Reactivity of a phosphanylalane complex towards Lewis bases

Article abstract of DOI:10.1002/ejic.200300637

The reactivity of the Lewis acid/base stabilized complex of phosphanylalane [(CO)₅W(H₂PAlH₂·NMe₃)] (1) towards the Lewis bases THF and NMe₃ has been investigated. The reaction with THF leads to decomposition of the complex. One of the decomposition products was identified as containing the anion [{(CO) ₅W}₂PH₂]^- (2). This anion could be synthesized independently by reaction of [(CO)₅WTH₃] with KH in the presence of [(CO)₅W(THF)] and was isolated as the tetraphenylphosphonium salt [Ph₄P][{(CO)₅W) ₂PH₂] (2a). The treatment of 1 with NMe3 leads to the formation of [(CO)₅W(H₂PAlH₂·2 NMe ₃)] (3) containing a five-coordinate aluminum atom. Compound 3 exhibits a fast exchange of the NMe₃ ligands in solution containing an excess of NMe3. The products were characterized by spectroscopic methods and X-ray crystallography. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200300637

FULL PAPER
Reactivity of a Phosphanylalane Complex towards Lewis Bases
Ulf Vogel,[a] Karl-Christian Schwan,[a] and Manfred Scheer*[a]
Dedicated to Prof. R. Schmutzler on the occasion of his 70th birthday
Keywords: Aluminum / Phosphorus / Hydrides / Reactivity / Lewis bases
The reactivity of the Lewis acid/base stabilized complex of
treatment of
1 with NMe3 leads to the formation of
phosphanylalane [(CO)5W(H2PAlH2·NMe3)] (1) towards the
[(CO)5W(H2PAlH2·2 NMe3)] (3) containing a five-coordinate
Lewis bases THF and NMe3 has been investigated. The reac- aluminum atom. Compound 3 exhibits a fast exchange of the
tion with THF leads to decomposition of the complex. One of
the decomposition products was identified as containing the
anion [{(CO)5W}2PH2]− (2). This anion could be synthesized
independently by reaction of [(CO)5WPH3] with KH in the
NMe3 ligands in solution containing an excess of NMe3. The
products were characterized by spectroscopic methods and
X-ray crystallography.
presence of [(CO)5W(THF)] and was isolated as the tetra- ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
phenylphosphonium salt [Ph4P][{(CO)5W}2PH2] (2a). The
Germany, 2004)
Introduction
tion,[4] whereas the boron compound was accessible by a salt
elimination route.[5] Herein we report on the reactivity of 1
towards the Lewis bases THF and NMe3, respectively.
Compounds containing bonds between group 13 and
group 15 elements are especially interesting due to their po-
tential use as molecular precursors for the generation of thin
films of group 13/15 semiconductors. Compounds of the type
(R2EEЈRЈ2)n (R, RЈ: organic substituents, EЈ: group 13 ele-
ment, E: group 15 element) have been intensively investi-
gated[1] and usually form oligomeric structural frameworks.
These compounds are monomeric if they possess bulky R
and RЈ groups to block the intermolecular aggregation. To
obtain monomers, the steric influence of the substituents can
be neglected if both a Lewis base is coordinated at the group
13 element and the group 15 element still possesses bulky
substituents or if, besides the Lewis base at the group 13
element, the lone pair of the group 15 element is occupied
by a Lewis acid. Examples of the former mode are the com-
pounds [Mes2EAlH2·NMe3],[2] obtained by the treatment of
Results and Discussion
Decomposition of 1 in THF
Upon dissolving in THF, 1 reacted with vigorous H2
evolution [Equation (1)]. The 31P NMR spectrum of the re-
action mixture gave some hints of the possible formation of
an anionic complex with the formula of 2. The 31P{1H}
NMR spectrum of the reaction mixture shows two main P
containing products as single peaks having tungsten satel-
lites which split into triplets when the proton coupled spec-
trum was recorded. Compound 2 shows a triplet at
Ϫ267.7 ppm (1JP,H ϭ 268, 1JW, P ϭ 146 Hz). The other prod-
uct, whose structure could not be assigned yet, shows a trip-
1
let at Ϫ100.3 ppm (1JP,H ϭ 340, JW, P ϭ 220 Hz). The ratio
ClAlH2·NMe3 with LiEMes2 (E
ϭ
P, As), and
[(Me3Si)2EAlMe2·dmap][3] synthesized by treating oligomers
of the type [Me2AlE(Me3Si)2]n (E ϭ P, As; n ϭ 2, 3) with
the Lewis base N,NЈ-dimethylaminopyridine (dmap). We de-
veloped the latter concept of monomeric group 13/15 com-
pounds by the stabilization of the hydrogen substituted par-
ent compounds [(CO)5W(PH2EЈH2·NMe3)] (1: EЈ ϭ Al, 2:
EЈ ϭ Ga, 3: EЈ ϭ B). These phosphanylalane and -gallane
complexes were synthesized by a hydrogen elimination reac-
of the integrals of the tungsten satellites towards the central
peak of 2 suggests that two tungsten atoms are bound to
each phosphorus atom as in [{(CO)5W}2PH2]Ϫ. By adding
Ph4PBr to the mixture of reaction (1) some yellow crystals
appeared which were identified crystallographically by their
unit cell to be [Ph4P][{(CO)5W}2PH2] (2a) (cf. discussion
below).
[a]
Institut für Anorganische Chemie, Universität Karlsruhe (TH),
(1)
76128 Karlsruhe, Germany
Fax: (internat.) ϩ 49-(0)721-6087021
E-mail: mascheer@chemie.uni-karlsruhe.de
2062
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejic.200300637
Eur. J. Inorg. Chem. 2004, 2062Ϫ2065

Reactivity of a Phosphanylalane Complex towards Lewis Bases
FULL PAPER
In order to develop a more efficient approach to 2a it in 2a. This can be explained by the low steric shielding of
was synthesized by the reaction of [(CO)5WPH3] with KH the H substituents at the P atom. Complex 2a represents
in the presence of [(CO)5W(THF)] [Equation (2)]. Cation the first parent compound (R
ϭ H) of the class
exchange using PPh4Br and crystallization from CH2Cl2/ [(LnM)2PR2]Ϫ, which exists amongst only a few organic
n-hexane afforded pure [PPh4][{(CO)5W}2PH2] (2a) which substituted examples.[8]
showed identical NMR spectra to the decomposition prod-
uct 2. The IR spectrum of 2a revealed a PH stretching ab-
sorption at 2306 cmϪ1 as well as three CO valence stretch-
ing modes at 2048, 1930 and 1872 cmϪ1 for the two W(CO)5
moieties showing a local C4v symmetry.
Reaction of 1 with NMe3
In contrast to the reaction with THF, 1 did not show
decomposition when allowed to react with the nitrogen-cen-
tered Lewis base NMe3. The product of this reaction is
complex 3 which contains a pentacoordinated Al atom in
a trigonal bipyramidal arrangement containing two NMe3
molecules [Equation (3)]. A similar reaction is also known
from H3Al·NMe3 with NMe3 which forms the adduct
H3Al·2 NMe3,[9] exhibiting a trigonal bipyramidal coordi-
nated aluminum atom.[10] The solid-state Raman spectrum
of 3 showed bands in the region of the terminal CO stretch-
ing frequencies as well as for the PH valence at 2331 and
2315 cmϪ1 and one AlH stretch at 1744 cmϪ1. The EI-mass
spectrum did not show a molecular ion peak. However,
[(CO)5WPH2AlH2·NMe3]ϩ was detected as the ion with the
highest mass. Moreover, signals for its degradation, re-
sulting from CO and NMe3 loss were also found. The
31P{1H} NMR spectrum of 3 shows a singlet at δ ϭ
(2)
The X-ray Crystal Structure Analysis of 2a
The molecular structure of 2a shows a [PPh4]ϩ cation
and a [{(CO)5W}2PH2]Ϫ anion. An ORTEP plot of the
anion is depicted in Figure 1, while selected bond lengths
and angles are listed in Table 1.
Ϫ251 ppm which exhibits tungsten satellites (1JW, P
ϭ
1
149 Hz). The H NMR spectrum reveals a doublet for the
PH2 protons at δ ϭ 1.58 ppm (1JP,H ϭ 268 Hz), a singlet
for the NMe3 groups at δ ϭ 1.71 ppm and a broad signal
for the AlH2 protons at δ ϭ 3.15 ppm.
(3)
In the presence of an excess of trimethylamine, 3 shows
dynamic behavior in solution which can be attributed to
fast exchange of the coordinated trimethylamine molecules.
Figure 1. Molecular structure of the anion of 2a in the crystal (OR-
TEP plot, 50% probability displacement ellipsoids)
1
The variable temperature H NMR spectra are shown in
Figure 2. At low temperatures two signals can be detected
for the NMe3 groups: one can be assigned to coordinated
(A) and one to free trimethylamine (B). With rising tem-
perature, the two signals are shifted towards each other, and
at the coalescence temperature of ca. Ϫ45 °C only one
broad signal is observed. At higher temperatures only one
signal is detected for coordinated and free trimethylamine
(C). For this process the free activation enthalpy at the co-
˚
Table 1. Selected bond lengths [A] and angles [°] for 2a
W1ϪP
WϪCtrans
W1ϪPϪW2
2.579(2)
1.978(8)
126.79(7)
W2ϪP
WϪCcis
2.580(2)
2.029(9)
[a]
[a]
[a]
Averaged bond lengths.
alescence temperature was calculated to be 45.3 kJ·molϪ1
.
The anion of 2a (Figure 1) shows a PH2 group which is
coordinated to two W(CO)5 moieties. The WϪP bond
lengths are 2.579(2) and 2.580(2) A, respectively, and the
The Solid-State Structure of 3
˚
W1ϪPϪW2 angle is 126.79(7)°. Comparison of these val-
The solid-state structure of 3 was determined by a single-
ues with the compounds [Cp(CO)3W(µ-PPh2)W(CO)5] crystal X-ray diffraction study. Selected bond lengths and
[6]
˚
[WϪPϪW 118.4(1)°; WϪP 2.626(3) A], [Cp(CO)2Fe(µ- angles are reported in Table 2. An ORTEP plot of the mo-
[7]
˚
PPh2)W(CO)5] (WϪPϪFe 118.42(6)°; WϪP 2.581(1) A]
lecular structure of 3 is depicted in Figure 3. The central
and [Et4N][CpЈ(CO)2Mn(µ-PPh2)W(CO)5] (CpЈ
ϭ
η5- motif of the crystal structure of 3 is a H2AlPH2 moiety
C5H4Me) [WϪPϪMn 119.8(1)°; WϪP 2.622(3) A] show which is connected to a W(CO)5 fragment by the P atom.
that, in particular, the WϪPϪW angle is significantly larger Two NMe3 molecules are coordinated to the Al atom,
[8]
˚
Eur. J. Inorg. Chem. 2004, 2062Ϫ2065
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 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2063

U. Vogel, K.-C. Schwan, M. Scheer
FULL PAPER
the aluminum atom by the second NMe3 group. The slightly
˚
˚
longer PϪW bond (3: 2.566(1) A, 1: 2.549(1) A] and the
larger WϪPϪAl angle (3: 128.58(6)°, 1: 118.44(4)°] in 3
further support this explanation.
Conclusion
The results have shown that the Lewis-acid/base stabil-
ized phosphanylalane is very sensitive towards reactions
with different Lewis bases. The ability of the Al atom to
achieve pentacoordination enables firstly an addition of the
Lewis base which leads, depending upon its nature, to stable
adducts (as in the case of NMe3) or to decomposition as in
the case of THF via cleavage of the AlϪP bond and re-
moval of the Al moiety.
Experimental Section
1
Figure 2. Variable temperature H NMR spectra of a mixture of 3
and an excess of NMe3 in CD2Cl2; at Ϫ70 °C the spectrum shows
signals for coordinated NMe3 (A), free NMe3 (B) and the PH2
protons (D); at Ϫ30 °C only the PH2 protons and one signal for
NMe3 (C) are detected; impurities are marked with *
General Remarks: All manipulations were carried out under an at-
mosphere of dinitrogen using standard Schlenk techniques. All sol-
vents were dried via standard procedures and distilled freshly be-
fore use. NMe3 was dried by condensing it over Na/benzophenone
at Ϫ78 °C and stirring the mixture until the solution showed a dark
blue color. PPh4Br was heated to 100 °C in vacuo for one hour
to remove traces of moisture. [(CO)5W(H2PAlH2·NMe3)] (1) was
prepared according to our published method.[4] All NMR spectra
were recorded on a Bruker AC 250 spectrometer with δ referenced
to external SiMe4 (1H) or H3PO4 (31P), respectively. IR spectra were
measured on a Bruker IFS 28 instrument and Raman spectra on a
Bruker FRA 106 spectrometer. All mass spectra were recorded on
a Varian MAT 711 instrument at 70 eV.
˚
Table 2. Selected bond lengths [A] and angles [°] for 3
WϪP
2.566(1)
2.160(4)
1.988(5)
128.58(6)
94.2(1)
PϪAl
AlϪN2
WϪCcis
N1ϪAlϪP
N1ϪAlϪN2
2.432(2)
2.155(4)
2.034(5)
94.7(1)
AlϪN1
WϪCtrans
AlϪPϪW
[a]
[a]
N2ϪAlϪP
171.1(2)
[a]
Averaged bond lengths.
[Ph4P][{(CO)5W}2PH2] (2a): To a solution of [(CO)5W(THF)],
which was produced by irradiating [W(CO)6] (352 mg, 1.00 mmol)
in THF (50 mL), [(CO)5WPH3] (358 mg, 1.00 mmol) and KH
(40 mg, 1.00 mmol) were added subsequently. After the gas evol-
ution had ceased the mixture was stirred for three hours to ensure
complete reaction. To the clear yellow solution solid PPh4Br
(419 mg, 1.00 mmol) was added resulting in the formation of a
white solid which was separated by filtration. The filtrate was re-
duced to dryness in vacuo and the remaining residue dissolved in
CH2Cl2 (10 mL). After removal of the insoluble material by fil-
tration the solution was layered with n-hexane (20 mL) affording
yellow crystals of 2a after two days. Yield 643 mg (63%). IR
(CH2Cl2): ν˜ ϭ 3055 (m), 2987 (w), 2306 (w), 2048 (m), 1930 (vs),
1872 (s), 1440 (m), 1422 (m), 1271 (vs), 1259 (vs), 1109 (w), 896
1
(w) cmϪ1
.
1H NMR (250 MHz, CD2Cl2): δ ϭ 1.91 (d, JP,H
ϭ
268 Hz, 2 H, PH2), 7.52Ϫ7.92 (m, 20 H, PPh4) ppm. 31P{1H}
Figure 3. Molecular structure of 3 in the crystal (ORTEP drawing,
50% probability displacement ellipsoids)
1
NMR (101 MHz, CD2Cl2): δ ϭ Ϫ267.7 (s, JP,W ϭ 146 Hz, PH2),
23.0 (s, PPh4) ppm. 31P NMR (101 MHz, CD2Cl2): δ ϭ Ϫ267.7 (t,
1JP,H ϭ 268, JP,W ϭ 146 Hz, PH2), 23.0 (s, PPh4) ppm.
1
which thus exhibits a coordination number of five in a dis-
torted trigonal bipyramidal arrangement. Both trimeth-
ylamine ligands occupy the apical positions of the trigonal
bipyramid with similar AlϪN bond lengths of 2.160(4) and
[(CO)5W(H2PAlH2·2 NMe3)] (3): NMe3 (0.36 mmol) was con-
densed into a solution of [(CO)5W(H2PAlH2·NMe3)] (53 mg,
0.12 mmol) in n-hexane (20 mL) at Ϫ196 °C. The reaction mixture
was allowed to warm to ambient temperature over 20 minutes. Any
insoluble material formed was removed by filtration, and the solu-
tion was kept at Ϫ20 °C. Light yellowish colored crystals of 3 were
formed over two days. Yield 32 mg (53%). Raman (solid state): ν˜ ϭ
3004 (w), 2977 (m), 2929 (m), 2905 (m), 2855 (m), 2788 (w), 2331
˚
2.155(4) A, respectively. The N1ϪAlϪN2 angle is 171.1(2)°.
˚
At 2.432(2) A the AlϪP bond length in 3 is significantly
[4]
˚
longer than in 1 [2.377(1) A], although in both com-
pounds the aluminum atom is pentacoordinate (1 reveals
an intermolecular dimerization via H bridges). The longer
(m), 2315 (m), 2063 (s), 1956 (vs), 1936 (w), 1904 (s), 1880 (w),
AlϪP bond in 3 can be attributed to the steric shielding at 1744 (w, br), 821 (w), 435 (m), 434 (m), 116 (m) cmϪ1. H NMR
1
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Eur. J. Inorg. Chem. 2004, 2062Ϫ2065

Reactivity of a Phosphanylalane Complex towards Lewis Bases
FULL PAPER
Table 3. Crystallographic data for 2a and 3
2
3
Empirical formula
Mr
T [K]
C34H22O10P2W2
1020.16
200(1)
C11H22AlN2O5PW
504.11
200(1)
Crystal size
Space group
Crystal system
0.20 ϫ 0.15 ϫ 0.02
P21/n
monoclinic
14.231(3)
14.377(3)
17.742(4)
0.30 ϫ 0.20 ϫ 0.10
P21/n
monoclinic
11.559(2)
10.957(2)
15.371(3)
˚
a (A)
˚
b (A)
˚
c (A)
α [°]
β [°]
γ [°]
90
92.10(3)
90
90
102.11(3)
90
1903.4(7)
Ϫ3
˚
V [A
]
3627.7(12)
Z
4
4
dc [g cmϪ3
]
1.868
6.478
1.759
6.216
µc [mmϪ1
]
2θ range [°]
hkl range
3.64 Յ 2θ Յ 52.00
Ϫ17 Յ h Յ 17,-16 Յ k Յ 15,-21 Յ l Յ 21
5.18 Յ 2θ Յ 52.00
Ϫ13 Յ h Յ 14,-13 Յ k Յ 13,-17 Յ l Յ 18
Data/restraints/parameters
No. of unique data
Independent reflections [I Ͼ 2 σ(I)]
Goodness-of fit on F2
6631/0/441
6631 (Rint ϭ 0.0594)
4879
3519/0/200
3519 (Rint ϭ 0.1318)
3256
0.903
1.056
[b]
R1 [a], wR2 [I Ͼ 2 σ(I)]
0.0340, 0.0732
0.0522, 0.0774
1.041, Ϫ1.364
0.0325, 0.0856
0.0346, 0.0867
1.665, Ϫ2.111
R1 [a], wR2 [all data]
Largest diff. peak/hole [e·A
[b]
Ϫ3
˚
]
[a]
[b]
2
2 2
2 2 1/2
R ϭ |Fo| Ϫ |Fc||/|Fo|. wR2 ϭ [w(Fo Ϫ Fc ) ]/[(Fo ) ]
1
(250 MHz, [D8]toluene, Ϫ50 °C): δ ϭ 1.58 (d, JP,H ϭ 268 Hz, 2
H, PH2), 1.71 (s, 18 H, NMe3), 3.15 (br. s, 2 H, AlH2) ppm.
31P{1H} NMR (101 MHz, [D8]toluene, Ϫ70 °C): δ ϭ Ϫ251 (s,
1JP,W ϭ 149 Hz, PH2) ppm. 31P NMR (101 MHz, [D8]toluene, Ϫ70
°C): δ ϭ Ϫ251 (t, 1JP,W ϭ 268, 1JP,W ϭ 149 Hz, PH2) ppm. EI-MS
(70 °C): m/z ϭ 445 (Mϩ Ϫ NMe3, 1%), 417 (Mϩ Ϫ NMe3 Ϫ CO,
1%), 386 (Mϩ Ϫ2 NMe3, 2%), 358 (Mϩ Ϫ2 NMe3 Ϫ CO, 13%),
330 (Mϩ Ϫ2 NMe3 Ϫ 2 CO, 5%), 302 (Mϩ Ϫ2 NMe3 Ϫ 3 CO,
16%), 302 (Mϩ Ϫ2 NMe3 Ϫ 3 CO, 16%), 272 (Mϩ Ϫ2 NMe3 Ϫ 4
CO Ϫ 2 H, 16%), 244 (Mϩ Ϫ2 NMe3 Ϫ 5 CO Ϫ2 H, 11%).
bridge CB2 1EZ, UK; Fax: (internat.) ϩ44-1223-336-033; E-mail:
deposit@ccdc.cam.ac.uk].
Acknowledgments
This work was comprehensively supported by the Deutsche For-
schungsgemeinschaft and the Fonds der Chemischen Industrie.
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CCDC-218817 and -218818 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the
Cambridge Crystallographic Data Center, 12, Union Road, Cam-
Received July 9, 2003
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