Synthesis of aminophosphane complexes: Searching the boundary between phosphanide and phosphinidenoid complex chemistry

Article abstract of DOI:10.1002/ejic.201101437

Aminophosphane complexes 3a-e have been prepared by two different pathways: (1) the thermal reaction of 2H-azaphosphirene complex 1 with primary or secondary amine derivatives at 75 °C (3a,b,d,e) or (2) the reaction of chlorophosphane complex 2 with sodium diphenylamide (3c). In the latter case, complex 3c was obtained together with the diphosphene complex 6, thus providing evidence for the transient formation of Na/X phosphinidenoid complexes 4a,b and/or the terminal phosphinidene complex 5. Preliminary deprotonation studies, carried out on complex 3a by using lithium diisopropylamide in TMEDA in the presence of 12-crown-4 at low temperature, yielded a mixture of the Li/NMe ₂ phosphinidenoid complex 7 together with the nonligated phosphane derivative 8, which could not be separated. Complexes 3a,b,d,e and 6 were characterized by NMR and IR spectroscopy, MS, and elemental analysis. The structures of complexes 3c-e and 6 were confirmed by single-crystal X-ray diffraction analysis. Aminophosphane complexes 3a-e have been prepared by two routes. Complex 3c was obtained along with diphosphene complex 6, giving evidence for the formation of transient Na/X phosphinidenoid complexes 4a,b and/or phosphinidene complex 5. Initial studies on the deprotonation of 3a led to the formation of the Li/NMe₂ phosphinidenoid complex 7a along with the nonligated phosphane derivative 8. Copyright

Full text of DOI:10.1002/ejic.201101437

FULL PAPER
DOI: 10.1002/ejic.201101437
Synthesis of Aminophosphane Complexes: Searching the Boundary between
Phosphanide and Phosphinidenoid Complex Chemistry
Lili Duan,[a] Gregor Schnakenburg,[a] Jörg Daniels,[a] and Rainer Streubel*[a]
Dedicated to Professor U. Zenneck on the occasion of his 65th birthday
Keywords: Amines / Phosphanes / Phosphorus / Tungsten / Reaction mechanisms
Aminophosphane complexes 3a–e have been prepared by
two different pathways: (1) the thermal reaction of 2H-aza-
tonation studies, carried out on complex 3a by using lithium
diisopropylamide in TMEDA in the presence of 12-crown-4
phosphirene complex 1 with primary or secondary amine de- at low temperature, yielded a mixture of the Li/NMe2 phos-
rivatives at 75 °C (3a,b,d,e) or (2) the reaction of chlorophos-
phane complex 2 with sodium diphenylamide (3c). In the lat-
ter case, complex 3c was obtained together with the diphos-
phene complex 6, thus providing evidence for the transient
formation of Na/X phosphinidenoid complexes 4a,b and/or
phinidenoid complex 7 together with the nonligated phos-
phane derivative 8, which could not be separated. Com-
plexes 3a,b,d,e and 6 were characterized by NMR and IR
spectroscopy, MS, and elemental analysis. The structures of
complexes 3c–e and 6 were confirmed by single-crystal X-
the terminal phosphinidene complex 5. Preliminary depro- ray diffraction analysis.
stability, we became interested in examining the scope of
Introduction
this protocol and the properties of the complexes formed
after deprotonation. Herein we report the synthesis of new
1,1Ј-bifunctional aminophosphane complexes and, in a pre-
liminary study, the deprotonation of a (dimethylamino)-
phospahne derivative.
Phosphanides I and their complexes II (Scheme 1) are
key reagents and ligands in both main-group and transi-
tion-metal chemistry; for example, lithium phosphanides[1]
enable the formation of single and/or multiple bonds be-
tween phosphorus and carbon and/or metal atoms. Al-
though much more reactive and short-lived, phosphanyl-
idenes III[2] and their terminal complexes IV[2,3] have at-
tracted the attention of experimental and theoretical chem-
ists for more than four decades, and in particular the latter
have become important building blocks in organophos-
phorus chemistry.
Results and Discussion
Secondary phosphane derivatives RP(H)X, which con-
tain P–H and P–X bonds (X = Cl, OR, NR2, NHR), are
relatively rare, because they are, in general, thermally un-
stable and can easily eliminate HX to form phosphanyl-
idenes[6] or diphosphanes,[7] and/or undergo rearrangement
reactions to form phosphane oxide compounds.[8] Thus, the
classical complexation of a “free” phosphane derivative is
not a viable method. Therefore, we used the protocols
shown in Scheme 2 to prepare (amino)(organo)phosphane
complexes: (1) 2H-azaphosphirene complex 1[9] was heated
in the presence of primary and secondary amines in toluene
at 75 °C to yield 3a,b,d,e, and (2) the chlorophosphane com-
plex 2[10] was treated with sodium diphenylamide in diethyl
Scheme 1. Phosphanides I and their complexes II, phosphanyl-
idenes III and their complexes IV, and M/X phosphinidenoid com-
plexes V (R, RЈ = organic substituent; M = alkali metal; MLn
transition-metal fragment; X = Hal or alkoxy group).
=
Recently, Li/X phosphinidenoid complexes V were pre- ether at –30 °C to give 3c.
pared by deprotonation of halogenophosphane complexes
The aminophosphane complexes 3a–e were obtained in
using lithium diisopropylamide (LDA) in the presence of good yields following column chromatography at low tem-
12-crown-4.[4,5] Because such complexes show low thermal perature or by washing with n-pentane (3a,d). Complexes
3a–e were fully characterized by NMR and IR spec-
[a] Institut für Anorganische Chemie, Universität Bonn,
troscopy, mass spectrometry, and elemental analysis. The
structures of complexes 3c–e were unambiguously con-
firmed by single-crystal X-ray diffraction.
Gerhard-Domagk-Str. 1, 53121 Bonn, Germany
Fax: +49-228-739616
E-mail: r.streubel@uni-bonn.de
2314
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2012, 2314–2319

Aminophosphane Complexes
Scheme 2. Synthesis of aminophosphane complexes 3a–e.
Figure 1. Molecular structure of complex 3c in the crystal. All hy-
drogen atoms except Hp are omitted for clarity. Selected bond
lengths [Å] and bond angles [°]: P–Hp 1.29(3), P–W 2.5305(7), P–
N 1.717(2), P–C1 1.819(3), N–C8 1.488(3); N–P–W 118.13(8), N–
P–C1 104.09(11), W–P–C1 121.58(9).
The 31P NMR resonances of complexes 3a–e were ob-
served in the range of δ ≈ 5–46 ppm with coupling constants
1
1J(W,P) = 250–260 Hz and J(P,H) = 320–357 Hz, which are
consistent with those of the aminophosphane complexes
published earlier by Mathey and co-workers.[3a,3b,11] In the
13C NMR analysis, the carbon atoms directly bound to the
phosphorus atom (abbrev. CP) resonate at δ ≈ 22 ppm with
a very small phosphorus–carbon coupling constant of ca.
1
4–8 Hz. The H NMR spectra show the P–H proton signal
at δ ≈ 7 ppm. The IR spectra of complexes 3a–e (KBr pel-
lets) display ν(P–H) stretching absorptions between 2220
and 2310 cm–1, which are also in line with values reported
previously.[11a,12,13] Selected NMR and IR data are given in
Table 1.
Table 1. Selected NMR and IR data for complexes 3a–e.
Complex
δ [ppm]/J [Hz]
δ(13CP)/
ν(P–H)[b] [cm–1]
˜
δ(31P)/
δ(1H)/
1J(W,P)
1J(P,C)
1J(P,H)
[a]
3a
3b
3c
3d
3e
46.1/
249.2
31.0/
249.2
23.7/
263.2
11.4/
255.6
5.3/253.0
22.6/2.9
22.7/3.9
–
7.03/
342.9
7.18/
342.5
–
2270
not observed
–
Figure 2. Molecular structure of complex 3d in the crystal. All hy-
drogen atoms except Hp1 are omitted for clarity. Selected bond
lengths [Å] and bond angles [°]: P1–Hp1 1.28(4), P1–N1 1.682(3),
P1–C1 1.834(4), P1–W1 2.5049(10), N1–C8 1.476(4); N1–P1–W1
117.68(11), N1–P1–C1 104.32(16), W1–P1–C1 117.79(12).
22.3/7.8
22.4/br
7.09/
320.2
7.49/
357.7
2226
2310
[a] Carbon atoms directly bound to the phosphorus atom. [b] ν
˜
values of P–H stretching absorptions.
From Table 1 it is apparent that (diorganoamino)phos-
phane complexes 3a–c have 31P resonances that are shifted
downfield relative to those of (organoamino)phosphane
complexes 3d,e. Note that the ν(P–H) stretching absorption
was not observed for complex 3b, although well-established
by its P–H coupling constant in the NMR spectra. A sim-
ilar observation was reported by Marinetti and Mathey[11a]
for [(CO)5W(Ph)P(H)NEt2]; the reason for this phenome-
non was and still is unclear.
Figure 3. Molecular structure of complex 3e in the crystal. All hy-
drogen atoms except Hp are omitted for clarity. Selected bond
lengths [Å] and bond angles [°]: P–N 1.691(11), P–C1 1.835(13), P–
W 2.516(3), N–C8 1.430(18); N–P–C1 107.8(6), C1–P–W 127.1(4),
The molecular structures of complexes 3c–e were con-
firmed by single-crystal X-ray diffraction analysis (Fig-
ures 1, 2, and 3); all bond lengths and angles are within the
normal range. One structural feature deserves mention: The W–P–N 108.0(4).
Eur. J. Inorg. Chem. 2012, 2314–2319
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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L. Duan, G. Schnakenburg, J. Daniels, R. Streubel
FULL PAPER
orientation of the C–H bond of the CH(SiMe3)2 group rela- al.[16] The only hint of steric crowding can be derived from
tive to the P–W bond shows an s-trans conformation for the two-fold s-trans conformation of the C–H and P–W
complexes 3c,e, whereas it is s-cis for complex 3d.
bond [of CH(SiMe3)2] in 6.
Remarkably, in the synthesis of complex 3c, the (Z)-di-
phosphene complex 6[14] was also formed (ratio 6/3c ≈
1:1.5), which provides some evidence for the intermediate
formation of the phosphinidene complex 5. As the route
to 6 is not apparent, we propose two different pathways
(Scheme 3). As an alternative to chloro substitution to yield
the aminophosphane complex 3c, deprotonation of 2 may
occur to give the Na/Cl phosphinidenoid complex 4a. Alter-
natively, after the formation of complex 3c, the Na/NPh2
phosphinidenoid complex 4b may be also formed by depro-
tonation. Both phosphinidenoid complexes 4a,b may un-
dergo elimination to give the diphosphene complex 6, prob-
ably via the terminal phosphinidene complex 5.
Figure 4. Molecular structure of complex 6 in the crystal. All hy-
drogen atoms are omitted for clarity. Selected bond lengths [Å] and
bond angles [°]: P–Pi 2.050(3), P–W 2.5156(17), P–C1 1.819(6); W–
P–Pi 125.99(4), W–P–C1 121.9(2), C1–P–Pi 111.7(2).
In a preliminary study we examined the deprotonation
of complex 3a with LDA in the presence of 12-crown-4 at
–78 °C. The 31P{1H} NMR spectrum (Figure 5) displays a
broadened quartet at δ = 101.8 ppm [1J(P,Li) = 62.1 Hz] and
a sharp singlet at δ = 39.1 ppm together with signals repre-
senting small amounts of other unidentified byproducts
(Ͻ5%). Despite the absence of tungsten satellites, the quar-
tet was tentatively assigned to the Li/NMe2 phosphinid-
enoid complex 7 (Scheme 4) because of the downfield-
shifted 31P resonance and the phosphorus–lithium cou-
pling.[17] As the singlet at δ = 39.1 ppm shows no tungsten–
phosphorus coupling but a large phosphorus–proton cou-
pling [1J(P,H) = 195.9 Hz], we tentatively assigned this signal
to the (free) ligand 8. The ratio of these two major products
changed over time; the signal intensity of complex 7 de-
creased after 50 h and that of compound 8 increased, the
ratio of 7/8 changing from ca. 3:1 to ca. 1:1. Unfortunately,
Scheme 3. Proposed pathways for the formation of complex 6.
The 31P resonance of complex 6 appears at δ =
324.4 ppm [J(W,P) = 146.5, 115.9 Hz], which is close to the
values of related complexes (Z)-[(OC)5W(Mes)P=P(Mes)-
W(CO)5] (Mes = 2,4,6-trimethylphenyl; δ = 313.6 ppm) and
(E)-[(OC)5W{(Me3Si)2HC}P=P{CH(SiMe3)2}W(CO)5] (δ
= 342.2 ppm).[15] However, the tungsten–phosphorus cou-
pling constants are different for complexes with (E) and (Z)
configurations. For example, the latter complex with (E)
configuration has J(W,P) = 268 Hz, which is larger than that
of the former (Z)-diphosphene complex [J(W,P) = 116 Hz].
The 31P NMR spectroscopic data for complex 6 is much
closer to that of the diphosphene complex described by
Yoshifuji et al. [δ = 332 ppm; J(W,P) = 145, 116 Hz].[16]
The molecular structure of complex 6 was also con-
firmed by single-crystal X-ray diffraction (Figure 4). Al-
though the first impression is that of a sterically crowded
molecular compound, the P–P bond length in complex 6
[2.050(3) Å] is very similar to that of the (only other) (Z)-
Figure 5. 31P NMR spectrum of the reaction solution of complex
diphosphene complex [2.041(4) Å] reported by Yoshifuji et 3a and LDA showing tentative assignments.
2316 Eur. J. Inorg. Chem. 2012, 2314–2319
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© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Aminophosphane Complexes
X-ray Crystallographic Analysis of 3c–e and 6: Data were collected
with a Nonius–KappaCCD diffractometer at 123 K by using Mo-
Kα radiation (λ = 0.71073 Å). The structures were refined by full-
matrix least squares on F2 (SHELXL-97[21]). All non-hydrogen
atoms were refined anisotropically. The hydrogen atoms were in-
cluded in calculated positions by using a riding model. CCDC-
855282 (3c), -855283 (3d), -855284 (3e), and -855285 (6) contain
the supplementary crystallographic data. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
the mechanism for the decomposition of complex 7 remains
unclear as neither complex 7 nor compound 8 could be ob-
tained by column chromatography or crystallization.
Synthesis of Complex 3a: Dimethylamine (0.5 mL, 1.0 mmol) was
added to a stirred solution of 2H-azaphosphirene complex 1
(617 mg, 1.0 mmol) in toluene (30 mL) and heated at 75 °C for 3 h.
After removal of all volatiles in vacuo (ca. 10–2 mbar), the final
Scheme 4. Synthesis of complexes 7 and 8 by reaction of complex
3a with LDA.
Although the phosphorus–lithium coupling con- product 3a was purified by washing with n-pentane at low tempera-
stant[17,18] strongly suggests complex 7, the data of deriva-
tive 8 are similar to those of one of the very few 1,1Ј-bifunc-
ture (–60 °C). Yellow solid; yield: 173 mg (0.31 mmol, 31%); m.p.
4
35 °C. 1H NMR: δ = 0.25 [s, 9 H, Si(CH3)3], 0.26 [d, J(P,H)
=
2
4
0.6 Hz, 9 H, Si(CH3)3], 1.16 [dd, J(P,H) = 6.0, J(H,H) = 2.5 Hz, 1
tional P–H phosphane derivatives, [(Me3Si)2HCP(H)-
3
1
H, PCH], 2.76 [d, J(P,H) = 10.9 Hz, 6 H, N(CH3)2], 7.03 [d, J(P,H)
=342.9 Hz,1H,PH]ppm.13C{1H}NMR:δ=0.0[d,3J(P,C)=2.6 Hz,Si-
(CH3)3], 0.5 [d, 3J(P,C) = 3.2 Hz, Si(CH3)3], 22.6 [d, 1J(P,C) = 3.9 Hz,
1
N(SiMe3)2] [δ = 5.9 ppm; J(P,H) = 210.0 Hz], to have been
reported previously.[19] Note that deprotonation of H/NR2
phosphane complexes with LDA seems not to be the pre-
dominant process and/or the products formed do not pos-
sess sufficiently high thermal stability, which is in stark con-
trast to Li/OR phosphinidenoid complexes with alkyl or
2
2
PCH], 42.8 [d, J(P,C) = 5.2 Hz, N(CH3)2], 195.1 [d, J(P,C) = 7.1,
1J(W,C) = 126.0 Hz, cis-CO], 201.8 [d, J(P,C) = 22.6 Hz, trans-CO]
2
ppm. 31P{1H} NMR: δ = 46.1 [dsat
,
1J(W,P) = 249.2, J(P,H)
=
1
342.1 Hz] ppm. IR (KBr): ν = 1917 [vs, ν(CO)], 2069 [s, ν(CO)],
˜
aryl groups R,[20] which can be used as reagents at ambient 2270 [w, ν(PH)], 2958 [w, ν(CH/CH3)] cm–1. MS (EI): m/z (%) =
559.1 (38) [M]+·, 531.1 (30) [M – CO]+·, 503.1 (34) [M – 2 CO]+·,
temperature.
475.0 (100) [M – 3 CO]+·, 417.0 (80) [M – 5 CO]+·, 234.1 (52) [M –
W(CO)5]+·, 73.0 (70) [SiMe3]+·. C14H26NO5PSi2W (559.36): calcd.
C 30.06, H 4.69, N 2.50; found C 30.88, H 4.39, N 2.56.
Conclusions
Synthesis of Complex 3b: Diethylamine (0.1 mL, 1.0 mmol) was
New 1,1Ј-bifunctional aminophosphane complexes 3a–e added to a solution of 2H-azaphosphirene complex 1 (617 mg,
1.0 mmol) in toluene (30 mL) at 75 °C. The reaction mixture was
heated whilst stirring for 3 h. After removal of all volatiles in vacuo
(ca. 10–2 mbar), the final product 3b was purified by column
chromatography at low temperature on silica gel (–20 °C,
2ϫ11 cm, petroleum ether/Et2O = 9:1). Yellow viscous liquid;
yield: 123 mg (0.21 mmol, 21%). 1H NMR: δ = 0.25 [s, 9 H,
have been synthesized by two routes. In the case of 3c, an
especially interesting observation was that the targeted
complex 3c was formed together with the (Z)-diphosphene
complex 6, which provides the first hint of transient Na/X
phosphinidenoid complexes 4a,b and/or the terminal phos-
phinidene complex 5. The results of a preliminary study on
the deprotonation of complex 3a showed the formation of
a main product, tentatively assigned to the Li/NMe2 phos-
phinidenoid complex 7 featuring a P–Li bond. Interestingly,
2
Si(CH3)3], 0.26 [s, 9 H, Si(CH3)3], 1.08 [d, J(P,H) = 1.7 Hz, 1 H,
3
PCH], 1.13 [t, J(H,H) = 14.2 Hz, 6 H, NCH2CH3], 3.10 (m, 4 H,
1
NCH2CH3), 7.18 [d, J(P,H) = 342.5 Hz, 1 H, PH] ppm. 13C{1H}
3
NMR (75.5 MHz, CDCl3): δ = 0.0 [d, J(P,C) = 3.2 Hz, Si(CH3)3],
3
3
complex 7 decomposes to yield the P–H phosphane deriva- 0.2 [d, J(P,C) = 3.2 Hz, Si(CH3)3], 11.2 [d, J(P,C) = 4.5 Hz,
1
2
NCH2CH3], 22.7 [d, J(P,C) = 3.9 Hz, PCH], 43.4 [d, J(P,C)
=
tive 8 by an unknown pathway. Future work will address
the latter as well as try to unveil a slowly emerging struc-
ture–reactivity relationship of M/X phosphinidenoid com-
plexes.
2
1
5.2 Hz, NCH2CH3], 196.0 [d, J(P,C) = 6.5, J(W,C) = 125.4 Hz, cis-
CO], 197.0 [d, J(P,C) = 23.3 Hz, trans-CO] ppm. 31P{1H} NMR: δ
2
1
1
= 31.0 [dsat, J(W,P) = 249.2, J(P,H) = 342.0 Hz] ppm. IR (KBr): ν
˜
= 1932 [vs, ν(CO)], 2069 [s, ν(CO)] cm–1. MS (EI): m/z (%) = 587.1
(40) [M]+·, 559.1 (8) [M – CO]+·, 531.1 (18) [M – 2 CO]+·, 503.1
(95) [M – 3 CO]+·, 445.1 (38) [M – 5 CO]+·, 262.1 (90) [M –
W(CO)5]+·, 73.0 (58) [SiMe3]+·. C16H30NO5PSi2W (587.41): calcd.
C 32.72, H 5.15, N 2.38; found C 33.25, H 5.23, N 2.29.
Experimental Section
General: All operations were performed in typical flame-dried
Schlenk glassware under argon that had been purified and dried.
Solvents were used after distillation from sodium wire/benzophen-
one. NMR spectra were recorded with a Bruker Avance 300 spec-
trometer at 25 °C in CDCl3 solutions. Chemical shifts are given in
ppm relative to tetramethylsilane (1H: 300.1 MHz; 13C: 75.5 MHz)
and 85% H3PO4 (31P: 121.5 MHz). Mass spectra were recorded
with a Kratos MS 50 spectrometer (EI, 70 eV); only m/z values
are given. IR spectra were recorded with an FT-IR Nicolet 380
spectrometer. Melting points were measured with a Büchi 535 cap-
illary apparatus. Elemental analyses were performed by using an
Elementa (vario EL) analytical gas chromatograph.
Synthesis of Complexes 3c and 6: A solution of chlorophosphane
complex 2 (550 mg, 1.0 mmol) in diethyl ether (10 mL) was added
to a stirred solution of sodium diphenylamide (210 mg, 1.1 mmol)
in diethyl ether (10 mL) at –30 °C. The reaction solution was stirred
for 3 h and warmed up to room temperature. After removal of all
volatiles in vacuo (ca. 10–2 mbar), the final products were purified
by column chromatography on silica gel [–20 °C, 2ϫ11 cm, petro-
leum ether/Et2O = 100:0 (for 1st fraction), 90:10 (for 2nd fraction)].
3c: Yellow solid, crystallized from Et2O at –30 °C; yield: 68 mg
(0.1 mmol, 10%); m.p. 39 °C. 31P{1H} NMR: δ = 23.7 [dsat, 1J(W,P)
1
= 263.2 Hz, J(P,H) = 330.6 Hz] ppm.
Eur. J. Inorg. Chem. 2012, 2314–2319
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L. Duan, G. Schnakenburg, J. Daniels, R. Streubel
FULL PAPER
6: Pink solid, crystallized from Et2O at –30 °C; yield: 220 mg
ether (1 mL)] in TMEDA (1 mL) and cooled to –78 °C. The reac-
1
(0.21 mmol, 21%); m.p. 143–145 °C. H NMR: δ = 0.17 [s, 36 H, tion mixture was stirred for 1 h, and then a 31P{1H} NMR spec-
2
1
Si(CH3)3], 3.40 [d, J(P,H) = 2.2 Hz, 2 H, PCH] ppm. 13C{1H}
trum was recorded. 7: δ = 101.8 [q, J(P,Li) = 62.1 Hz] ppm. 8: δ =
NMR: δ = 1.8 [s, Si(CH3)3], 33.2 [d, 1J(P,C) = 36.7 Hz, PCH], 196.4
39.1 [s, J(P,H) = 195.9 Hz] ppm.
1
2
2
[d, J(P,C) = 4.0 Hz, cis-CO], 201.8 [d, J(P,C) = 14.4 Hz, trans-CO]
ppm. 31P{1H} NMR: δ = 324.2 [ssat 1J(W,P) = 146.5, J(P,H)
, =
1
115.9 Hz] ppm. IR (KBr): ν = 1254 [w, ν(P=P)], 1927 [s, ν(CO)],
˜
Acknowledgments
1987 [m, ν(CO)], 2062 [m, ν(CO)], 2077 [s, ν(CO)] cm–1. MS (EI):
m/z (%) = 1028.0 (25) [M]+·. C24H38O10P2Si4W2 (1028.55): calcd.
C 28.03, H 3.72; found C 28.47, H 4.26.
We would like to acknowledge financial support by the Deutsche
Forschungsgemeinschaft (DFG) (STR411/26-2 and STR411/29-1)
and the Cost Action (cm0802 “PhoSciNet”).
Synthesis of Complex 3d: Isopropylamine (0.14 mL, 1.0 mmol) was
added to a stirred solution of 2H-azaphosphirene complex 1
(617 mg, 1.0 mmol) in toluene (30 mL) at 75 °C, and the reaction
mixture was stirred for 3 h. After removal of all volatiles in vacuo
(ca. 10–2 mbar), the final product 3d was purified by washing with
n-pentane at low temperature (–60 °C). Yellow solid, crystallized
from n-pentane at –30 °C; yield: 200 mg (0.33 mmol, 33%); m.p.
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Angew. Chem. Int. Ed. Engl. 1975, 14, 571–572.
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1
4
73 °C. H NMR: δ = 0.25 [d, J(P,H) = 0.6 Hz, 9 H, Si(CH3)3], 0.29
4
2
[d, J(P,H) = 0.4 Hz, 9 H, Si(CH3)3], 0.96 [d, J(P,H) = 6.2 Hz, 1 H,
PCH], 1.18 [d, J(H,H) = 6.4 Hz, 6 H, NCH(CH3)2], 3.26 (br., 1 H,
2
3
1
NH), 3.40 [q, J(P,H) = 7.0 Hz, 1 H, NCH(CH3)2], 7.09 [d, J(P,H)
=
=
320.2 Hz, 1 H, PH] ppm. 13C{1H} NMR: δ = –1.3 [d, J(P,C)
3
2.3 Hz, Si(CH3)3], 0.0 [d, 3J(P,C) = 3.2 Hz, Si(CH3)3], 22.3 [d, 1J(P,C)
3
= 7.8 Hz, PCH], 22.7 [d, J(P,C) = 4.5 Hz, NCH(CH3)2], 46.2 [d,
2J(P,C) = 3.2 Hz, NCH(CH3)2], 195.1 [d, J(P,C) = 7.1 Hz, cis-CO],
2
197.4 [d, 2J(P,C) = 22.0 Hz, trans-CO] ppm. 31P{1H} NMR: δ = 11.4
1
[dsat
,
1J(W,P) = 255.6 Hz, J(P,H) = 320.4 Hz] ppm. IR (KBr): ν =
˜
1920 [vs, ν(CO)], 2068 [s, ν(CO)], 2226 [w, ν(PH)], 2956 [w, ν(CH/
CH3)] cm–1. MS (EI): m/z (%) = 573.0 (49) [M]+·, 545.0 (41) [M –
CO]+·, 517.0 (39) [M – 2 CO]+·, 489.0 (85) [M – 3 CO]+·, 461.0
(20) [M – 4 CO]+·, 433.0 (71) [M – 5 CO]+·, 73.0 (82) [SiMe3]+·.
C15H28NO5PSi2W (573.39): calcd. C 31.42, H 4.92, N 2.44; found
C 31.80, H 4.98, N 2.21.
Synthesis of Complex 3e: Aniline (92 μL, 1.0 mmol) was added to
a stirred solution of 2H-azaphosphirene complex 1 (617 mg,
1.0 mmol) in toluene (30 mL) at 75 °C, and then the reaction mix-
ture was stirred for 3 h. After removal of all volatiles in vacuo (ca.
10–2 mbar), the final product 3e was purified by column
chromatography on silica gel (–20 °C, 2ϫ9.5 cm, petroleum ether/
Et2O = 9:1). Yellow solid, crystallized from n-pentane at –30 °C;
yield: 297 mg (0.49 mmol, 49%); m.p. 90 °C. 1H NMR: δ = 0.20
4
4
[d, J(P,H) = 0.4 Hz, 9 H, Si(CH3)3], 0.28 [d, J(P,H) = 0.8 Hz, 9 H,
Si(CH3)3], 1.83 [dd, 2J(P,H) = 13.6 Hz, J(H,H) = 7.6 Hz, 1 H, PCH],
3
3
3.97 (br., 1 H, NH), 6.85 [d, J(H,H) = 7.5 Hz, 2 H, o-Ph], 7.00 [t,
3J(H,H) = 7.6 Hz, 1 H, p-Ph], 7.33 [t, J(H,H) = 7.4 Hz, 2 H, m-Ph],
3
7.49 [d, J(P,H) = 357.7 Hz, 1 H, PH] ppm. 13C{1H} NMR: δ = 0.0
1
[d, 3J(P,C) = 1.3 Hz, Si(CH3)3], 15.1 [d, 1J(P,C) = 7.8 Hz, PCH], 115.9
[d, 3J(P,C) = 4.5 Hz, o-Ph], 120.0 (s, p-Ph), 128.1 (s, m-Ph), 141.2 [d,
2J(P,C) = 9.7 Hz, ipso-Ph-C], 195.1 [d, J(P,C) = 6.5 Hz, cis-CO],
2
196.6 [d, J(P,C) = 23.2 Hz, trans-CO] ppm. 31P{1H} NMR: δ = 5.3
2
1
[dsat
,
1J(W,P) = 253.0 Hz, J(P,H) = 357.3 Hz] ppm. IR (KBr): ν =
˜
1904 [s, ν(CO)], 1918 [s, ν(CO)], 1946 [vs, ν(CO)], 1986 [m, ν(CO)],
2071 [s, ν(CO)], 2310 [w, ν(PH)], 2960 [w, ν(CH/CH3)], 3419 [br.,
ν(NH)] cm–1. MS (EI): m/z (%) = 607.1 (40) [M]+·, 579.1 (9) [M –
CO]+·, 551.1 (8) [M – 2 CO]+·, 523.1 (100) [M – 3 CO]+·, 73.0 (42)
[SiMe3]+·. C18H26NO5PSi2W (607.40): calcd. C 35.59, H 4.31, N
2.31; found C 35.73, H 4.61, N 2.06.
[14] a) J. Borm, L. Zsolnai, G. Huttner, Angew. Chem. 1983, 95,
1018–1018; Angew. Chem. Int. Ed. Engl. 1983, 22, 977–978; b)
G. Huttner, J. Borm, L. Zsolnai, J. Organomet. Chem. 1986,
304, 309–321.
Generation of Complexes 7 and 8: A solution of 3a (56 mg,
0.1 mmol) and 12-crown-4 (16 μL) in tetramethylethylenediamine
(TMEDA; 1 mL) was added dropwise to a solution of LDA
[0.11 mmol; freshly prepared from n-butyllithium (75 μL, 1.6 m,
0.11 mmol) and diisopropylamine (20 μL, 0.1 mmol) in diethyl
[15] H. Lang, O. Orama, G. Huttner, J. Organomet. Chem. 1985,
291, 293–309.
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Eur. J. Inorg. Chem. 2012, 2314–2319

Aminophosphane Complexes
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Inorg. Chem. 2011, 567–572.
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Received: December 23, 2011
Published Online: March 15, 2012
Eur. J. Inorg. Chem. 2012, 2314–2319
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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