthal-
ocyaninato)metal compounds R8PcMN 36Ϫ43. Our aim
was to introduce a nitrido bridge between a transition metal
and a main group element in phthalocyanine system.
Nitrogen-bridged compounds with different stabilities in
solution are formed in the reaction of tBu4PcReN (2) with
different boron electrophiles. The effect of alkyl substituents
instead of the halogen substituents on the boron atom on
the stability of nitrido bridge between rhenium and boron
in phthalocyanines has been studied.
1
tungsten and silicon is probably sp2 hybridized and the H
signal of the methyl groups at silicon is shifted downfield
due to the ring current effect. This shift is also seen in the
1H NMR spectrum of (C5H11)8PcWNSiMe3 [20]. The eight
pentyl substituents in the periphery of phthalocyanine 56
give five proton signals in the 1H NMR spectrum at
δ ϭ 0.91 (H-6), 1.37 (H-5), 1.59 (H-4), 2.41 (H-3) and 2.72
(H-2). The signals for the eight aromatic protons of
(C5H11)8PcWNGeMe3 (56) appear as a multiplet at δ ϭ
7.37Ϫ7.91. The methyl group at germanium in 56 is down-
field shifted to δ ϭ 1.3 due to the ring current of phthalocy-
anine, due probably to the sp2 hybridization of the nitrogen
atom between tungsten and germanium. The 13C NMR
In comparison to alkyl ligands, halogen ligands on
the boron atom lead to a higher stability, i.e. the nitrogen-
bridged ReϪNϪBX3 compounds decompose slower in so-
lution as the analogous nitrogen-bridged ReϪNϪBR3 com-
888
Z. Anorg. Allg. Chem. 2003, 629, 880Ϫ892

Synthesis of Nitrido(phthalocyaninato)metal(V) Complexes RnPcMN (M ϭ Re, Mo, W)
MS (FAB) (NBA, 50°C): m/z ϭ 1049.4 [Mϩ]. MS (FD) (toluene, 35°C):
pounds. The stability of the nitrogen-bridged compounds
increases (in solution): tBu4PcReNBPh3 (48) < tBu4PcReN-
BEt3 (49) Յ tBu4PcReNBCl2Ph (46) < tBu4PcReNBCl3
(45) < tBu4PcReNBF3 (44) ഠ tBu4PcReNB(C6F5)3 (47).
The reaction of nitride 2 with GaCl3, GaBr3, AlCl3 and
InCl3 leads to analogous nitrogen-bridged rhenium phthal-
ocyanine compounds. The stability of tBu4PcReNGaCl3
(51) and tBu4PcReNGaBr3 (52) is comparable with 45 or
46, and that of tBu4PcReNAlCl3 (50) and tBu4PcReNInCl3
(53) with 48 and 49. The compounds are more stable in the
solid state than in solution.
m/z ϭ 1048.9 [Mϩ]. IR (KBr): ν˜ ϭ 964 m cmϪ1 (ReϵN). UV/VIS (toluene):
λ ϭ 351.5, 368.5, 633.0, 672.0, 703.0 nm. 13C-DEPT NMR (CD2Cl2): δ ϭ
124.5 (C-b), 36.6 (C-3), 25.1 (C-2), 14.8 (C-1).
Nitrido(octamethylphthalocyaninato)tungsten(V) (38)
98.3 mg (0.63 mmol) of 4,5-dimethyl-1,2-dicyanobenzene (30) and
42.5 mg (0.14 mmol) of nitridotungsten trichloride were melted at
220°C under Argon for 15 min. The residue was extracted with
hexane, toluene and acetonitrile in a Soxhlet for 12 h each. Yield:
52.0 mg (45 %), dark green, amorphous solid.
MS (FAB) (NBA, 50°C): m/z ϭ 824.0 [MϩϩH]. IR (KBr): ν˜ ϭ 982 vw cmϪ1
(WϵN). UV/VIS (DMSO): λ ϭ 367.5, 764.5 nm. ESR (solid state, RT):
g ϭ 1.89.
Treatment of tBu4PcReN (2) with tBuMe2SiCl gives the
unstable complex tBu4PcReNSitBuMe2ϩClϪ (54).
For the preparation of nitrogen-bridged tungsten phthal-
ocyanine compounds, the reduction of (C5H11)8PcWN (9)
with C8K followed by treatment with tBuMe2SiCl and
Me3GeCl, respectively, is promising. Experimental and
analytical studies support that nitrido-bridged compounds
are formed in each case.
Nitrido(octa-n-propylphthalocyaninato)tungsten(V) (39)
187.5 mg (0.88 mmol) of 4,5-dipropyl-1,2-dicyanobenzene (31) and
59.7 mg (0.20 mmol) of nitridotungsten trichloride were melted at
220°C for 15 min under Argon. The crude product was extracted
first with hexane in a Soxhlet and then precipitated out several
times (5 ϫ) from toluene/hexane. Yield: 15 mg (7 %), dark green
solid.
IV Experimental Part
MS (FD) (toluene, 30°C): m/z ϭ 1046.4 (Mϩ). MS (FAB) (NBA, 50°C):
m/z ϭ 1046.9 (Mϩ). IR (KBr): ν˜ ϭ 957 w cmϪ1 (WϵN). UV/VIS (toluene):
λ ϭ 374, 759.5 nm. ESR (toluene, RT): g ϭ 1.89.
The solvents were dried according to the usual procedures [43],
distilled and stored under argon. 4,5-Di-n-alkylphthalonitrile [al-
kyl ϭ methyl (30), propyl (31), butyl (32), pentyl (33), hexyl (34),
heptyl (35) [44,45], 4-tert-butylphthalonitrile [46], ammonium per-
rhenate [47], nitrido(tetra-tert-butylphthalocyaninato)rhenium(V)
(2) [11,16] and nitrido(octa-n-pentylphthalocyaninato)tungsten (9)
[19,20] were synthesized according to literature procedure. Ϫ EA:
C, H, N: Carlo Erba Elemental Analyzer 1104 and 1106; Cl: mer-
curymetric titration according to Schöniger [48]. Ϫ MS: Varian
MAT 711 A (FD); Finnigan ISQ 70, Varian MAT 711 A (FAB).
Ϫ FT-IR: Bruker IFS 48. Ϫ UV/VIS: Shimadzu UV-2101 PC, Shi-
madzu UV-365. Ϫ ESR: Bruker ESP 300 (X-Band).Ϫ NMR:
Bruker ARX 250 (250.1 MHz, 62.9 MHz, 80.3 MHz), Bruker ARX
400 (400.1 MHz).
Nitrido(octa-n-butylphthalocyaninato)tungsten(V) (40)
151.1 mg (0.63 mmol) of 4,5-dibutyl-1,2-dicyanobenzene (32) and
42.5 mg (0.14 mmol) of nitridotungsten trichloride were melted at
220°C under argon for 15 min. After Soxhlet extraction of the
crude product with hexane it was precipitated out several times (5
ϫ) from dichloromethane/hexane. Yield: 13 mg (8 %), dark green
solid.
MS (FD) (toluene, 35°C): m/z ϭ 1158.5 (Mϩ). IR (KBr): ν˜ ϭ 953 vw cmϪ1
(WϵN). UV/VIS (toluene): λ ϭ 373.5, 763.0 nm. ESR (toluene, RT): g ϭ
1.89.
1 Nitrido(phthalocyaninato)metal(V) Complexes
Nitrido(octa-n-hexylphthalocyaninato)tungsten(V) (41)
Nitrido(octamethylphthalocyaninato)rhenium(V) (36)
341 mg (1.15 mmol) of 4,5-dihexyl-1,2-dicyanobenzene (34) and 70
mg (0.23 mmol) of nitridotungsten trichloride were melted at 220°C
for 15 min under an inert atmosphere. After a Soxhlet extraction
with hexane, 41 was dissolved in hexane. The excess phthalonitrile
34 was removed at 155°C/8·10Ϫ2 mbar. Yield: 68 mg (22 %), dark
green solid.
53.6 mg (0.2 mmol) NH4ReO4 and 156.2 mg (1 mmol) 4,5-di-
methylphthalonitrile (30) were melted at 280°C for 50 min. The
solid residual melt was finely powdered and extracted with aceton-
itrile, toluene and hexane, respectively, in a Soxhlet for 5 d each.
Yield: 56.0 mg (34 %), bluish-green, microcrystalline solid.
MS (FD) (toluene, 35°C): m/z ϭ 1382.3 (Mϩ). IR (KBr): ν˜ ϭ 955 w cmϪ1
(WϵN). UV/VIS (toluene): λ ϭ 374.0, 762.0 nm. ESR (toluene, RT): g ϭ
1.89.
MS (FAB) (NBA, 50°C): m/z ϭ 825.1 [Mϩ]. IR (KBr): ν˜ ϭ 988 m cmϪ1
(ReϵN). UV/VIS (DMSO): λ ϭ 363.5, 626.5, 694.0 nm. 1H NMR (solid
state, RT): δ ϭ 7.7 (H-b), 3.9 (H-1). 13C-CP/MAS NMR (solid state, RT):
δ ϭ 121.60 (C-b), 22.18 (C-1).
Nitrido(octa-n-heptylphthalocyaninato)tungsten(V)
(42)
Nitrido(octa-n-propylphthalocyaninato)rhenium(V) (37)
751.9 mg (3.542 mmol) of 4,5-dipropylphthalonitrile (31) and 190.0
mg (0.708 mmol) NH4ReO4 were melted in a Schlenk tube for 50
min at 280°C. Die bluish-black residue was chromatographed on
Al2O3 (neutral, 10 % H2O) with toluene as eluent. After Soxhlet
extraction with hexane 29 mg of (C3H7)8PcReN (37) was obtained.
Yield: 29.0 mg (4 %), bluish-green, microcrystalline solid.
204.1 mg (0.63 mmol) of 4,5-diheptyl-1,2-dicyanobenzene (35) and
42.5 mg (0.14 mmol) of nitridotungsten trichloride were melted for
15 min at 220°C. The crude product was washed with hexane till
all the excess of phthalonitrile 35 had been removed. The hexane
insoluble solid 42 was purified by extraction with hexane in a
Soxhlet apparatus for 12 h. Yield: 31 mg (15 %), dark green solid.
Z. Anorg. Allg. Chem. 2003, 629, 880Ϫ892
889

S. Verma, M. Hanack
MS (FD) (toluene, 30°C): m/z ϭ 1495.1 (Mϩ). UV/VIS (toluene): λ ϭ 373.5,
763.0 nm. ESR (toluene, RT): g ϭ 1.89.
tBu4PcReNB(C6F5)3 (47)
The reaction was conducted with 50.0 mg (0.053 mmol) of
tBu4PcReN (2) and 27.3 mg (0.053 mmol) B(C6F5)3. Yield: 77.2
mg (ca. 100 %), yellowish green solid. C66H48BF15N9Re (1449.16):
C 55.44 (calc. 54.70); H 3.14 (3.34); N 8.37 (8.70)%.
MS (FAB) (NBA, 50°C): m/z ϭ 937.3 (Mϩ Ϫ B(C6F5)3). IR (KBr): ν˜ ϭ
3448 w, 2964 m, 1642 m, 1614 m, 1515 s, 1468 vs, 1396 w, 1366 w, 1330 s,
1283 m, 1258 m, 1195 w, 1156 w, 1095 vs, 1052 w, 980 s, 936 m, 897 vw, 857
vw, 835 w, 794 vw, 758 w, 673 w cmϪ1. UV/VIS (CH2Cl2): λ ϭ 352.5, 681.5,
715.5 nm. 11B NMR (CD2Cl2, RT): δ ϭ Ϫ6.50.
Nitrido(octamethylphthalocyaninato)molybdenum(V)
(43)
95.7 mg (0.61 mmol) of 4,5-dimethyl-1,2-dicyanobenzene (30) and
65.0 mg (0.14 mmol) ditosyliminomolybdenum dichloride were
melted for 15 min at 220°C under Argon. The residue was purified
by a Soxhlet extraction with hexane, toluene and acetonitrile for
12 h each. Yield: 25.0 mg (25 %), dark green, amorphous solid.
MS (FAB) (NBA, 50°C): m/z ϭ 735.1 (Mϩ). IR (KBr): ν˜ ϭ 991 w cmϪ1
(MoϵN). UV/VIS (DMF): λ ϭ 344.0, 710.0 nm. ESR (solid state, RT):
g ϭ 1.97.
tBu4PcReNBPh3 (48)
The reaction was conducted with 20 mg (0.02 mmol) of tBu4PcReN
(2) and 5.2 mg (0.02 mmol) BPh3. Yield: 25.0 mg (99 %), bluish
green solid.
MS (FAB) (NBA, 50°C): m/z ϭ 1102.4 (Mϩ Ϫ Ph), 938.3 (Mϩ Ϫ BPh3). IR
(KBr): ν˜ ϭ 2961 vs, 2903 w, 2864 w, 1614 w, 1483 m, 1437 m, 1393 m, 1364
m, 1331 vs, 1281 m, 1258 vs, 1202 w, 1148 m, 1092 vs, 1051 s, 1024 s, 935 w,
2 Reaction of tBu4PcReN (2) with Electrophiles
tBu4PcReN (2) was dissolved in ca. 5 ml dichloromethane and co-
oled to Ϫ5°C. The electrophile was added dropwise to this solu-
tion. The colour of the solution changes from blue to green. The
solution was stirred for 6 h at Ϫ5°C and the solvent was removed
at Ϫ5°C.
893 vw, 856 vw, 829 m, 802 m, 768 w, 754 m, 698 s, 669 w, 601 vw cmϪ1
.
UV/VIS (CH2Cl2, glass plates): λ ϭ 344.5, 664.0, 695.5 nm. 11B NMR
(CD2Cl2): δ ϭ 45.7 (decomposition product).
tBu4PcReNBEt3 (49)
tBu4PcReNBF3 (44)
The reaction was carried out with 20.0 mg (0.02 mmol) of
tBu4PcReN (2) and 0.02 ml (0.02 mmol) of a 1 M BEt3 solution
(THF). Yield: 22.0 mg (ca. 100 %), bluish green solid.
MS (FAB): m/z ϭ 1008.3 (Mϩ ϩ 2H Ϫ Et), 1006.3 (Mϩ Ϫ Et), 937.3 (Mϩ
Ϫ BEt3). IR (KBr): ν˜ ϭ 3213 s, 2963 s, 2905 vw, 1782 w, 1699 w, 1612 w,
1568 w, 1520 vs, 1479 vs, 1445 vs, 1396 vs, 1367 vs, 1350 s, 1331 s, 1281 w,
1259 s, 1196 s, 1092 s, 1049 s, 1024 m, 937 vw, 831 m, 804 s, 766 w, 754 m,
667 w cmϪ1. IR (CH2Cl2): ν˜ ϭ 3055 w, 2988 w, 1421 w, 1265 vs, 1096 w,
1015 w, 897 w, 804 w, 743 vs, 706 vs cmϪ1. UV/VIS (CH2Cl2, glass plates):
λ ϭ 341.5, 657.5, 696.0 nm. 11B NMR (CD2Cl2): δ ϭ Ϫ0.2 (tBu4PcReN-
BEt3); 32.0, 55.3 (decomposition products).
The reaction was conducted with 50.0 mg (0.053 mmol) of
tBu4PcReN (2) and 9.9 mg (0.07 mmol) BF3·OEt2. Yield: 53.6 mg
(ca. 100 %), yellowish-green solid.
MS (FAB) (NBA, 50°C): m/z ϭ 938.2 (MϩϪBF3). IR (KBr): ν˜ ϭ 3422 w,
2958 m, 2866 w, 1612 s, 1483 m, 1395 m, 1365 m, 1328 vs, 1282 m, 1258 m,
1199 m, 1092 vs, 1051 vs, 964 w, 936 m, 895 w, 832 m, 766 vs, 754 vs, 693 w,
670 m, 599 vw, 564 vw, 533 w, 522 w, 441 vw cmϪ1. UV/VIS (CH2Cl2): λ ϭ
360.5, 676.0 nm. 11B NMR (CDCl3): δ ϭ Ϫ2.0.
tBu4PcReNBCl3 (45)
tBu4PcReNAlCl3 (50)
The reaction was conducted with 80.0 mg (0.085 mmol) of
tBu4PcReN (2) and 0.085 ml (0.085 mmol) of 1 M BCl3 solution
(CH2Cl2). Yield: 89.8 mg (ca. 100 %), green solid. C48H48BCl3N9Re
(1054.4): C 51.73 (calc. 54.69); H 4.23 (4.59); N 11.38 (11.97); Cl
9.50 (9.96)%.
The reaction was carried out in a solvent mixture of THF and
CH2Cl2 with 30.0 mg (0.032 mmol) of tBu4PcReN (2) and 4.3 mg
(0.032 mmol) of AlCl3. Yield: 34.0 mg (99 %), green solid.
MS (FAB) (NBA, 30°C): m/z ϭ 938.4 (Mϩ Ϫ AlCl3). IR (KBr): ν˜ ϭ 3404
vs, 2962 vs, 1617 m, 1483 w, 1396 w, 1333 w, 1259 w, 1200 vw, 1096 m, 1052
w, 937 vw, 804 w, 754 vw, 668 w cmϪ1. UV/VIS (CH2Cl2, glass plates): λ ϭ
366.0, 696.0 nm.
MS (FAB) (NBA, 50°C): m/z ϭ 1018.4 (Mϩ Ϫ Cl), 937.4 (Mϩ Ϫ BCl3). IR
(KBr, argon): ν˜ ϭ 3219 s, 2961 m, 1684 w, 1653 w, 1616 w, 1558 w, 1522 vs,
1474 vs, 1458 vs, 1437 vs, 1396 vs, 1367 vs, 1348 s, 1281 w, 1259 s, 1196 s,
1092 s, 1049 m, 1024 m, 937 vw, 833 m, 804 s, 768 w, 754 w, 667 m cmϪ1
.
tBu4PcReNGaCl3 (51)
IR (KBr, air): ν˜ ϭ 3217 vs, 2963 s, 2907 m, 1518 s, 1464 vs, 1410 vs, 1369 s,
1196 s cmϪ1. IR (CH2Cl2): ν˜ ϭ 3055 w, 2988 w, 1616 vw, 1421 vw, 1265 vs,
1200 vw, 1157 vw, 1090 w, 1018 w, 897 w, 739 vs, 706 vs cmϪ1. UV/VIS
(toluene): λ ϭ 365.0, 627.0, 667.0, 696.5, 719.5 nm. UV/VIS (CH2Cl2): λ ϭ
356.0, 721.0 nm. 11B NMR (CD2Cl2): δ ϭ 3.4.
The reaction was carried out in a mixture of hexane, CH2Cl2 and
THF with 80.0 mg (0.085 mmol) of tBu4PcReN (2) and 15.0 mg
(0.085 mmol) of GaCl3. Yield: 94.5 mg (ca. 100 %), green solid.
C48H48Cl3GaN9Re (1113.3): C 51.60 (calc. 51.79); H 4.62 (4.35); N
10.66 (11.32)%.
MS (FAB) (NBA, 50°C): m/z ϭ 938.4 (Mϩ Ϫ GaCl3ϩH). IR (KBr): ν˜ ϭ
3448 m, 2960 s, 2866 m, 1612 s, 1482 s, 1395 s, 1365 s, 1331 vs, 1282 m, 1258
s, 1200 m, 1149 m, 1093 vs, 1051 s, 935 s, 833 s, 766 w, 754 s, 694 w, 670 m
cmϪ1. UV/VIS (CH2Cl2): λ ϭ 350.5, 720.5 nm.
tBu4PcReNBCl2Ph (46)
The reaction was conducted with 80.0 mg (0.085 mmol) of
tBu4PcReN (2) and 13.6 mg (0.085 mmol) BCl2Ph. Yield: 93.2 mg
(ca. 100 %), green solid. C54H53BCl2N9Re (1096.0): C 61.60 (calc.
59.18); H 4.65 (4.87); N 10.66 (11.50); Cl 6.79 (6.47)%.
MS (FAB) (NBA, 35°C): m/z ϭ 1059.9 (Mϩ Ϫ Cl), 938.2 (Mϩ Ϫ BCl2Ph).
IR (KBr): ν˜ ϭ 2959 s, 2903 m, 1612 m, 1603 m, 1483 m, 1441 m, 1393 s,
1366 s, 1335 vs, 1281 m, 1258 m, 1200 m, 1150 m, 1090 s, 1051 m, 1024 m,
962 vw, 935 m, 831 m, 766 w, 754 m, 700 m, 671 w cmϪ1. UV/VIS (CH2Cl2):
λ ϭ 371.5, 733.5 nm. 11B NMR (CD2Cl2): δ ϭ 30 (decomposition product).
tBu4PcReNGaBr3 (52)
The reaction was carried out in a mixture of hexane and CH2Cl2
with 20.0 mg (0.021 mmol) of tBu4PcReN (2) and 6.6 mg (0.021
mmol) of GaBr3. Yield: 26.2 mg (99 %), green solid.
890
Z. Anorg. Allg. Chem. 2003, 629, 880Ϫ892

Synthesis of Nitrido(phthalocyaninato)metal(V) Complexes RnPcMN (M ϭ Re, Mo, W)
MS (FAB) (NBA, 50°C): m/z ϭ 937.6 (Mϩ Ϫ GaBr3). IR (KBr): ν˜ ϭ 2964
schungsgemeinschaft“ (Schwerpunkt „Nitridobrücken“, II C10-
3221008) for financial support.
s, 2866 m, 1522 m, 1261 vs, 1097 vs, 1022 vs, 864 m, 800 vs, 667 m cmϪ1
UV/VIS (CH2Cl2): λ ϭ 350.5, 691.0, 721.5 nm.
.
tBu4PcReNInCl3 (53)
References
The reaction was carried out in a mixture of THF, CH2Cl2 and
hexane with 30.0 mg (0.032 mmol) of tBu4PcReN (2) and 7.1 mg
(0.032 mmol) of InCl3. Yield: 37.0 mg (ca. 100 %), green solid.
MS (FAB) (NBA, 50°C): m/z ϭ 938.4 (Mϩ Ϫ InCl3ϩH). IR (KBr): ν˜ ϭ
3439 vs, 2962 s, 1611 m, 1481 w, 1393 w, 1332 m, 1260 vs, 1200 vw, 1095 vs,
1021 vs, 933 vw, 803 vs, 751 vw cmϪ1. UV/VIS (CH2Cl2, glass plates): λ ϭ
349.5, 694.5 nm.
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[tBu4PcReNSitBuMe2]ϩClϪ (54)
The reaction was carried out in a mixture of CH2Cl2 and toluene
with 20.0 mg (0.02 mmol) of tBu4PcReN (2) and 3.2 mg (0.02
mmol) of tBuMe2SiCl. Yield: 22.4 mg (ca. 100 %), dark green solid.
MS (FAB) (NBA, 50°C): m/z ϭ 938.6 (Mϩ Ϫ tBuMe2Si), 1053.4 (Mϩ). IR
(KBr): ν˜ ϭ 3448 m, 2959 s, 1615 w, 1573 w, 1523 s, 1485 w, 1394 w, 1368 m,
1334 m, 1260 vs, 1194 vw, 1091 vs, 1049 vs, 935 vw, 802 s, 754 vw, 669 vw
cmϪ1. UV/VIS (toluene, glass plates): λ ϭ 369.0, 666.0, 696.0, 725.5 nm.
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3 Reduction of 9 with C8K Followed by Reaction with
Electrophiles
(C5H11)8PcWNSitBuMe2 (55)
8.0 mg (0.060 mmol) of C8K was added at room temperature to a
solution of 43.0 mg (0.034 mmol) (C5H11)8PcWN (9) in 4 ml THF
whence the solution became dark violet. After 3 h, 5.1 mg (0.034
mmol) of tert.-butyldimethylchlorsilane was added and the initial
brownish-orange solution was left for 17 h when it changed it’s
colour to green. The solution was filtered, the solvent removed and
the product extracted with hexane. Yield: 42.0 mg (89%), green
solid.
MS (FD) (toluene, 30°C): m/z ϭ 1271.5 (Mϩ Ϫ SitBuMe2). IR (KBr): ν˜ ϭ
2959 s, 2926 s, 2858 m, 1620 m, 1468 w, 1331 vw, 1261 s, 1090 s, 1028 m,
895 vw, 806 s cmϪ1. UV/VIS (toluene): λ ϭ 358.5, 725.5 nm. UV/VIS (THF):
λ ϭ 357.5, 723.0 nm. 1H NMR (THF-d8): δ ϭ 0.91 (9H, H-2), 1.02 (24H,
H-8), 1.29 (6H, H-1),1.37 (16H, H-7), 1.61 (16H, H-6), 2.37 (16H, H-5), 2.72
(16H, H-4), 7.29-7.68 (8H, H-arom.).
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(C5H11)8PcWNGeMe3 (56)
8.0 mg (0.060 mmol) of C8K was added to a solution of 43.0 mg
(0.034 mmol) (C5H11)8PcWN (9) in 4 ml THF at room temperature
with stirring. The dark red violet solution was stirred for 18 h.
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colour of the solution turned to brownish-green. After 25 h a green
solution was obtained which was filtered and the filtrate was evap-
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(85%), green solid.
MS (FAB) (NBA, 30°C): m/z ϭ 1270.4 (Mϩ Ϫ GeMe3). IR (KBr): ν˜ ϭ 2963
m, 1262 vs, 1096 vs, 1020 vs, 864 m, 801 vs, 394 s cmϪ1. UV/VIS (toluene):
λ ϭ 367.0, 731.5 nm. 1H NMR (THF-d8): δ ϭ 0.91 (24H, H-6), 1.29 (9H,
H-1), 1.37 (16H, H-5), 1.59 (16H, H-4), 2.40 (16H, H-3), 2.72 (16H, H-2),
7.37-7.91 (8H, H-arom.). 13C NMR (THF-d8): δ ϭ 13.3 (C-6), 20.45 (C-1),
22.4 (C-5), 30.6 (C-4), 31.7 (C-3), 32.8 (C-2), 123.2 (C-b), 127.1 (C-c), 129.2
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